US0085.07726B2
(12) United States Patent (10) Patent No.: US 8,507,726 B2 Studer et al. (45) Date of Patent: *Aug. 13, 2013
(54) PHOTOINITIATOR MIXTURES 2010/01701 42 A1 7/2010 Posselt et al. 2010/0240774 A1 9/2010 Subkowski 2011/0134554 A1 6/2011 Matsumoto (75) Inventors: Katia Studer, Rixheim (FR); Sébastien 2011/O159050 A1 6, 2011 Hafner et al. Villeneuve, Huningue (FR); Akira 2011/O170209 A1* 7/2011 Matsumoto et al...... 359,891 Matsumoto, Amagasaki (JP); Hisatoshi Kura, Takarazuka (JP); Jan Siltemeyer, FOREIGN PATENT DOCUMENTS Village Neuf (FR) WO 2007/071497 A 6, 2007 WO 2009,147031 A2 12/2009 (73) Assignee: BASFSE, Ludwigshafen (DE) OTHER PUBLICATIONS (*) Notice: Subject to any disclaimer, the term of this Copending U.S. Appl. No. 1 1/887.282, filed Aug. 17, 2007. patent is extended or adjusted under 35 Copending U.S. Appl. No. 13/127,068, filed May 2, 2011. U.S.C. 154(b) by 86 days. * cited by examiner This patent is Subject to a terminal dis claimer. Primary Examiner — Sanza McClendon (74) Attorney, Agent, or Firm — Shruti Costales (21) Appl. No.: 13/127,068 (57) ABSTRACT (22) PCT Filed: Oct. 23, 2009 Photoinitiators mixture comprising (i) at least one compound selected from the group consisting of alpha-hydroxy ketones, (86). PCT No.: PCT/EP2009/063963 monoacylphosphine oxides, bisacylphosphine oxides, keto Sulfones, benzil ketals, benzoin ether, phenylglyoxylates, S371 (c)(1), borates and titanocenes; and (ii) at least one compound of the (2), (4) Date: May 24, 2011 formula (I) or (I) R. R. RandR'R' independently of each other for example are hydrogen or C-Calkyl R-7, Rs. R. R's (87) PCT Pub. No.: WO2010/060702 and R' independently of each other for example are hydro PCT Pub. Date: Jun. 3, 2010 gen, C-C alkyl which optionally is substituted or phenyl which optionally is substituted, exhibit excellent photoiniti (65) Prior Publication Data ating properties. US 2011/0218266A1 Sep. 8, 2011 (30) Foreign Application Priority Data (I) R7 Nov. 3, 2008 (EP) ...... O81681.45 A O=C Ro (51) Int. Cl. 1.Xs sas C07C 259/00 (2006.01) Rs (52) U.S. Cl. R 2 i. USPC ...... 564/254; 564/253: 522/33:522/39; OEC Ev N., ME CEO 522/63; 522/9:522/8: 522/11:522/49; 522/57; x1 NC 522/71; 522/74; 522/81: 522/113:522/114; O-NEC CEN - O 522/100: 522/101: 522/150:522/153: 522/154; \ / / 522/178; 522/181522/182; 522/183; 35.9/891 R R (58) Field of Classification Search (I) USPC ...... 522/33, 39, 65, 9, 8, 11, 49, 57,71, R 522/74, 81,113, 114, 100, 101, 150, 153, st 522/154, 178, 181, 182, 183 O=C Ro See application file for complete search history. Xy. - (56) References Cited R 21 OC Q = N = 9 CO U.S. PATENT DOCUMENTS (-N=C- x SC -C=N-) 2009,004 1922 A1 2/2009 Kuhnleet al. N / \ A 2009, O136433 A1 5, 2009 Subkowski et al. R R" 2010, OO86881 A1 4/2010 Matsumoto 2010, O136467 A1 6/2010 Matsumoto 2010, O136491 A1 6/2010 Matsumoto 2010, 01666.27 A1 7, 2010 Baus et al. 16 Claims, No Drawings US 8,507,726 B2 1. 2 PHOTOINITIATOR MIXTURES -continued (I) The invention pertains to photoinitiator mixtures of alpha hydroxyketone, mono- or bisacylphosphine oxides, ben Jr. Zophenones, thioxanthones, ketosulfones, benzil ketals, phe O=CR) nylglyoxylates, borates or titanocenes photoinitiators and \ SA specific Oxime ester compounds and their use as photoinitia Rs tors in photopolymerizable compositions. R 21 i. Alpha-hydroxyketones are known to be photoinitiators, as OC O = N = O C=O, for example disclosed in U.S. Pat. Nos. 4.347,111, 4,321,118, 10 (-N=c- x SC -c=N-) WO 04/092287, U.S. Pat. Nos. 4,672,079,4987,159 or WO \ A \ A 02/85832. Mono- or bisacylphosphine oxides also are known R R from e.g. U.S. Pat. No. 4,324,744, EP 40721 (=Derwent wherein 91349 D/50), U.S. Pat. No. 4,737,593, GB 2259704 or U.S. 15 Pat. No. 6,020,528. Ketosulfone photoinitiators are for R and R' independently of one another are hydrogen, example known from WO 00/031030. In WO 06/120212, C-C cycloalkyl or C-C alkyl which is unsubstituted or U.S. Pat. Nos. 6,048,660, 4,475.999 and 4,038,164 phenylg substituted by one or more halogen, phenyl and/or CN; or lyoxylates are described as photoinitiators. Borates as photo R and R are C-Calkenyl; or initiators are for example shown in U.S. Pat. No. 51,766,984 RandR' are phenyl which is unsubstituted or substituted by or GB 2307474 and titanocenes are for example disclosed in one or more C-Calkyl, halogen, CN, OR, SR and/or U.S. Pat. Nos. 5,008,302 and 5,340,701. NRR, or Further, a wide variety of oxime ester compounds is used as RandR are C-Calkoxy, benzyloxy; or phenoxy which is photoinitiator, in particular in electronic applications as for unsubstituted or substituted by one or more C-Calkyl example in color filter resists, also the color filter black 25 and/or halogen; matrix, etc. as disclosed for example in WO 02/100903. RandR' independently of one another are hydrogen; unsub In photopolymerization technology there still exists a need stituted C-Coalkyl or C-Coalkyl Substituted by one or for highly reactive, easy to prepare and easy to handle pho more halogen, OR, SR C-Coheteroaryl, Cs-Co-phe toinitiators. For example in color filter resist applications, noxycarbonyl, C-Coheteroaryloxycarbonyl, NRSR highly pigmented resists are required for the high color qual 30 ity property. With the increase of the pigment content, the COOR, CONRR, curing of color resists becomes more difficult. The same applies for the curing of inks, for example offset inks, which also are loaded with pigments. Further, the curing of adhe sives affords appropriate photoinitiators, Hence, a photoini 35 R20 tiator having a higher sensitivity and excellent resolution properties than current initiation systems is required. In addi tion, also such new photoinitiators must meet the high phenyl and/or by phenyl which is substituted by OR SR requirements of the industry regarding properties like, for and/or NRSR, wherein the unsubstituted or substituted example, high solubility, thermal stability and storage stabil C-Coalkyl optionally contains one or more C-C multiple ity. 40 bonds; or Surprisingly, it now has been found, that a mixture of above R and R' are NRR, mentioned photoinitiators and selected oxime ester com pounds perfoms unexpectedly better than the known photo O initiator compounds alone. 45 Subject of the invention therefore is a photoinitiator mix N-O-C-R ture comprising (i) at least one compound selected from the group consisting of alpha-hydroxy ketones, monoacylphosphine oxides, bisacylphosphine oxides, ketosulfones, benzil ketals, ben 50 Zoin ether, phenylglyoxylates, borates and titanocenes; and or C-Cocycloalkyl; (ii) at least one compound of the formula (I) and (I) or are C-Coalkyl which is interrupted by one or more O and which optionally is substituted by one or more halogen, OR, phenyl and/or phenyl substituted by OR, SR and/or (I) 55 NRR; or RandR' are phenyl which is unsubstituted or substituted by R7 one or more C-Calkyl, phenyl, halogen, OR, SR and/or o=t^ R9 NRR, or X& R and Rare C-Coalkanoyl or benzoyl which is unsubsti Rs it 60 tuted or substituted by one or more C-Calkyl, phenyl, R 21 i. OR, SR and/or NRSR; or R and R are C-C alkoxycarbonyl which is optionally o= =y-N-G = =o interrupted by one or more O and/or optionally substituted O-NEC CEN-O by one or more hydroxyl groups; or \ / \ W 65 R and R' are phenoxycarbonyl which is unsubstituted or Substituted by C-Calkyl, halogen, phenyl, OR, SR and/ or NRSR; or US 8,507,726 B2 3 4 R and R are CN, CONRR, NO, S(O), C-Calkyl: C-Coheteroaryl, C-Coheteroaryl-(CO)O, S(O)-phenyl which optionally is substituted by C-Coheteroaryl-S, CONRR C-C alkyl or SO C-Calkyl, or are SOO-phenyl which optionally is substituted by C-C alkyl: or are diphenyl phosphinoyl or di-(C-Calkoxy)-phosphi noyl; or R20 R and Rare phenyl or ray phenyl substituted by halogen, C-Coalkyl, (A) 10 C-Chaloalkyl, SR, OR, or NRSR, and which unsubsti O tuted or substituted, interrupted or non-interrupted C-Coalkylene optionally contains one or more C-C mul -M2-CH-C-Air, tiple bonds; (B) R is hydrogen, C-Coalkyl or phenyl-C-C-alkyl, or 15 R is C-Coalkyl which is substituted by OH, SH, —CN, C-Calkenoxy, OCHCHCN, OCH-CH(CO)O(C- --K YR. O Calkyl). O(CO)—(C-C alkyl). O(CO)-phenyl, (CO)OH \ Ž, and/or (CO)O(C-C alkyl); or (C) R is C-Coalkyl which is interrupted by one or more O; or O Rs' R is (CH2CH2O), H., (CH2CH2O)(CO)—(C-Calkyl). C C-Csalkanoyl, C-Calkenyl, C-Calkenoyl or \ N1 N YR Cs-Cocycloalkyl which optionally is interrupted by O.S, CO, NRs; or 4N O 25 R is benzoyl which is unsubstituted or substituted by one or more C-Calkyl, halogen, OH and/or C-Calkoxy; or m is 1 or 2; R is phenyl, naphthyl or C-Coheteroaryl, each of which is Ars is phenyl, naphthyl or coumarinyl, each of which is Sub unsubstituted or substituted by halogen, OH, C-C alkyl, stituted once or more times by halogen, C-C alkyl, C-C alkoxy, CN, NO, phenyl-C-C-alkyloxy, phenoxy, C-C cycloalkyl, benzyl and/or phenoxycarbonyl: or each 30 C-C alkylsulfanyl, phenylsulfanyl, N(C-C alkyl). of which is substituted by phenyl or by phenyl which is diphenylamino and/or substituted by one or more OR, SR and/or NRs R; or each of which is substituted by C-Calkoxycarbonyl R" O optionally interrupted by one or more O and/or optionally 35 | Substituted by one or more hydroxyl groups; or each of -C=N-O-C-R"; which is substituted by OR, SR SOR SOR and/or NRSR; n is 1-20; M is a direct bond, cyclohexylene or C-Coalkylene or R is hydrogen, C-Coalkyl, C2-C2alkenyl, C-Coalkylene-X—, which C-Coalkylene or 40 Cs-Cocycloalkyl, phenyl-C-C-alkyl, wherein the C-Coalkylene-X— is optionally interrupted by one or C-Coalkyl, C-Calkenyl, Cs-Cocycloalkyl, phenyl more 0 and/or optionally substituted by one or more halo C-C alkyl optionally is interrupted by O, S, CO, NRs; or gen, OR, phenyl orphenyl substituted by OR, SR and/or Ra is C-Calkyl which is substituted by OH, SH, CN, NRSR: or M is phenylene, naphthylene or phenylene C-Calkenoxy, OCHCHCN, OCH-CH(CO)O(C- X—, each of which is unsubstituted or substituted by one 45 Calkyl), O(CO)—(C-C alkyl), O(CO)-phenyl, (CO)OH or more C-Calkyl, phenyl, halogen, OR, SR and/or or (CO)O(C-C alkyl); or NRR, or M is C-Coalkylene-C(O)—X—, R is (CHCHO)H, (CHCHO)(CO)—(C-C alkyl). C-Coalkylene-X—C(O)—, phenylene-C(O)—X— or C-Csalkanoyl, C-Calkenyl, C-Calkenoyl; or C-Coalkylene-phenylene-X—: Ra is benzoyl which is unsubstituted or substituted by one or M is a direct bond, cyclohexylene, C-Coalkylene or 50 more C-Calkyl, halogen, —OH, C-Calkoxy or C Coalkylene-X—, which C-Coalkylene or C-C alkylsulfanyl; or C-Coalkylene-X— is optionally interrupted by one or R is phenyl, naphthyl or C-Coheteroaryl, each of which is more 0 and/or optionally substituted by one or more halo unsubstituted or Substituted by halogen, C-C alkyl, gen, OR, phenyl orphenyl substituted by OR, SR and/or C-C alkoxy, CN, NO, phenyl-C-C-alkyloxy, phenoxy, NRSR; or 55 C-C alkylsulfanyl, phenylsulfanyl, N(C-C alkyl). M is phenylene, naphthylene or phenylene-X—, each of diphenylamino, (CO)O(C-Calkyl), (CO)—C-Calkyl, which is unsubstituted or substituted by one or more (CO)N(C-Calkyl) or C-Calkyl, phenyl, halogen, OR, SR and/or NRSR, or M is C-Coalkylene-C(O)—X—, C-Coalkylene-X—C (O)—, phenylene-C(O)—X—, C-Coalkylene-phe 60 R" O nylene-X— or phenylene-(CO)-phenylene; | X is O, S or NRs: X is O, S, SO or SO: X is a direct bond, C-Coalkylene which optionally is inter Rs and R independently of each other are hydrogen, rupted by O, CO or NRs, and which uninterrupted or inter 65 C-Coalkyl, C-C hydroxyalkyl, C-Coalkoxyalkyl, rupted C-Coalkylene is unsubstituted or Substituted by C-Csalkenyl, Cs-Cocycloalkyl, phenyl-C-C-alkyl, one or more halogen, OR, COOR, NRSR C-Csalkanoyl, C-C2-alkenoyl, benzoyl; or US 8,507,726 B2 5 Rs and R are phenyl, naphthyl or C-Coheteroaryl, each of Rs and Ro and R's and R's together are which is unsubstituted or substituted by C-C alkyl, ben Zoyl or C-C alkoxy; or R10 R11 R12 R3 R14 R15 RandR together with the N-atom to which they are attached | | | | form a 5- or 6-membered saturated or unsaturated ring -CEC-CEC - O - CEC-C-O- which optionally is interrupted by O.S or NR, and which ring is unsubstituted or Substituted by one or more Ro, R. RandR independently of one another are hydro C-Coalkyl, C-Coalkoxy, =O, SR, OR or NR7Rs. gen, C-C-alkyl which optionally is substituted by one or (CO)Ro, NO, halogen, C-Chaloalkyl, CN, phenyl, 10 more halogen, phenyl, CN, OH, SH, C-Calkoxy, (CO) OH or (CO)O(C-C alkyl); or R. R. R. and R are phenyl which optionally is substi R" O tuted by one or more C-Calkyl, halogen, CN, OR, SR or NRSR; or 15 Rio R, R2 and R are halogen, CN, OR, SR or NRSR; Ra and Rs independently of each other are hydrogen, or by C-Cocycloalkyl which optionally is interrupted by C-C alkyl which optionally is substituted by one or more O, S, CO or NR; or halogen, phenyl, CN, OH, SH, C-Calkoxy, (CO)OH or Rs and R together with the N-atom to which they are attached (CO)O(C-C alkyl); or Ra and Rs are phenyl which form a heteroaromatic ring system, which heteroaromatic optionally is substituted by one or more C-Calkyl, halo ring system is unsubstituted or Substituted by one or more gen, CN, OR, SR or NRSR; C-Coalkyl, C-Chaloalkyl, C-Coalkoxy, =O, SR, R7 and Rs independently of each other are hydrogen, OR, NR7Rs (CO)R. C-Coalkyl, C-Chaloalkyl, C-Cocycloalkyl or phenyl: 25 O R7 and Rs together with N-atom to which they are attached R" O form a 5- or 6-membered saturated or unsaturated ring, -CEN-O-C-R", which optionally is interrupted by O.S or NR; or R, and Rs independently of one another are 30 C-C alkylene or C-Calkenylene which is attached to halogen, NO, CN, phenyl or by Cs-Cocycloalkyl which one of the C-atoms of the phenyl or naphthyl ring to which optionally is interrupted by O, S, CO or NR; the NR7Rs is attached, wherein said C-C alkylene or R" has one of the meanings as given for R; C-Calkenylene optionally is interrupted by O, CO or R" has one of the meanings as given for R. NR, and to which C-Csalkylene or C-Calkenylene 35 optionally a benzene ring is condensed; R, is hydrogen, C-Coalkyl, C-Csalkyl which is Substituted Ro is hydrogen, OH, C-Coalkyl, C-Chaloalkyl, by halogen, phenyl, OH, SH, CN, C-Calkenoxy, C-Coalkyl which is interrupted by O, CO or NR, OCHCHCN, OCHCH(CO)O(C-C alkyl), O(CO)— Cs-Cocycloalkyl which optionally is interrupted by O. S. (C-C alkyl), O(CO)-phenyl, (CO)OH or (CO)O(C- CO or NR, or is phenyl, naphthyl, phenyl-C-C-alkyl, Calkyl); or 40 SR, OR or NRRs: R, is C-C alkyl which is interrupted by one or more O; or Ro is COOR, CONRR (CO)R; or Rao has one of the meanings as given for Rs and Re; R, is (CH2CH2O), H., (CH2CH2O)(CO)—(C-Calkyl). R is COOR, CONRR (CO)R; C-Calkenyl or C-Cacycloalkyl; or or R has one of the meanings as given for Rs: R, is phenyl, biphenylyl, naphthyl or C-Coheteroaryl, each 45 R is hydrogen, C-Coalkyl, C-Coalkenyl: of which optionally is substituted by one or more Cs-Cocycloalkyl which optionally is interrupted by O.S, C-Coalkyl, halogen, C-Chaloalkyl, CN, NO, OR, CO or NRs or is C-Cocycloalkenyl: or is C-Coalkyl SR, SOR SOR or NRR, wherein the substituents which is substituted by one or more halogen, SR, OR, OR, SR or NRSR optionally form 5- or 6-membered COOR, NRSR, C-Coheteroaryl, C-Coheteroaryl rings via the radicals R. R. Rs and/or R with one of the 50 (CO)O, CONRR, carbon atoms of the phenyl, biphenylyl, naphthyl or C-Coheteroaryl ring; Rs and Ro and R's and R' independently of each other are R20 hydrogen, C-C alkyl which optionally is Substituted by 55 one or more halogen, phenyl, CN, OH, SH, C-Calkoxy, (CO)OH or (CO)O(C-C alkyl); or orphenyl; or R is C-Coalkyl which is interrupted by one Rs and R. and R's and R's are phenyl which optionally is or more O and/or optionally is substituted by one or more substituted by one or more C-Calkyl, halogen, CN, OR, halogen, SR, OR, COOR NRR, C-Coheteroaryl, SR or NRSR; or 60 C-Coheteroaryl-(CO)O, CONRR, Rs and RandR's and R's are halogen, CN, OR, SR, SOR, SOR or NRR, wherein the substituents OR, SR or NRSR optionally form 5- or 6-membered rings via the R20 radicals R. R. Rs and/or R with one of the carbon atoms 65 of the phenyl or with the substituent R, or one of the carbon atoms of the naphthylene or phenylene group of M, or US 8,507,726 B2 7 8 or phenyl: Zophenone compound or a thioxanthone compound; and or R is phenyl, naphthyl, coumarinyl or C-Coheteroaryl, optionally each of which optionally is substituted by one or more (d) other additives. C-C alkyl, phenyl, halogen, C-Chaloalkyl, CN, NO, To be used in the photopolymerizable composition, each SR, OR, NRSR or by Cs-Cocycloalkyl which option component of the photoinitiator mixture, that is the com ally is interrupted by O, CO or NRs: pound of the formula (I) or (I) and the compound selected from the group consisting of alpha-hydroxy ketones (HK). or R is C-Coalkanoyl, or benzoyl which is unsubstituted monoacylphosphine oxides (MPO), bisacylphosphine oxides or substituted by one or more C-Calkyl, halogen, phenyl, (BPO), benzophenones (BP), thioxanthones (TX), ketosul SR, OR or NRSR; 10 fones (KS), benzil ketals (BK), benzoin ether (BK), phenylg or R is C-Calkoxycarbonyl which optionally is inter lyoxylates (PG), borates (BT) and titanocenes (TI) can be rupted by one or more O and/or optionally is substituted by added in a stepwise manner to the formulation. It is, however, one or more OH: also possible to make a mixture of the oxime ester (I) or (I) or R is phenoxycarbonyl which is unsubstituted or substi 15 and (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), tuted by one or more C-Calkyl, C-Chaloalkyl, halogen, (BT) and/or (TI) by various methods prior to the use in the phenyl, SR, OR or NRSR; photopolymerizable composition. Methods to prepare Such mixtures are known to the person skilled in the art. For or R2 is NRSR; example, every component is dissolved in a solvent to make a or R forms a ring with one of the C-atoms of the phenyl ring homogeneous solution, which is concentrated to dryness to to which the group give a mixture, or, filtration of a dispersion, wherein every component is dispersed in a poor solvent or a reactive diluent, O gives the desired mixture. It is also possible to mix every component by using a blender. Another method is, for N-O-C-R 25 example, to dissolve the oXime ester compound(s) (I) or (I) in melted alpha-hydroxy keton compound(s) (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), (BT) and/or (TI) at a temperature, that is higher than its melting point, or the other is attached, wherein said formed ring is unsubstituted or 30 way around. Cooling the liquid to room temperature gives a Substituted; mixture according to the present invention. R has one of the meanings as given for R, and The ratio of the compound of the formula (I) or (I) and the R2 is hydrogen, C-Coalkyl, C-Chaloalkyl, C2-Coalkyl compound of the formula (HK), (MPO), (BPO), (BP), (TX), which is interrupted by O. S or CO, or is phenyl-C- (KS), (BK), (PG), (BT) and/or (TI) is for example from 0.1: Calkyl, Cs-Cocycloalkyl which optionally is interrupted 35 99.9 to 50:50, especially 0.5: 99.5 to 40:60, in particular 1: 99 by O.S or CO, or is phenyl. to 20:80. Further subject of the invention is a photopolymerizable Oxime esters of formula (I) or (I) are prepared from the composition comprising corresponding oximes by methods described in the literature, (a) at least one ethylenically unsaturated photopolymerizable for example by reaction of the corresponding oximes with an compound and 40 acyl halide, in particular a chloride, oran anhydride in an inert (b) a photoinitiator mixture as defined above, solvent such as for example diethyl ether, t-butyl methyl as well as a photopolymerizable composition comprising ether, tetrahydrofurane (THF), ethyl acetate, toluene, (a) at least one ethylenically unsaturated photopolymerizable Xylenes, acetone, methyl ethyl ketone, dichloromethane, aminoacrylate compound or at least one ethylenically 45 chloroform, chlorobenzene, dimethylacetoamide or dimeth unsaturated photopolymerizable acrylate and a H-donor ylformamide in the presence of a base, for example triethy and lamine, diisopropylethyl-amine, potassium hydroxide, (b1) a photoinitiator mixture consisting of at least one com Sodium hydroxide, sodium hydride, 2.6-lutidine or pyridine, pound of the formula I or I" as defined above and a ben or in a basic solvent such as pyridine. For example:
Hal-C-R O O O R-C-O-C-R base US 8,507,726 B2 9 10 -continued R M OCAsé R9 - R 2
OEC o N o CEO h NEC 31 SC CEN h \ / \ / R2 R" (I) O
M R 7 Hal-C-R OC R9 O X&1a. - 21 --R-C-O-C-R base O O o N o HO-NEC N /X1 SX\ A CEN-OH R2 R" (II) R M 7 OC 1.Xs sa - R 2 i. OEC -N=C-O ( FV 33N AR y O-e-N- CEO T \ A / R2 R' (I)
40 R. R. R. R. R. Rs and Ro are as defined above, Hal -continued means a halogen atom, in particular Cl. Compounds of the - formula I or I', wherein R and R', are not identical, can be OC Ro prepared by using a mixture of the corresponding acyl as \ vs halides, or by stepwise esterification. Such reactions are well Rs known to those skilled in the art, and are generally carried out 21 attemperatures of -15 to +50° C., preferably 0 to 25°C. N The compounds of formula (II) or (II) can be for example 50 HO-NEC X1 SX CEN - OH synthesized from the corresponding ketones in a selective \ / \ / manner according to the scheme below. R2 R' (II)
R7 55 M R. R. R. Rs and Ro are as defined above. OEC 1S, R9 Another convenient synthesis of oximes is the nitrosation \ SAS of “active' methylene groups with nitrous acid or an alkyl Re-i nitrite. Both alkaline conditions, as described for example in 2 HO-NH or its sal Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, HONH2 or its salt 60 1988), pp 199 and 840, and acidic conditions, as described, o N o solventbase for example, in Organic Synthesis coll. Vol V. pp. 32 and 373, OC 31, SC CO coll. Vol. III, pp 191 and 513, coll. Vol. II, pp. 202, 204 and \ / / 363, are suitable for the preparation of the oximes used as R2 R" starting materials in the invention. Nitrous acid is usually 65 generated from sodium nitrite. The alkyl nitrite can be for example methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamyl nitrite. US 8,507,726 B2 11 12 Every Oxime ester group can exist in two configurations, -continued (Z) or (E). It is possible to separate the isomers by conven (Ib) tional methods, but it is also possible to use the isomeric mixture as such as photoinitiating species. Therefore, the invention also relates to photoinitiator mixtures as Oxime ester component comprising mixtures of configurational iso mers of compounds of the formula (I) or (I'). Interesting are compounds of the formula (I) or (I), wherein the group CO(R7) is bound in para-position to the 10 N-phenyl bond, i.e. a compound of the formula (Ia) or (Ia):
15 wherein R. R. R. R. R. Rs and Ro are as defined above. (Ia) Preferred are compounds of the formula (I) or (I), wherein the group CO(R-7) is bound in para-position to the N-phenyl bond and wherein the bond of the central N-atom is in para position of the phenyl ring to the bond of the oxime ester group, i.e. a compound of the formula (Ic) or (Ic):
(Ic) 25
30
(Ia)
35 1so (Ic)
40
wherein R. R. R. R. R. Rs and Ro are as defined above. 45 Interesting are compounds of the formula (I) or (I), wherein the bond of the central N-atom is in para-position of the phenyl ring to the bond of the oxime ester group, i.e. a compound of the formula (Ib) or (Ib): 50 wherein R. R. R. R. R. Rs and R are as defined above. R and R' are for example hydrogen, C-Cscycloalkyl, unsubstituted C-C alkyl or C-C alkyl which is substi (Ib) tuted as indicated above; or are phenyl which is unsubstituted or substituted by one or more C-Calkyl, halogen, CN, OR, R 55 A SR and/or NRSR; in particular R and R' are O=C Ro C-C scycloalkyl, C-C alkyl or phenyl, preferably X& C-C alkyl, in particular C-C alkyl, especially methyl. 21 Preferably R and R', are C-Coalkyl which is unsubsti 60 tuted or substituted by halogen, OR, COOR, SR, phenyl, N NRR or
R 2C O Ol Cn o?C No.1 N1 VR, R,/NN no.1 C so US 8,507,726 B2 13 14 or are unsubstituted phenyl or phenyl which is substituted by R is preferably C-Coalkyl, C-Csalkanoyl phenyl-C- one or more C-Calkyl, SR, OR or NRSR. In particular R Calkyl, C-Coheteroaryl, unsubstituted phenyl or phenyl and R' are C-Coalkyl which is unsubstituted or is Substi Substituted by C-Coalkyl, halogen, tuted by COOR or R" O
R22 Rs and R are for example hydrogen, C-Coalkyl, 10 C-Chydroxyalkyl, C-Coalkoxyalkyl, phenyl-C-C-alkyl, or are especially C-Calkyl which is unsubstituted or is phenyl, or together with the N-atom to which they are substituted by COOR or attached form a 5- or 6-membered saturated or unsaturated ring which optionally is interrupted by O, or preferably hydrogen, phenyl, C-Coalkyl, or together with the N-atom 15 to which they are attached form a heteroaromatic ring system, R22 in particular carbazolyl. R, in particular denotes phenyl, naphthyl or C-Coheteroaryl, phenyl substituted by one or more SR, or are for example methyl, butyl or heptyl. OR, NRSR, halogen, C-Csalkyl or CN; especially unsub X preferably is O. stituted phenyl, phenyl substituted by SR NRR, R and R preferably are (CO)R. C-Calkyl, CN or one or more OR or halogen, naphthyl or R is for example C-Coalkyl, C-Csalkanoyl phenyl-C- C-Coheteroaryl (for example thienyl). Calkyl, C-Cocycloalkyl which is uninterrupted or inter Rs and R. preferably are hydrogen. rupted by O, or is phenyl, C-Coheteroaryl. Preferably R is Preferred are compounds of the formula (I), (Ia), (Ib) and C-Coalkyl or C-C scycloalkyl which optionally is inter 25 (Ic). rupted by one or more O, in particular it is C-Csalkyl or In particular preferred in the photoinitiator mixture as C-C cycloalkyl which is interrupted by O. described above areas oxime compounds of formula (I) or (I)
(1) (2) O O y O O YO CH3 CH3 O O CH3 C O CH3 N N CH3
He1 N "s' H3C s O ". O (3) (4) O O O. O O Y O N1 Y CHO CH CH3 CH3 R O O CH3 HC-C-O N S N O OCH H3C s HC s *
O
US 8,507,726 B2 21 22 -continued (24) (25) O CH CH O O O N-O-C-CH C C-C-n-CH C C-C-n-CH N N N N O-C-CH O-C-CH | O O
O n-C6H13-C-C=O n-CH-C-C=N-O-C-CH N O N O || O-C-CH O-C-CH
2O Especially preferred are the above compounds of formula -continued (I), that is the compounds of the above structures (1)-(24). R33 In particular preferred are the compounds (1), (2), (7), (8), R32- - C C-: (9), (12) and (14). | || H In accordance with the invention a combination of the 25 R34 O compounds of the formula I or I" and the known photoinitiator R33 compounds selected from the group consisting of alpha-hy- R.-- E droxy ketones, monoacylphosphine oxides, bisacylphos- | || phine oxides, ketosulfones, benzil ketals, phenylglyoxylates, R34 O OH borates and titanocenes is used as a photoinitiator mixture for " CH the polymerization of ethylenically unsaturated components HO- - C and a combination of compounds of the formula I and ben- | || Zophenones or thioxanthones is used for the polymerization CH, O of (1) at least one ethylenically unsaturated photopolymeriZ- 35 able aminoacrylate compound or (2) an ethylenically unsat- H3C CH3, urated component in the presence of a co-initiator. The co- CH3 initiator is for example a tertiary amine, triethanolamine, 21 N-methyldiethanolamine, p-dimethylamino-benzoate or HO Michler's ketone; other coinitiators are for example thiols, 40 CH3 O S. thioethers, disulfides, phosphonium salts, phosphine oxides or phosphines, as described, for example, in EP 438123, in CH3 GB 2180358 and in JP Kokai Hei 6-683.09. CH3 CH The alpha-hydroxy ketone compound in the photoinitiator / \ mixture as described above for example is of the formula 45 10-iss, CH3, (HK), it, 3 CH3 s (HK) R-C-C O- or O R32 | || 50 R34 O R30 C-C-R, k O-(CH2)5-C x OCH2CH2-O- R31 Hs wherein 55 He-to-city--ocich-O-()---o:&H R is hydrogen or C-C-alkoxy; 3 Ro is hydrogen, C-Cls-alkyl, C-Chydroxyalkyl, C-Cls- (H, alkoxy, —O(CH2CH2O). Ras, C-Cisalkyl-S , O-(CH2)5- C ocich-O-()---o: HC=CH-, HC–C(CH)—, NRR, 60 & &H,
CH a, b and c are 1-3: p is 2-10; G3 al- p G4, 65 q is 1-20; Gs and Gindependently of one another are end groups of the polymeric structure, preferably hydrogen or methyl; US 8,507,726 B2 23 24 Rs2 is hydroxy, C, -Co-alkoxy, or —O(CH2CH2O), C p is 2-10; C-alkyl; q is 1-20; R and R independently of one another are hydrogen, C1-Co-alkyl, C1-Co-alkoxy or —O(CH2CH2O). C Gs and Gindependently of one another are end groups of the C-alkyl, or unsubstituted phenyl or benzyl; or phenyl or 5 polymeric structure, preferably hydrogen or methyl; benzyl Substituted by C-C2-alkyl; or RandR together Rs2 is hydroxy or —O(CH2CH2O). C1-Co-alkyl; with the carbon atom to which they are attached form a R and Raindependently of one another are C-C-alkyl, or cyclohexyl ring; R and R together with the carbon atom to which they with the proviso that R, R and R not all together are are attached form a cyclohexyl ring; C1-Co-alkoxy or —O(CH2CH2O). C1-Co-alkyl; 10 Rss is hydrogen, Rs is hydrogen,
O O CH3 15 f". -C-CH=CH or -Ö-CH=CH or -C-CFCH2:
R and R-7 independently of each other are hydrogen, Re and R-7 independently of each other are hydrogen, C-Coalkyl, C-Cohydroxyalkyl, C-Coalkyl inter C-Coalkyl, C-Cohydroxyalkyl, C-Coalkyl inter rupted by one or more O or NRs, wherein the interrupted rupted by one or more O or NRs, wherein the interrupted C-Coalkyl optionally is substituted by one or more OH: C-Coalkyl optionally is substituted by one or more OH: and Rs is hydrogen C-Coalkyl or C-Coalkyl interrupted by and one or more O. Rss is hydrogen C-Coalkyl or C-Coalkyl interrupted by Preferred are compounds of the formula (HK), wherein 25 one or more O. R is hydrogen or C-C-alkoxy; Specific examples are: Ro is hydrogen, C-Cls-alkyl, C-Chydroxyalkyl, C-Cls 1-Hydroxy-cyclohexyl-phenyl-ketone, alkoxy, —O(CH2CH2O), Ras, NRRs7, 1-4-(2-hydroxyethoxy)-phenyl-2-hydroxy-2-methyl-1- 30 propan-1-one, t 2-hydroxy-2-methyl-1-phenyl-propan-1-one, H-C G4, 2-hydroxy-1-(4-4-(2-hydroxy-2-methyl-propionyl)-ben ol p Zyl-phenyl)-2-methyl-propan-1-one, t 35 2-hydroxy-1-(4-4-(2-hydroxy-2-methyl-propionyl)-phe R32-C-C C - noxyl-phenyl)-2-methyl-propan-1-one, | || H R34 O R33 CH3, H 40 R32-C-C - fit / N' CH3 | || HO-(-1S R34 O OH CH3 N
th 45 Ho-j- HC C /\, CHO HO Yeh, H3C CH3, 50 oligo2-hydroxy-2-methyl-14-(1-methylvinyl)phenylpro HO-h-Ct (21 panone. 2-hydroxy-1-1-4-(2-hydroxy-2-methyl-propionyl)-phe CH3 OIS N nyl-1,3,3-trimethyl-indan-5-yl)-2-methyl-propan-1-one. Compounds of the formula (HK) are known in the art and CH O 55 the compounds as well as their preparation are for example described in U.S. Pat. Nos. 4,347,111, 4,321,118, WO ". 04/092287, U.S. Pat. Nos. 4,672,079, 4,987,159 and WO HO-C-Cth / \ CH-ch 02/85832, the disclosure of which hereby is incorporated by 60 reference. The person skilled in the art is well aware of such CH, O -( )– compounds, as a host of the compounds also is commercially available, for example under the trademarks IRGACURER) t and DAROCURR, provided by Ciba Inc.: ESACURE(R), pro vided by Lamberti SPA. re---()-- 65 R34 O The monoacylphosphine oxide compound in the photoini tiator mixture as described above for example is of the for mula (MPO), US 8,507,726 B2 25 26 halogen, C-C2-alkyl, C2-Co-alkenyl, C-C2-alkoxy, (MPO) C-C alkylthio or NRR, O O Ras and R independently of one another are hydrogen, R-P-C-R4, unsubstituted C-C2-alkyl or C-C2-alkyl Substituted by 5 OH or SH wherein the alkyl chain optionally is interrupted R40 by one to four oxygenatoms; or Ras and Raindependently of one another are C-C2-alkenyl, cyclopentyl, cyclo wherein hexyl, benzyl or phenyl; and Rao and R independently of one another are unsubstituted Rao is C1-Co-alkyl or C-Co-alkenyl. C-Co-alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or 10 Preferred are compounds of the formula (BPO), wherein biphenylyl; or C-Co-alkyl, cyclohexyl, cyclopentyl, phe R and R' independently of one another are phenyl substi nyl, naphthyl or biphenylyl substituted by one or more tuted by one or more halogen, C-C-alkyl or C-C- halogen, C-C2-alkyl, C-C2-alkoxy, C-C alkylthio or alkoxy; NRR, or are OC-Calkyl; 15 Ras is unsubstituted C-Co-alkyl, C-Co-alkyl substituted R is unsubstituted cyclohexyl, cyclopentyl, phenyl, naph by (CO)OR, thyl or biphenylyl, or cyclohexyl, cyclopentyl, phenyl, or R4s is unsubstituted phenyl orphenyl, Substituted by one or naphthyl or biphenylyl substituted by one or more halogen, more C-C2-alkoxy; and C-C-alkyl or C-C-alkoxy; or R is a 5- or 6-membered Rao is C1-Co-alkyl. heterocyclic ring comprising an Satom or Natom; and Specific examples are Ras and R independently of one another are hydrogen, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide: unsubstituted C-C2-alkyl or C-C2-alkyl substituted by bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine OH or SH wherein the alkyl chain optionally is interrupted oxide, by one to four oxygenatoms; or Ras and Raindependently bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine of one another are C-C2-alkenyl, cyclopentyl, cyclo 25 oxide. hexyl, benzyl or phenyl. Compounds of the formula (BPO) are known in the art and Preferred are compounds of the formula (MPO), wherein the compounds as well as their preparation is for example Rao and R independently of one another are unsubstituted described in U.S. Pat. No. 4,737,593, GB 2259704, WO phenyl or OC-Calkyl; and 00/32612 or WO 05/014605. Several of the compounds also R is phenyl substituted by one or more halogen, C-C-alkyl 30 are commercially available, for example under the trademark or C-C-alkoxy; or R is a 5- or 6-membered heterocyclic IRGACURER) provided by Ciba Inc. ring comprising an Satom or Natom; and The benzophenone compound in the photoinitiator mix Specific examples are: ture as described above for example is of the formula (BP) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: ethyl(2.4.6 trimethylbenzoyl phenyl)phosphinic acid ester. 35 Compounds of the formula (MPO) are known in the art and O (BP) the compounds as well as their preparation is for example described in U.S. Pat. No. 4,324,744 and EP 40721 (=Der M M went 91349 D/50). The person skilled in the art is familiar 40 3)-1-(i. with Such compounds and several of the compounds also are RK\- / \ 7 R. commercially available, for example under the trademarks R55 R52 DAROCURR) and IRGACURE(R) provided by Ciba Inc. The bisacylphosphine oxide compound in the photoinitia wherein tor mixture as described above for example is of the formula Rso, Rs. Rs.2, Rs. Rs and Rss independently of one another (BPO), 45 are hydrogen, C-C2-alkyl, C-Ca-halogenalkyl, halogen, N(C-C-alkyl) phenyl, (CO)ORs, ORs7, C-C alkyl which is substituted by (BPO) O O O || || || 50 C1-C4alkyl Re-c-f-c-Rs - N'-C1-C4alkyl halogen, R45 C1-C4alkyl wherein 55 Ra and R' independently of one another are unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, --( )—cies or are cyclohexyl, cyclopentyl, phenyl, naphthyl or biphe nylyl Substituted by one or more halogen, C-C-alkyl or C-C-alkoxy; or R is a 5- or 6-membered heterocyclic 60 ring comprising an Satom or Natom; and --K)--creas O Ras is unsubstituted C-Co-alkyl, C-Co-alkenyl, C-Co alkyl substituted by one or more halogen, C-C2-alkoxy, " / \ C-C alkylthio, NRR or (CO)OR, --K)--- O; or R4s is unsubstituted cyclohexyl, cyclopentyl, phenyl, 65 (H, - naphthyl or biphenylyl; or is cyclohexyl, cyclopentyl, phe nyl, naphthyl or biphenylyl substituted by one or more US 8,507,726 B2 27 28 or Rso additionally is
O O H 2 G1 C - HG2 -O-C-C-O-(CH2)4-O-C-C-O y
C-O-C-C". O- C C-C-O-C-C-O". . C. H. H. H H H2 H 2 3 2
O
th -C-O-CHCH-- 2 sh O-C-CH st O-CHCHCH-i- O-C ( ) 8
O
X is 1-10, in particular 1–5: -continued y is 2-20; ict-o-co-ch=cts Z is 1-6, in particular 1-2; 35 - N'-C1-C4alkyl halogen the sum of d and e is from 10-16, in particular from 12-14, C1-C4alkyl where d is greater thane, and Rs is C-C alkyl, and or Rs, is C-C alkyl which is interrupted by 1-6 O and Rs7 is C-C alkyl which is unsubstituted or is substituted by 40 which is unsubstituted or substituted by one or more OH, O CH -C-CH=CH or -C-C=CH2. halogen, or
C 1- C4alkyl Preferred are compounds of the formula (BP), wherein Rso is hydrogen, C-C2-alkyl, C-Ca-halogenalkyl, halogen, N(C-C-alkyl) phenyl, (CO)ORs, ORs7,
O O CH -S { ) C-Clalkyl, -S { ) C-C-C2alkyl, -S { ) C-C-N/ VO, CH O O
2
O O H -O-C-C--O-(CH2)4-O-C-C-O C l HG,y US 8,507,726 B2 29 30 -continued O CH CH O C-O-C-C-HO-C-HC-C-O-C-C-OHC H. H. H H H. H 2 3 2
O
O O CH O |
--to-cicho--to-cich,+-o-8
O O
Rs and Rs independently of one another are hydrogen, a mixture of C-C2-alkyl, or phenyl: Rs. Rs and Rss independently of one another are hydrogen or C-C2-alkyl: 25 X is 1-10, in particular 1–5: y is 2-20; Z is 1-6, in particular 1-2; the sum of d and e is from 10-16, in particular from 12-14, CH O where d is greater thane, and 30 C C - O H H2 H Rs is C-C2alkyl, and --i-o-2 Rs7 is C-C-alkyl. Specific examples are: O benzophenone, 2,4,6-trimethylbenzophenone, 4-methylben- 35 Zophenone, 3-methylbenzo-phenone, 2-methylbenzophe none, 4-chlorobenzophenone, 4-(4-methylthio)phenyl phenyl-methanone, 3,3'-dimethyl-4-methoxy benzophenone, methyl-2-methylbenzoate, 4-phenyl-ben Zophenone, 4,4'-bis(dimethylamino)-benzophenone,
O
C
O O
with X=1-20 (Omnipol BP); 50 with Zabout 2 and
O CH3
O e-to-clich-to-i- sito-clich,+r-o-8 ( ) O O O US 8,507,726 B2 31 32 with the sum of dande is about 14, where d is greater than with y=about 13 (Speedcure 7020, provided by Lambson) e (Speedcure 7005, provided by Lambson), and any blends or admixtures of the above mentioned com pounds. Compounds of the formula (BP) are well known in the art and the compounds as well as their preparation is for example described in WO 03/033452. 10 Many of the compounds also are commercially available, SX". for example under the trademark DAROCURR) provided by Ciba Inc., ESACURE(R), provided by Lamberti SPA, Speed cure, provided by Lambson or Omnipol provided by IGM. with y=about 14 (Speedcure 7006, provided by Lambson); 15 The thioxanthone compound in the photoinitiator mixture O as described above for example is of the formula (TX),
S O O G1y
25 SX." (TX) O R58 with y=about 12 (Speedcure 7003, provided by Lambson); N sa as 30 Rao 21 S 2x1 R59,
35 C y wherein
40 Rss Rso and Reo independently of one another are hydrogen, halogen, C-C2alkoxy,
O
H O s O CH3 CH3 O C-O-C-C-HO-C C-C-O-C-C-O-H-C H i. H 2 - H. H. H 3
O s
O CH O
2 --to-clich-to-i-to-clich-,8 -o-
O S O US 8,507,726 B2 33 34 or C-C alkyl which is unsubstituted or is substituted by R and R independently of one another are hydrogen, one or more OH, C, -Co-alkyl, C, -Co-alkoxy or —O(CH2CH2O). C Co-alkyl, or unsubstituted phenyl or benzyl, or phenyl or benzyl Substituted by C-C2-alkyl; or RandR together 5 with the carbon atom to which they are attached form a cyclohexyl ring; Res and Ree independently of each other are hydrogen, - N'-C1-C4alkyl halogen; C-Coalkyl, C-Cohydroxyalkyl, or Res and R together with the N-atom to which they are bonded forman aliphatic C1-C4alkyl 10 or aromatic 5- or 6-membered ring, which optionally com prises as further heteroatom an N or O-atom; and R7 is hydrogen, C-C alkyl or C-C alkyl Substituted by X is 2-10; OH. y is 2-20; A specific example is the photoinitiator Esacure 1001 Z is 1-6, in particular 1-2; and 15 available from Lamberti: the sum of d and e is from 10-16, in particular from 12-14, 1-4-(4-benzoylphenylsulfanyl)phenyl-2-methyl-2-(4-me where d is greater than e. thylphenylsulfonyl)propan-1-one:
O O CH | 3 C S c--so CH CH3
25 Preferred are compounds of the formula (TX), wherein Compounds of the formula (KS) are known in the art and Ro is hydrogen; and the compounds as well as their preparation are for example Rss and Rso are hydrogen, halogen, C-Csalkyl or described in WOOO/031030. Esacure 1001 M is commer C-Calkoxy. cially available. Specific examples are 30 a blend of 2-isopropylthioxanthone and 3-isopropylthioxan The benzil ketal or benzoin ether compound in the photo thone, initiator mixture as described above for example is of the a blend of 2-chlorothioxanthone and 3-chlorothioxanthone, 2,4-dimethylthioxanthone, formula (BK) 2,4-diethylthioxanthone, 35 1-chloro-4-propoxy-thioxanthone. Compounds of the formula (TX) are known in the art and the compounds as well as their preparation is for example described in WO 03/033492. Many of the compounds also are commercially available for example under the trademark 40 (BK) Omnipol from IGM. O Rio The ketosulfone compound in the photoinitiator mixture as | described above for example is of the formula (KS), C- -R72, R71 (KS) 45 O O R33 Q-C { ) S { ) c--so| wherein R 34 50 R7 is hydrogen or phenyl: Rzo and R-7, when R-7 is hydrogen, are C-C alkoxy: wherein Ro and R, , when R is phenyl, independently of one R is C-C alkyl, phenyl, naphthyl, wherein the phenyland another are hydrogen or C-Calkoxy. naphthyl are unsubstituted or are substituted by one or more C-C alkyl, halogen, C-Chalogenoalkyl, 55 Preferred are compounds wherein R, is phenyl. Q is Specific examples are 2-ethoxy-1,2-diphenylethanone, 2-isopropoxy-1,2-diphe R64 R nylethanone, 2-isobutoxy-1,2-diphenylethanone, 2-bu toxy-1,2-diphenylethanone, a blend of benzoin n-butyl and M O Q-C- 60 isobutyl ether, 2.2-dimethoxy-1,2-diphenylethanone, 2.2- R-K / k diethoxy-1,2-diphenylethanone, alpha,alpha-diethoxyac etophenone, alpha,alpha-di-(n-butoxy)-acetophenone. Q is OH or NRSR; Compounds of the formula (BK) are known in the art and R. R. and Reindependently of one another are hydrogen, 65 the compounds as well as their preparation are for example halogen, C-C alkyl, CN, C-Calkoxy, phenyl, SR, or described in U.S. Pat. Nos. 4,318,791, 4,321,118 or 4,308, NRSRs: 400. Many of the compounds are commercially available. US 8,507,726 B2 35 36 The phenylglyoxylate compound in the photoinitiator mix Y is a cation, for example a dye cation, an ammonium, phos ture as described above for example is of the formula (PG) phonium or Sulfonium cation. In preferred compounds of the formula (BT) Roo is C-C alkyl: 5 Ro, Ro and Ros are identical and are phenyl which is Sub (PG) stituted by halogen, C-Chalogenoalkyl, C-Calkoxy O O or C-C alkyl, especially by halogen or || || C-Chalogenoalkyl; and C-C-ORso, Y is tetraalkylammonium, for example tetrabutylammonium. Compounds of the formula (BT) are known in the art and 10 the compounds as well as their preparation is for example described in U.S. Pat. Nos. 5,176,984, 5,151,520, 4,954,414 or GB 2307473. wherein The titanocene compound in the photoinitiator mixture as Rso is hydrogen, C-C2-alkyl or 15 described above for example is of the formula (TI)
Rod-Ti-Roo,
wherein Ro and Rs independently of one another are cyclopentadi 25 enyl optionally mono-, di-, or tri-Substituted by C-Cls Rs. Rs. Rs. Rs and Rss independently of one another are alkyl, C-C-alkoxy, cyclopentyl, cyclohexyl or halogen; hydrogen, unsubstituted C-C2-alkyl or C-C2-alkyl Sub Roe and Ro, are phenyl having at least one For CF. Substituent stituted by OH, C-C-alkoxy, phenyl, naphthyl, halogen in ortho position to the Ti-C bond and having at least a or CN: further substituent which is unsubstituted pyrrolinyl or wherein the alkyl chain optionally is interrupted by one or 30 polyoxa-C-Coalkyl or which is pyrrolinyl polyoxa-C- more oxygen atoms; or Rs. Rs. Rs. Rs and Rss indepen Coalkyl substituted by one or two C-C2-alkyl, di(C- dently of one another are C-C-alkoxy, C-C-alkylthio or C2-alkyl)aminomethyl, morpholinomethyl, C-C-alk NRsRs7, enyl, methoxymethyl, ethoxymethyl, trimethylsilyl, Rs and Rs7 independently of one another are hydrogen, formyl, methoxy or phenyl; or Roe and Ro, are unsubstituted C-C2-alkyl or C-C2-alkyl Substituted by 35 OH or SH wherein the alkyl chain optionally is interrupted by one to four oxygenatoms; or Rs and Rs7 independently of one another are C-C2-alkenyl, cyclopentyl, cyclo hexyl, benzyl or phenyl; and Y is C-C2-alkylene optionally interrupted by one or more 40 OXygen atoms. Specific examples are oXo-phenyl-acetic acid 2-2-(2-oxo-2-phenyl-acetoxy)- ethoxy-ethyl ester, methyl alpha-oxo benzeneacetate, 45 Gs is O, S, or NR; ethyl alpha-oxo benzeneacetate. Ros, Roo and Roo independently of one another are hydrogen, Compounds of the formula (PG) are known in the art and halogen, C-C2-alkenyl, C-C alkoxy, C-C2-alkoxy the compounds as well as their preparation are for example interrupted by one to four oxygen atoms, cyclohexyloxy, described in WOO6/120212, U.S. Pat. Nos. 6,048,660, 4,475, cyclopentyloxy, phenoxy, benzyloxy, unsubstituted phenyl 999 and 4,038,164. The compounds mentioned as specific 50 or biphenyl or phenyl or biphenyl substituted by C-C- examples above are also commercially available. alkoxy, halogen, phenylthio or C-C-alkylthio. The borate compound in the photoinitiator mixture as with the proviso that Ros and Roo are not both hydrogen and described above for example is of the formula (BT) that with respect to the residue
55 (BT) R98 / Ny-R 60 FN wherein R100 R. R. R. and R independently of one another are C-C alkyl, phenyl, naphthyl, anthryl or biphenylyl, at least one Substituent Ros or Roo is C-Calkoxy or wherein the phenyl, naphthyl, anthryl and biphenylyl are 65 C-Calkoxy interrupted by one to four oxygen atoms, unsubstituted or are Substituted by one or more halogen, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy; C-Chalogenoalkyl, C-Calkoxy or C-C alkyl, and and Rio is C-Csalkyl, phenyl or cyclophenyl. US 8,507,726 B2 37 38 Specific examples are: bis(..eta.5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H O pyrrol-1-yl)-phenyl)-titanium and bis(2,6-difluorophenyl) | bis(1,2,3,4,5-eta)-1-methyl-2,4-cyclopentadien-1-yl-ti tanium. Rs and Reindependently one another are hydrogen, phenyl or Compounds of the formula (TI) are known in the art and the C-Coalkyl, or Rs and R together with the N-atom to compounds as well as their preparation is for example which they are attached form a heteroaromatic ring system, described in U.S. Pat. Nos. 5,008,302, 5,340,701 and in par in particular carbazolyl; ticular in U.S. Pat. No. 5,075,467. 10 R, is phenyl, naphthyl or C-Coheteroaryl, each of which optionally is substituted by one or more C-Calkyl, halo The compounds specified above are also commercially gen, CN, OR, SR, or NRSR; available under the trademark IRGACURE(R), provided by Rs and R are hydrogen; Ciba Inc. Ro is (CO)R; and Preferred is a photoinititator mixture as defined above, R is (CO)R. wherein the component (i) comprises an alpha-hydroxy 15 Interesting are photoinitiator mixtures comprising ketone, monoacylphosphine oxide, bisacylphosphine oxide, at least one compound of the formula I or I" and at least one ketosulfone or benzil ketal. alpha-hydroxy ketone, e.g. of the formula (HK) as defined above; or Preferred is further a photoinitiator mixture as defined at least one compound of the formula I or I" and at least one above, wherein the compounds of the formula I or (I) ketosulfone, e.g. of the formula (KS) as defined above; or R and R' are C-C alkyl; at least one compound of the formula I of I" and at least one R and R' independently of one another are unsubstituted monoacylphosphine oxide, e.g. of the formula (MPO) as C-Coalkyl or C-Coalkyl substituted by COOR or defined above; or at least one compound of the formula I or I" and at least one 25 bisacylphosphine oxide, e.g. of the formula (BPO) as defined above. In the above mixtures preferably as oxime compound com R20 pounds of the formula I are used. Interesting are for example mixtures comprising as com 30 ponent (i) at least on compound of the formula I or I', prefer X is O: ably of the formula I and as component (ii) at least one compound selected from benzophenone, 2,4,6-trimethylben R is C-Coalkyl, C-Csalkanoyl or phenyl-C-C-alkyl, or Zophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzoyl R is C-Cocycloalkyl which optionally is interrupted by diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phe O; nylphosphine oxide, phenyl-1-hydroxycyclohexyl ketone, R is C-Coalkyl, C-Csalkanoyl, phenyl-C-C-alkyl or 35 2-hydroxy-2-methyl-1-phenyl-propanone, 2-hydroxy-1-4- C-Coheteroaryl; or R is phenyl which is unsubstituted or 4-(2-hydroxy-2-methyl-propionyl)-benzyl-phenyl)-2-me Substituted by C-Coalkyl, halogen or thyl-propan-1-one,
O CH
CHO21su | \ V CH3
O O
Ol C -O------H H O
(wherein x=2-20),
O O CH 3
CH3
and any combination of said compounds (as component (ii)). US 8,507,726 B2 39 40 In particular preferred are photoinitiator mixtures compris Naphthyl is 1-naphthyl or 2-naphthyl. ing (ii) at least one compound of the formula I or I", preferably Coumarinyl is for example 1-coumarinyl: I, especially a compound wherein R and Rare identical and are methyl and R, is phenyl substituted by methyl, and (i) bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 5 2-hydroxy-1-(4-4-(2-hydroxy-2-methyl-propionyl)-ben Zyl-phenyl)-2-methyl-propan-1-one,
O O O O 10 or 4-coumarinyl or 5-coumarinyl. C-C-(OCH2CH2)4-O-C-C s Phenylene is 1.2-phenylene, 1,3-phenylene or 1.4-phe K)- -() nylene, preferably 1.4-phenylene. Naphthylene is for example 1.2-, 1.3-, 1.4-, 1.5-, 1.6-, 1.8- 15 2.3-, 2,6- or 2.7-naphthlene. C-Coalkyl is linear or branched and is, for example, H3C CH C-C is , C-C , C-C2 , C-C , C1-C - or th O / \ CH3 C-C alkyl or C-C - or Ca-Calkyl. Examples are methyl, ethyl, propyl, isopropyl. n-butyl, Sec-butyl, isobutyl, tert-bu tyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethyl hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl. CH3 hexadecyl, octadecyl and icosyl. HC X2 C-C alkyl, C-C alkyl, C-C alkyl, C-Csalkyl and N/ N C-Calkyl have the same meanings as given above for C-Coalkyl up to the corresponding number of C-atoms. 25 C-Coalkyl which is interrupted by one or more 0 is for example interrupted 1-9, 1-5, 1-3 or once or twice by O. Two O-atoms are separated by at least one methylene group, pref or oligo2-hydroxy-2-methyl-14-(1-methylvinyl)phenyl erably at least two methylene groups, namely ethylene. The propanone. alkyl groups are linear or branched. For example the follow Further of interest in the context of the present invention 30 ing structural units will occur, —CH2—CH2—O—CH2CH, are photopolymerizable compositions comprising CHCHO), CH, whereiny=1-9, -(CH-CHO), CHCH, CH, CH(CH)—O CH CHCH or (a) at least one ethylenically unsaturated photopolymerizable - CH-CH(CH) O CH-CH. In case that aminoacrylate compound or an ethylenically unsaturated C-Coalkyl interrupted by one or more O or NRs similar component in the presence of a H-donor (co-initiator) and structures, wherein one or more 0 are replaced by NRs are 35 formed. (b1) a photoinitiator mixture consisting of at least one com C-Coalkylene is linear or branched and is, for example, pound of the formula I or I", preferably I, as defined above C-C , C-C2 , C1-Co-, C-C , C1-C - or and a benzophenone compound, e.g. of the formula (BP) as C-C alkylene or C-C - or Ca-Calkylene. Examples are defined above; methylene, ethylene, propylene, methylethylene, butylene, methylpropylene, ethylethylene, 1,1-dimethylethylene, 1,2- as well as 40 dimethylethylene, pentylene, hexylene, heptylene, 2-ethyl photopolymerizable compositions comprising hexylene, octylene, nonylene, decylene, dodecylene, tetrade (a) at least one ethylenically unsaturated photopolymerizable cylene, pentadecylene, hexadecylene, octadecylene and aminoacrylate compound or an ethylenically unsaturated icosylene. C-Coalkylene has the same meanings as given above for C-Coalkylene up to the corresponding number of component in the presence of a H-donor (co-initiator) and 45 C-atoms. (b1) a photoinitiator mixture consisting of at least one com Cyclohexylene is 1.2-, 1.3- or 1,4-cyclohexylene. pound of the formula I or I", preferably I, as defined above C-Chydroxyalkyl means C-C alkyl, which substituted and a thioxanthone compound, e.g. of the formula (TX) as by one or two O-atoms. The alkyl radical is linear or defined above. branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, Preferred are photopolymerizable compositions compris 50 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hy ing droxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybu tyl, 2,3-dihydroxypropyl, or 2,4-dihydroxybutyl. (a) at least one ethylenically unsaturated photopolymerizable Cs-Cocycloalkyl in the context of the present application aminoacrylate compound or an ethylenically unsaturated is to be understood as alkyl which at least comprises one ring. component in the presence of a H-dondor (co-initiator) and 55 It is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclo b1) a pphotoinitiator mixture consisting9. of at least one com hexyl, cyclooctyl, especially cyclopenty1 and cyclohexyl. pound of the formula I as defined above and Omnipol BP Cs-Cocycloalkyl in the context of the present invention is (as defined above), Speedcure 7005 (as defined above). also meant to cover bicyclic rings, in other words a bridged Substituted aryl radicals phenyl, naphthyl, biphenylyl are ring, Such as for example substituted 1 to 7, 1 to 6 or 1 to 4 times respectively, in 60 particular one, two or three times. It is evident that a defined aryl radical cannot have more substituents than free positions at the aryl ring. Substituents on the phenyl ring are preferably in positions 65 C-CO 4 or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2.4.6-configuration on the phenyl ring. US 8,507,726 B2 41 42 and corresponding rings. Further examples are structures like C-Coalkoxyalkyl is C-Coalkyl, which is interrupted by one O-atom. C-Coalkyl has the same meanings as given above for C-Coalkyl up to the corresponding number of CH C-atoms. Examples are methoxymethyl, methoxyethyl, 31 3 methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl. —cil ( ) -CH porpoxymethyl, prpopxyethyl, propoxypropyl. C-Coalkanoyl is linear or branched and is, for example, C-Cls-, C-C-, C-C-, C-C-, C-C - or (alkylene) Cys-C)N C-C alkanoyl or C-C - or C-Csalkanoyl. Examples are H acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl, hex alkyl, 10 anoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, octadecanoyl, N -US y icosanoyl, preferably acetyl. H C-Csalkanoyl has the same meanings as given above for C-Coalkanoyl up to the corresponding number of C-atoms. 15 C-C alkoxycarbonyl is a linear or branched and is, for as well as bridged or fused ring systems, e.g. example, methoxycarbonyl, ethoxycarbonyl, propoxycarbo nyl. n-butyloxycarbonyl, isobutyloxycarbonyl, 1,1-dimethyl propoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially meth oxycarbonyl, ethoxycarbonyl, propoxycarbonyl. n-butyloxy As s As (alkylene) s carbonyl or iso-butyloxycarbonyl, preferably methoxycarbo nyl. etc. are also meant to be covered by the term. C-C alkoxycarbonyl which is interrupted by one or more Cs-Cocycloalkyl which optionally is interrupted by O, S, 25 O is linear or branched. Two O-atoms are separated by at least CO, NRs, has the meanings given above, wherein at least one two methylene groups, namely ethylene. CH-group of the alkyl is exchanged by either O, S, CO or Phenoxycarbonyl is phenyl-O CO—. Substituted phe NRs. noxycarbonyl radicals are substituted one to four times, for Examples are structures like example one, two or three times, especially two or three times. Substituents on the phenyl ring are preferably in posi 30 tions 4 or in 3.4-, 3,4,5-, 2,6-, 2,4- or 2.4.6-position on the lkyl phenyl ring, in particular in 4- or 3.4-position. y Phenyl-C-C-alkyl is for example benzyl, phenylethyl, C.-methylbenzyl or C.C.-dimethylbenzyl, especially benzyl. —ct (). —cil ( O) s C-Calkenyl radicals are mono- or polyunsaturated and 35 are for example C-Co-, C-C , C-C-alkenyl e.g. vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, - 2 N O 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 7-octenyl or dodece H nyl, especially allyl. C-Calkenyl radicals have the same meanings as given above for C-Calkenyl radicals up to the (alkylene) -Cys-C"s N 2 s 40 corresponding number of C-atoms. H C-Calkenoxy radicals may be mono- or polyunsaturated O s and are for example allyloxy, methallyloxy, butenyloxy, pen tenoxy, 1,3-pentadienyloxy, 5-hexenyloxy. N C." (alkylene) CycO CH C-Calkenoyl radicals are mono- or polyunsaturated and H O 45 are for example C-Co-, C-C-alkenoyl, e.g. propenoyl, H3C CH3 2-methyl-propenoyl, butenoyl, pentenoyl, 1,3-pentadienoyl, 5-hexenoyl. C-Calkenoyl radicals have the same meanings as given above for C-Calkenoyl radicals up to the corre (alkylene) -C) O sponding number of C-atoms. 50 Halogen is fluorine, chlorine, bromine and iodine, espe CH3 cially fluorine, chlorine and bromine, preferably fluorine and l-CH2 O chlorine. In the context of the present invention C-Coheteroaryl is etc. meant to comprise either one ring or a multiple ring system, C-C salkoxy is C-C salkyl, which is substituted by one 55 e.g. a fused ring-system. Examples are thienyl, benzobthie O-atom. C-C salkyl has the same meanings as given above nyl, naphtho2,3-bithienyl, thianthrenyl, dibenzofuryl, for C-Coalkyl up to the corresponding number of C-atoms. chromenyl, Xanthenyl, thioxanthyl, phenoxathiinyl, pyrrolyl, C-C alkoxy is linear or branched, for example, methoxy, imidazolyl pyrazolyl pyrazinyl, pyrimidinyl, pyridazinyl, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinoliz isobutyloxy, tert-butyloxy. 60 inyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, qui C-C alkylsulfanyl or C-C alkylthio is C-C alkyl, noxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, which is Substituted by one-S-atom. C-C alkyl has the same 6-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, meanings as given above for C-Coalkyl up to the corre phenanthrolinyl, phenazinyl, isothiazolyl phenothiazinyl, sponding number of C-atoms. C-C alkylsulfanyl is linear or isoxazolyl, furazanyl, phenoxazinyl, 7-phenanthryl, branched, for example, methylsulfanyl, ethylsulfanyl, pro 65 anthraquinone-2-yl (=9,10-dioxo-9,10-dihydroanthracen-2- pylsulfanyl, isopropylsulfanyl. n-butylsulfanyl, sec-butylsul yl), 3-benzobthienyl, 5-benzobthienyl, 2-benzob thie fanyl, isobutylsulfanyl, tert-butylsulfanyl. nyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzo US 8,507,726 B2 43 44 furyl, 2-Xanthenyl, 8-methyl-2-Xanthenyl, 3-Xanthenyl, -continued 2-phenoxyathiinyl, 2.7-phenoxathiinyl, 2-pyrrolyl, 3-pyrro lyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imi dazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-me e.g. thyl-3-pyrazolyl, 1-propyl-4-pyrazolyl 2-pyrazinyl, 5.6- dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-in dolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2.7- 21 21 dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 10 T- T 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, C C C C 3-methoxy-6-isoquinolyl 2-quinolyl, 6-quinolyl,7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazi nyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4- dimethoxy-6-phthalazinyl, 1.8-naphthyridin-2-yl 2-quinox 15 alinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2.3- N dimethoxy-6-quinoxalinyl 2-quinazolinyl, 7-quinazolinyl, N 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pte ridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carba Zolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-car bazolyl, B-carbolin-3-yl, 1-methyl-f-carbolin-3-yl, If, for example Rs, R. R. and Rare NRR, wherein the 1-methyl-3-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, substituents NRs R form 5- or 6-membered rings via the 3-acridinyl, 2-perimidinyl, 1-methyl-5-perimidinyl, radicals Rs and/or R with one of the carbon atoms of the 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 25 phenyl, group for example the following structure is formed 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothi azinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3- 21 furazanyl, 2-phenoxazinyl, 10-methyl-2-phenoxazinyl, etc. C-Chaloalkyl is C-C alkyl as defined above Substi 30 T tuted by halogen as defined above. The alkyl radical is for example mono- or poly-halogenated, up to the exchange of all -N H-atoms by halogen. It is for example CH, Hal, wherein C1 C2-alkyl x+y=2n+1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl 35 It is clear, that in the context of the present definitions and in or 2-bromopropyl, especially trifluoromethyl or trichlorom view of the examples these groups may bear further substitu ethyl. entS. If the substituents OR SR and NRs R on a phenyl, naph thyl or biphenylyl ring form 5- or 6-membered rings via the If the substituents OR, SR or NRSR on the phenyl group radicals R. R. Rs and/or R with further substituents on the 40 as Rs and/or R optionally form 5- or 6-membered rings via phenyl or naphthyl ring, or with a carbon atom of the phenyl, the radicals R. R. Rs and/or R with one of the carbonatoms naphthyl or biphenylyl ring, structures comprising two or of the phenyl, naphthyl group or that of the substituent R-7, for three rings (inclusive the phenyl ring) are obtained. Examples example structures comprising two or three rings (inclusive the phenyl rings) are obtained. Examples are 45
O O CCCCC 50 NCCO-CO O N S 1N4 1Na O 55 | s 2n S N 1s 60 hi, 21 4Y M N 65 - || H-R, C1-C12-alkyl N-N-1s US 8,507,726 B2 45 46 -continued containing a double bond are alkyl, hydroxyalkyl, cycloalkyl (which optionally interrupted by O) or aminoalkyl (meth) 21 4S acrylates, for example methyl, ethyl, propyl, butyl, hexyl, - -H-R. benzyl, 2-ethylhexyl, isobornyl, cyclohexyl, tetrahydrofurfu N-N-1s ryl 2-hydroxyethyl, 2-hydroxypropyl, methoxyethyl, ethoxy ethyl, glycerol, phenoxyethyl, methoxydiethylene glycol, st ethoxydiethylene glycol, polyethylene glycol, polypropylene glycol, glycidyl, N,N-dimethylaminoethyl, and N,N-diethy If Rs and R together with the N-atom to which they are laminoethyl (meth)acrylate. Silicone acrylates are also 10 advantageous. Other examples are acrylonitrile, acrylamide, attached form a heteroaromatic ring system, said ring system methacrylamide, N-substituted (meth)acrylamides such as is meant to comprise more than one ring, e.g. two or three N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acryla rings, as well as one or more than one heteroatoms, from the mide, N,N-dibutyl (meth)acrylamide, N-methyl (meth)acry same kind or different ones. Suitable heteroatoms are for lamide, N-ethyl (meth)acrylamide, N-butyl (meth)-acryla example, N. S. O or P. in particular N, S or O. Examples are, 15 mide, and N-(meth)acryloylmorpholine, vinyl esters such as carbazole, indole, isoindole, indazole, purine, isoquinoline, vinyl acetate, vinyl ethers such as isobutyl vinyl ether, Sty quinoline, carboline, phenothiazine etc. rene, alkyl- and halostyrenes, N-vinylpyrrolidone, N-vinyl If Rs and R or R, and Rs together with N-atom to which caprolactam, N-Vinylacetoamide, N-Vinylformamide, vinyl they are attached form a 5- or 6-membered saturated or unsat chloride or vinylidene chloride. urated ring, which optionally is interrupted by O.S or NR, Examples of monomers containing two or more double saturated or unsaturated rings are formed, for example aziri bonds are the diacrylates of ethylene glycol, propylene gly dine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1.3- col, neopentylglycol, hexamethylene glycol or of bisphenol diazine, 1,2-diazine, piperidine or morpholine. A, and 4,4'-bis(2-acryl-oyloxyethoxy)diphenylpropane, tri If R and R together with the carbon atom to which they methylolpropane triacrylate, pentaerythritol triacrylate or tet are attached form a cyclohexyl ring, structures like 25 raacrylate, vinyl acrylate, divinylbenzene, divinyl Succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris(2-acryloylethyl) isocyanurate. Examples of polyunsaturated compounds of relatively R30 C high molecular mass (oligomers) are acrylated epoxy resins, 30 polyesters containing acrylate-, vinyl ether- or, depending on the intended application, epoxy-groups, and also polyure R31 thanes and polyethers containing acrylates. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually prepared from maleic acid, phthalic acid are formed. 35 and one or more diols and have molecular weights of from Ra as a 5- or 6-membered heterocyclic ring comprising an about 500 to 3000. In addition it is also possible to employ S atom or N atomis for example furyl, thienyl, pyrrolyl, vinyl ether monomers and oligomers, and also maleate-ter oXinyl, dioxinyl or pyridyl. Said heterocyclic rings are unsub minated oligomers with polyester, polyurethane, polyether, stituted or are for example substituted once or more times by polyvinyl ether and epoxy main chains. Of particular Suitabil for example linear or branched C-C-alkyl such as methyl, 40 ity are combinations of oligomers which carry vinyl ether ethyl, propyl, butyl, pentyl or hexyl. Examples of Such rings groups and of polymers as described in WO 90/01512. How are dimethylpyridyl, dimethylpyrrolyl or methylfuryl. ever, copolymers of vinyl ether and maleic acid-functional The terms “and/or” or “or/and in the present context are ized monomers are also suitable. Unsaturated oligomers of meant to express that not only one of the defined alternatives this kind can also be referred to as pre-polymers. (substituents) may be present, but also several of the defined 45 Particularly suitable examples are esters of ethylenically alternatives (Substituents) together, namely mixtures of dif unsaturated carboxylic acids and polyols or polyepoxides, ferent alternatives (substituents). and polymers having ethylenically unsaturated groups in the The term “at least’ is meant to define one or more than one, chain or in side groups, for example unsaturated polyesters, for example one or two or three, preferably one or two. polyamides and polyurethanes and copolymers thereof, poly The term “optionally substituted” means, that the radical to 50 mers and copolymers containing (meth)acrylic groups in side which it refers is either unsubstituted or substituted. chains, and also mixtures of one or more such polymers. Throughout this specification and the claims which follow, Examples of unsaturated carboxylic acids are acrylic acid, unless the context requires otherwise, the word “comprise’, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, or variations such as “comprises” or “comprising, will be and unsaturated fatty acids such as linolenic acid or oleic acid. understood to imply the inclusion of a stated integer or step or 55 Acrylic and methacrylic acid are preferred. group of integers or steps but not the exclusion of any other Suitable polyols are aromatic and, in particular, aliphatic integer or step or group of integers or steps. and cycloaliphatic polyols. Examples of aromatic polyols are The preferences referring to the compounds of the formula hydroquinone, 4,4'-dihydroxydiphenyl, 2.2-di(4-hydrox I, I', (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), yphenyl)-propane, 2.2-bis(4-hydroxyphenyl)methane, 2.2- (BT) and (TI) as given hereinbefore and in the context of the 60 bis(4-hydroxyphenyl)hexafluoropropane, 9.9-bis(4-hydrox whole text, are intended not to refer to the compounds as Such yphenyl)fluorene, novolaks and resols. only, but to all categories of the claims. That is to the compo Examples of aliphatic and cycloaliphatic polyols are alky sitions, comprising the compounds, as well as the use or lenediols having preferably 2 to 12C atoms, such as ethylene process claims in which said compounds are employed. glycol, 1.2- or 1,3-propanediol. 1.2-, 1.3- or 1,4-butanediol. The unsaturated compounds (a) may include one or more 65 pentanediol, hexanediol, octanediol, dodecanediol, diethyl olefinic double bonds. They may be of low (monomeric) or ene glycol, triethylene gleyol, polyethylene glycols having high (oligomeric) molecular mass. Examples of monomers molecular weights of preferably from 200 to 1500, 1,3-cyclo US 8,507,726 B2 47 48 pentanediol. 1.2-, 1.3- or 1,4-cyclohexanediol. 1,4-dihy Typical examples of component (a) based on polyepoxides droxymethylcyclohexane, glycerol, tris(B-hydroxyethyl) are 2.2-bis(4-(2-hydroxy-3-acryl-oxy)propoxyphenyl amine, triethanolamine, trimethylolethane, propane, 2.2-bis(4-(2-hydroxy-3-acryloxy) trimethylolpropane, pentaerythritol, pentaerythritol monoox propoxyethoxyphenylpropane, 9.9-bis(4-(2-hydroxy-3- alate, ethers of pentaerythritol with ethylene glycolor propy acryloxy)propoxyphenylfluorene, 9.9-bis(4-(2-hydroxy lene glycol, ethers of dipentaerythritol with ethylene glycolor 3-acryl-oxy)propoxyethoxyphenylfluorine, and reaction propylene glycol, dipentaerythritol. 2.2-bis(4-(2-hydroxy products of epoxy resins based on novolacs with (meth) ethoxy)phenylmethane, 2.2-bis(4-(2-hydroxyethoxy)phe acrylic acid. nylpropane and 9.9-bis(4-(2-hydroxyethoxy)phenylfluo Also suitable as components (a) are the amides of identical 10 or different, unsaturated carboxylic acids with aromatic, rine pentaerythritol monooxalate, ethers of pentaerythritol cycloaliphatic and aliphatic polyamines having preferably 2 with ethylene glycol or propylene glycol, ethers of dipen to 6, especially 2 to 4, amino groups. Examples of Such taerythritol with ethylene glycol or propylene glycol, pen polyamines are ethylenediamine, 1.2- or 1,3-propylenedi taerythritol monooxalate, ethers of pentaerythritol with eth amine, 1.2-, 1.3- or 1,4-butylenediamine, 1.5-pentylenedi ylene glycol or propylene glycol, ethers of dipentaerythritol 15 amine, 1.6-hexylenediamine, octylenediamine, dodecylene with ethylene glycolor propylene glycol, and sorbitol. Other diamine, 1,4-diaminocyclohexane, isophoronediamine, Suitable polyols are polymers and copolymers containing phenylenediamine, bisphenylenediamine, di-3-aminoethyl hydroxyl groups in the polymer chain or in side groups, ether, diethylenetriamine, tri-ethylenetetramine, di(B-amino examples being homopolymers or copolymers comprising ethoxy)- or di(B-aminopropoxy)ethane. Other suitable vinyl alcohol or comprising hydroxyalkyl (meth)acrylates. polyamines are polymers and copolymers, preferably with Further polyols which are suitable are esters and urethanes additional amino groups in the side chain, and oligoamides having hydroxyl end groups. having amino end groups. Examples of Such unsaturated Other Suitable polyols are polymers and copolymers con amides are methylenebisacrylamide, 1.6-hexamethylenebi taining hydroxyl groups in the polymer chain or in side sacrylamide, diethylenetriaminetrismethacrylamide, bis groups, examples being polyvinyl alcohol and copolymers 25 (methacrylamidopropoxy)ethane, B-methacrylamidoethyl thereof or polyhydroxyalkyl methacrylates or copolymers methacrylate and N(B-hydroxyethoxy)ethylacrylamide. thereof. Further polyols which are suitable are oligoesters In particular in case of the photoinitiator mixture consist having hydroxyl end groups. ing of a compound of the formula I as defined above and a The polyols may be partially or completely esterified with benzophenone compound (BK) or a thioxanthone compound one carboxylic acid or with different unsaturated carboxylic 30 (TX) as defined above, the above mentioned aminoacrylates acids, and in partial esters the free hydroxyl groups may be are preferentially used as component (a). Specific examples modified, for example etherified or esterified with other car are given below in the context of the application in printing boxylic acids. inks. Examples of polyepoxides are those based on the above Suitable unsaturated polyesters and polyamides are mentioned polyols, especially the aromatic polyols, and 35 derived, for example, from maleic acid and from diols or epichlorohydrin. diamines. Some of the maleic acid can be replaced by other Examples of esters based on polyols are: trimethylolpro dicarboxylic acids. They can be used together with ethyleni pane tri(meth)acrylate, trimethylolpropane tri(acryloylox cally unsaturated comonomers, for example styrene. The ypropyl)ether, trimethylolethane tri(meth)acrylate, ethylene polyesters and polyamides may also be derived from dicar glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 40 boxylic acids and from ethylenically unsaturated diols or triethylene glycol di(meth)acrylate, tetraethylene glycol diamines, especially from those with relatively long chains di (meth)acrylate, tetramethylene glycol di(meth)acrylate, of for example 6 to 20 C atoms. Examples of polyurethanes neopentyl glycol di(meth)acrylate, pentaerythritol di(meth) are those composed of saturated or unsaturated diisocyanates acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol and of unsaturated or, respectively, Saturated diols. tetra(meth)acrylate, pentaerythritol tri(meth)acrylate 45 Polymers with (meth)acrylate groups in the side chain are monooxalate, dipentaerythritol di(meth)acrylate, dipen likewise known. They may, for example, be reaction products taerythritol tri(meth)acrylate, dipentaerythritol tetra(meth) of epoxy resins based on novolaks with (meth)acrylic acid, or acrylate, dipentaerythritol penta(meth)acrylate, dipen may be homo- or copolymers of vinyl alcohol or hydroxy taerythritol hexa(meth)acrylate, dipentaerythritol penta alkyl derivatives thereof which are esterified with (meth) (meth)acrylate mono(2-hydroxyethyl)ether, 50 acrylic acid, or may be homo- and copolymers of (meth) tripentaerythritol octa(meth)acrylate, 1,3-butanediol acrylates which are esterified with hydroxyalkyl (meth) di (meth)acrylate, 1,4-butanediol ditaconate, hexanediol acrylates. di (meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, Sor Other suitable polymers with acrylate or methacrylate bitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol groups in the side chains are, for example, solvent soluble or penta(meth)acrylate, Sorbitol hexa(meth)acrylate, oligoester 55 alkaline soluble polyimide precursors, for example poly (meth)acrylates, glycerol di(meth)acrylate and tri(meth)acry (amic acid ester) compounds, having the photopolymerizable late, di(meth)acrylates of polyethylene glycol with a molecu side groups either attached to the back-bone or to the ester lar weight of from 200 to 1500, pentaerythritol diitaconate, groups in the molecule, i.e. according to EP 624826. Such dipentaerythritol trisitaconate, dipentaerythritol pentaitacon oligomers or polymers can be formulated with the new pho ate, dipentaerythritol hexaitaconate, ethylene glycolditacon 60 toinitiators and optionally reactive diluents, like polyfunc ate, propylene glycol ditaconate, 1,3-butanediol ditaconate, tional (meth)acrylates in order to prepare highly sensitive 1,4-butanediol diitaconate, tetramethylene glycol ditacon polyimide precursor resists. ate, Sorbitol tetraitaconate, ethylene glycol dicrotonate, tet The photopolymerizable compounds can be used alone or ramethylene glycol dicrotonate, pentaerythritol dicrotonate, in any desired mixtures. It is preferred to use mixtures of ethylene glycol dimaleate, tiethylene glycol dimaleate, pen 65 polyol (meth)acrylates. taerythritol dimaleate, sorbitol tetramaleate, or mixtures Examples of the component (a) are also polymers or oli thereof. gomers having at least two ethylenically unsaturated groups US 8,507,726 B2 49 and at least one carboxyl function within the molecule struc -continued ture, Such as a resin obtained by the reaction of a saturated or unsaturated polybasic acid anhydride with a product of the (V-5) R50 O reaction of an epoxy compound and an unsaturated monocar | || boxylic acid, for example, photosensitive compounds as 5 CH=C-C-O-M-O described in JP 6-1638 and JP 10301276 and commercial O products such as EB9696, UCB Chemicals; KAYARAD TCR1025, Nippon Kayaku Co., LTD. Examples of the poly (V-6) basic acid anhydride are maleic anhydride, Succinic anhy R50 O dride, itaconic anhydride, phthalic anhydride, tetrahydro- 10 | || phthalic anhydride, hexahydrophthalic anhydride, CHEC-C-O-Mio methyltetrahydrophathalic anhydride, glutaric anhydride, glutaconic anhydride, citraconic anhydride, diglycolic anhy li dride, iminodiacetic anhydride, 1,1-cyclopentanediacetic (V-7) R50 O anhydride, 3.3-dimethylglutaric anhydride, 3-ethyl-3-meth | || ylglutaric anhydride, 2-phenylglutaric anhydride, homoph CH2=C-C-O-Mio O thalic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, and OH O biphenylether tetracarboxylic acid dianhydride. Other (V-8) example of the polymers or oligomers having at least two R50 O O ethylenically unsaturated groups and at least one carboxyl | || | CH2=C-C-O-Mio C-O-CH function within the molecule structure is an addition product O formed between a carboxyl group-containing resin and an 25 unsaturated compound having an O.B-unsaturated double HO bond and an epoxy group. As the carboxylic acid containing (V-9) polymer, the binder polymers which are resulting from the R50 O O reaction of an unsaturated carboxylic acid compound with | || one or more polymerizable compounds, for example, copoly CH=C-C-O-Mo-C-O-CH mers of (meth)acrylic acid, benzyl (meth)acrylate, styrene O and 2-hydroxyethyl (meth)acrylate, copolymers of (meth) acrylic acid, Styrene and C.-methystyrene, copolymers of (meth)acrylic acid, N-phenylmaleimide, styrene and benzyl (V-10) 35 R50 O O (meth)acrylate, copolymers of (meth)acrylic acid and sty | || rene, copolymers of (meth)acrylic acid and benzyl (meth) CH2=C-C-O-Mio CH-O-C acrylate, copolymers of tetrahydrofurfuryl (meth)acrylate, O styrene and (meth)acrylic acid, and the like. HO Examples of the unsaturated compounds having an epoxy 40 (V-11) R50 O group are given below in the formula (V-1)-(V-15); | || CH=C-C-O-Mo-CH O (V-1) OH R50 O R 45 | || R" O (V-12) CH=(--O-MA() R50 O | || (V-2) R50 O 50 CH=C-C-O O y | || CH=C-C-O (X O O (V-13)
(V-3) 55 R50 O R50 O | || | || CH=C-C-O O O CH=C-C-O-Mo O O 60 (V-4) (V-14) R50 O R50 O R50 CH=C-C-O-Mo CH=C-C-N-Mo 65 US 8,507,726 B2 51 52 -continued in particular from 70 to 40% by weight. In these compositions (V-15) the sum of the percentages given for water and prepolymer is in each case 100, with auxiliaries and additives being added in R50 O R50 varying quantities depending on the intended use. CH=C-C-N-Mo-O-Mio The radiation-curable, film-forming prepolymers which are dispersed in water and are often also dissolved are aque ous prepolymer dispersions of mono- or polyfunctional, eth ylenically unsaturated prepolymers which are known perse, can be initiated by free radicals and have for example a wherein Rso is hydrogen or methyl group, Mo is substituted 10 or unsubstituted alkylene having 1 to 10 carbon atoms. content of from 0.01 to 1.0 mol of polymerizable double Among these compounds, compounds having alicyclic bonds per 100 g of prepolymer and an average molecular epoxy groups are particularly preferred, because these com weight of, for example, at least 400, in particular from 500 to pounds have a high reactivity with carboxyl group-containing 10,000. Prepolymers with higher molecular weights, how resins, accordingly the reaction time can be shortened. These 15 ever, may also be considered depending on the intended compounds further do not cause gelation in the process of application. Use is made, for example, of polyesters contain reaction and make it possible to carry out the reaction stably. ing polymerizable C-C double bonds and having an acid On the other hand, glycidyl acrylate and glycidyl methacry number of not more than 10, of polyethers containing poly late are advantageous from the viewpoint of sensitivity and merizable C C double bonds, of hydroxyl-containing reac heat resistance because they have a low molecular weight and tion products of a polyepoxide, containing at least two can give a high conversion of esterification. epoxide groups per molecule, with at least one C.B-ethyleni Concrete examples of the abovementioned compounds are, cally unsaturated carboxylic acid, of polyurethane (meth) for example a reaction product of a copolymer of styrene, acrylates and of acrylic copolymers which contain C.f3-eth C.-methyl styrene and acrylic acid or a copolymer of methyl ylenically unsaturated acrylic radicals, as are described in EP methacrylate and acrylic acid with 3.4-epoxycyclohexylm 25 12339. Mixtures of these prepolymers can likewise be used. ethyl (meth)acrylate and as a commercial product Also suitable are the polymerizable prepolymers described in ACA200M, Daicel Industries. EP33896, which are thioether adducts of polymerizable pre As diluent, a mono- or multi-functional ethylenically polymers having an average molecular weight of at least 600, unsaturated compound, or mixtures of several of said com a carboxyl group content of from 0.2 to 15% and a content of pounds, can be included in the above composition up to 90%, 30 from 0.01 to 0.8 mol of polymerizable C C double bonds for example up to 70% by weight based on the solid portion of per 100 g of prepolymer. Other Suitable aqueous dispersions, the composition. based on specific alkyl (meth)acrylate polymers, are Subject of the invention also is a photopolymerizable com described in EP 41125, and suitable waterdispersible, radia position as described above, wherein the component (a) is a tion-curable prepolymers of urethane acrylates can be found resin obtained by the reaction of a Saturated or unsaturated 35 in DE 2936O39. polybasic acid anhydride with a product of the reaction of an Further additives which may be included in these radiation epoxy resin and an unsaturated monocarboxylic acid. curable aqueous prepolymer dispersions are dispersion aux Such components are for example described in JP06-1938, iliaries, emulsifiers, antioxidants, e.g. 2,2-thiobis(4-methyl JP08-278629, JP08-278630, JP10-301276, JP2001-40022, 6t-butylphenol) or 2,6-di-t-butylphenol, light stabilizers, JP10-221843, JP11-231523, JP2002-206014-A or JP2006 40 dyes, pigments, fillers. Such as glass or alumina, for example 53569-A, the disclosure of which hereby is incorporated by talc, gypsum, silicic acid, rutile, carbon black, Zinc oxide, reference. iron oxides, reaction accelerators, levelling agents, lubri The unsaturated compounds (a) can also be used as a mix cants, wetting agents, thickeners, flatting agents, antifoams ture with cationic photopolymerizable or non-photopolymer and other auxiliaries customary in paint technology. Suitable izable, film-forming components. These may, for example, be 45 dispersion auxiliaries are water-soluble organic compounds physically drying polymers or solutions thereof in organic which are of high molecular mass and contain polar groups, solvents, for instance nitrocellulose or cellulose acetobu examples being polyvinyl alcohols, polyvinylpyrrolidone or tyrate. They may also, however, be chemically and/or ther cellulose ethers. Emulsifiers which can be used are nonionic mally curable (heat-curable) resins, examples being polyiso emulsifiers and, if desired, ionic emulsifiers as well. cyanates, polyepoxides and melamine resins, as well as 50 In certain cases it may be of advantage to use mixtures of polyimide precursors. The use of heat-curable resins at the two or more of the photoinitiators of formula (I) or (I), same time is important for use in Systems known as hybrid preferably (I), in combination with the photoinitiators of for systems, which in a first stage are photopolymerized and in a mula (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), second stage are crosslinked by means of thermal aftertreat (BT), (TI); or to use mixtures of two or more of the photoini ment or vice versa. The resin can bear both the photopoly 55 tiators of formula (HK), (MPO), (BPO), (BP), (TX), (KS), merizable and the heat-curable groups. (BK), (PG), (BT), (TI) in combination with the photoinitiator The invention also provides compositions comprising as of formula (I) or (I), preferably (I); or to use mixtures of two component (a) at least one ethylenically unsaturated photo or more of the photoinitiators of formula (I) or (I), preferably polymerizable compound which is emulsified or dissolved in (I), in combination with two or more of the photoinitiators of water. Many variants of Such radiation-curable aqueous pre 60 formula (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), polymer dispersions are commercially available. A prepoly (BT), (TI) in the photopolymerizable composition. mer dispersion is understood as being a dispersion of water It is of course also possible to add other known photoini and at least one prepolymer dispersed therein. The concen tiators (c) of the alpha-amino ketones, e.g. (4-methylthioben tration of water in these systems is, for example, from 5 to Zoyl)-1-methyl-1-morpholinoethane (IRGACURER 907), 80% by weight, in particular from 30 to 60% by weight. The 65 (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane concentration of the radiation-curable prepolymer or pre (IRGACURER 369), (4-morpholino-benzoyl)-1-(4-methyl polymer mixture is, for example, from 95 to 20% by weight, benzyl)-1-dimethylaminopropane (IRGACURE(R) 379), (4- US 8,507,726 B2 53 54 (2-hydroxyethyl)aminobenzoyl)-1-benzyl-1-dimethylami or hydroxyphenyl-s-triazine type. These compounds can be nopropane), (3,4-dimethoxybenzoyl)-1-benzyl-1- used individually or in mixtures, with or without sterically dimethylaminopropane. hindered amines (HALS). Where the novel photoinitiator systems are employed in Examples of such UV absorbers and light stabilisers are hybrid systems, use is made, in addition to the novel free disclosed in WO 04/074328, page 12, line 9 to page 14, line radical hardeners, of cationic photoinitiators, of peroxide 23, said disclosure hereby is incorporated by reference. compounds, such as benzoyl peroxide (other Suitable peroX To accelerate the photopolymerization it is possible to add ides are described in U.S. Pat. No. 4,950,581 column 19, lines amines as component (d), for example triethanolamine, 17-25), of aromatic Sulfonium-, phosphonium- or iodonium N-methyldiethanolamine, ethyl-p-dimethylaminobenzoate, 10 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl-p-dimethy salts as described for example in U.S. Pat. No. 4,950,581, laminobenzoate, octyl-para-N,N-dimethyl-aminobenzoate, column 18, line 60 to column 19, line 10 or cyclopentadieny N-(2-hydroxyethyl)-N-methyl-para-toluidine or Michler's larene-iron(II) complex salts, for example (m-iso-propylben ketone. The action of the amines can be intensified by the Zene)(m-cyclopentadienyl)iron(II) hexafluorophosphate, as addition of aromatic ketones of the benzophenone type. well as Oxime Sulfonic acid esters, as are, for example 15 Examples of amines which can be used as oxygen Scavengers described in EP780729. Also pyridinium and (iso)quino are substituted N,N-dialkylanilines, as are described in linium salts as described e.g. in EP497531 and EP 441232 EP339841. Other accelerators, coinitiators and autoxidizers may be used in combination with the new photoinitiator mix are thiols, thioethers, disulfides, phosphonium salts, phos tures. phine oxides or phosphines, as described, for example, in The new photoinitiator mixtures, either alone or in mix EP438.123, in GB2180358 and in JP Kokai Hei 6-68309. tures with other known photoinitiators and sensitizers, can be It is further possible to add chain transfer agents which are used also in the form of a dispersion or emulsion in water or customary in the art to the compositions according to the aqueous solutions. In case the photoinitiator mixtures are invention as component (d). Examples are mercaptains, used in emulsions or dispersions conveniently customary dis amines and benzothiazol. persants or emulsifiers are added to prepare a stable emulsion 25 Photopolymerization can also be accelerated by adding or dispersion. Corresponding Suitable additives are known to further photosensitizers or coinitiators (as component (d)) the person skilled in the art. which shift or broaden the spectral sensitivity. These are, in The photopolymerizable compositions generally comprise particular, aromatic compounds, for example benzophenone 0.01 to 25% by weight, preferably 0.05 to 15% by weight, in and derivatives thereof, thioxanthone and derivatives thereof, particular 0.05 to 10% by weight of the photoinitiator mix 30 anthraquinone and derivatives thereof, coumarin and phe ture, based on the solid composition. The amount refers to the nothiazine and derivatives thereof, and also 3-(aroylmethyl sum of all photoinitiators added, if additionally to the photo ene)thiazolines, rhodanine, camphorquinone, but also eosine, initiator mixture comprising compounds of the formula (I) or rhodamine, erythrosine, Xanthene, thioxanthene, acridine, (I) and (HK), (MPO), (BPO), (BP), (TX), (KS), (BK), (PG), e.g. 9-phenylacridine, 1.7-bis(9-acridinyl)heptane, 1,5-bis(9- (BT), (TI) further initiators (c) are employed. Accordingly, 35 acridinyl)pentane, cyanine and merocyanine dyes. the amount either refers to the photoinitiator mixture (b) or The curing process can be assisted by adding photosensi the photoinitiators (b)+(c). tizers, in particular, in compositions which are pigmented (for In addition to the photoinitiator mixture the photopolymer example with titanium dioxide), and also by adding a com izable composition may include various additives (d). ponent which under thermal conditions forms free radicals, Subject of the invention therefore also is a photopolymer 40 for example an azo compound Such as 2.2’-azobis(4-meth izable composition as described above, additionally to the oxy-2,4-dimethylvaleronitrile), a triaZene, diazo Sulfide, pen photoinitiator (b) comprising at least one further photoinitia taZadiene or a peroxy compound, for instance a hydroperoX tor (c), and/or other additives (d). ide or peroxycarbonate, for example t-butyl hydroperoxide, Examples of these various additives (d) are thermal inhibi as described for example in EP245639. tors, which are intended to prevent premature polymerization, 45 The compositions according to the invention may comprise examples being hydroquinone, hydroquinone derivatives, as further additive (d) a photoreducable dye, e.g., Xanthene-, p-methoxyphenol, R-naphtholor Sterically hindered phenols, benzoxanthene-, benzothioxanthene, thiazine-, pyronine-, Such as 2,6-di-tert-butyl-p-cresol In order to increase the sta porphyrine- or acridine dyes, and/or trihalogenmethyl com bility on storage in the dark it is possible, for example, to use pounds which can be cleaved by irradiation. Similar compo copper compounds, such as copper naphthenate, Stearate or 50 sitions are for example described in EP445624. octoate, phosphorus compounds, for example triphenylphos Further additives known in the art may be added as com phine, tributylphosphine, triethyl phosphite, triphenyl phos ponent (d), as for example flow improvers, adhesion promot phite or tribenzyl phosphite, quaternary ammonium com ers, such as vinyltrimethoxysilane, vinyltriethoxysilane pounds, for example tetramethylammonium chloride or vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-ami trimethylbenzylammonium chloride, or hydroxylamine 55 nopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-ami derivatives, for example N-diethylhydroxylamine. To nopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, exclude atmospheric oxygen during the polymerization it is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylm either possible to perform the UV-exposure under inert atmo ethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri sphere or to add paraffin or similar wax-like Substances methoxysilane, 3-chloropropylmethyldimethoxysilane, which, being of inadequate solubility in the polymer, migrate 60 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltri to the Surface in the beginning of polymerization and form a methoxysilane and 3-mercaptopropyltrimethoxysilane. Sur transparent Surface layer which prevents the ingress of air. It factants, optical brighteners, pigments, dyes, wetting agents, is also possible to apply an oxygen-impermeable layer on top levelling assistants, dispersants, aggregation preventers, anti of the coating, for example poly(vinylalcohol-co-vinylac oxidants or fillers are further examples for additives (d). etate). Light stabilizers which can be added in a small quan 65 In order to cure thick and pigmented coatings it is appro tity are UV absorbers, for example those of the hydroxyphe priate to add glass microspheres or pulverized glass fibres, as nylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide described for example in U.S. Pat. No. 5,013,768. US 8,507,726 B2 55 56 Further Suitable components (d) are, as already mentioned 2095, 2096, 2105, 2150, PBR711, 821, 822, 823, 824, 827, above, Surfactants and dispersants and other components, in SOLSPERSER 24000, 31845,32500, 32550, 32600, 33500, particular to Support the application of pigments or colorants 34750, 36000, 36600, 37500, 39000, 41090, 44000, 53095 in the formulation. and combinations thereofas dispersant. It is preferred to apply a Surface treatment to the pigments Suitable texture improving agents are, for example, fatty in order to make the pigment easy to disperse and to stabilize acids such as Stearic acid or behenic acid, and fatty amines the resultant pigment dispersion. The Surface treatment Such as laurylamine and Stearylamine. In addition, fatty reagents are, for example, Surfactants, polymeric dispersants, alcohles or ethoxylated fatty alcohles polyols such as ali general texture improving agents, pigment derivatives and phatic 1,2-diols or epoxidized soybean oil, waxes, resin acids mixtures thereof. It is especially preferred when the colorant 10 and resin acid salts may be used for this purpose. composition according to the invention comprises at least one Suitable pigment derivatives are, for example, copper polymeric dispersant and/or at least pigment derivative. phthalocyanine derivatives such as Ciba’s Ciba R. EFKAR) Suitable Surfactants include anionic Surfactants such as 6745, Lubrizol's SOLSPERSER) 5000, 12000, BYK's SYN alkylbenzene- or alkylnahthalene-Sulfonates, alkylsulfosuc ERGIST 2100 and azo derivatives such as CibaR) EFKAR) cinates ornaphthalene formaldehyde Sulfonates; cationic Sur 15 6750, SOLSPERSER 22000 and SYNERGIST 2105. factants including, for example, quaternary salts such as ben The above mentioned dispersants and Surfactants for pig Zyl tributyl ammonium chloride; or non-ionic or amphoteric ments are for example employed in compositions of the Surfactants such as polyoxyethylene Surfactants and alkyl- or present invention which are used as resist formulations, in amidopropyl betaines, respectively. particular in color filter formulations. Illustrative examples of the surfactant include polyoxyeth Subject of the invention also is a photopolymerizable com ylenealkyl ethers such as polyoxyethylene lauryl ether, poly position as described above as further additive (d) comprising oxyethylene stearyl ether and polyoxyethylene oleyl ether; a dispersant or a mixture of dispersants as well as a photopo polyoxyethylene alkylphenyl ethers such as polyoxyethylene lymerizable composition as described above as further addi octylphenyl ether and polyoxyethylene nonylphenyl ether; tive (d) comprising a pigment or a mixture of pigments. polyethylene glycol diesters such as polyethylene glycol 25 The choice of additive(s) (d) is made depending on the field dilaurate and polyethylene glycol distearate; Sorbitan fatty of application and on properties required for this field. The acid esters; fatty acid modified polyesters; tertiary amine additives described above are customary in the art and accord modified polyurethanes; polyethyleneimines; those available ingly are added in amounts which are usual in the respective under the trade names of KP (a product of Shin-Etsu Chemi application. cal Co., Ltd), Polyflow (a product of KYOEISHACHEMI 30 Binders (e) as well can be added to the novel compositions. CAL Co., Ltd), F-Top (a product of Tochem Products Co., This is particularly expedient when the photopolymerizable Ltd), MEGAFAC (a product of Dainippon Ink & Chemicals, compounds are liquid or viscous substances. The quantity of Inc.), Fluorad (a product of Sumitomo 3M Ltd), Asahi Guard binder may, for example, be 2-98%, preferably 5-95% and and Surflon (products of Asahi Glass Co., Ltd); and the like. especially 20-90%, by weight relative to the overall solids These surfactants may be used alone or inadmixture of two 35 content. The choice of binder is made depending on the field O. O. of application and on properties required for this field, such as The Surfactant is generally used in an amount of 50 parts or the capacity for development in aqueous and organic Solvent less by weight, preferably 0 to 30 parts by weight, based on systems, adhesion to Substrates and sensitivity to oxygen. 100 parts by weight of the colorant composition. Examples of Suitable binders are polymers having a Polymeric dispersants include high molecular weight 40 molecular weight of about 2,000 to 2,000,000, preferably polymers with pigment affinic groups. Examples are: statis 3,000 to 1,000,000. tical co-polymers comprised from, for instance, styrene As the binder, which is alkaline developable, for example, derivatives, (meth)acrylates and (meth)acrylamides, and Such a homopolymer of a polymerizable compound having one or statistical co-polymers modified by post modification; block more acid groups and one or more polymerizable unsaturated co-polymers and/or comb polymers comprised from, for 45 bonds in the molecule, or a copolymer of two or more kinds instance, styrene derivatives, (meth)acrylates and (meth) thereof, and a copolymer of one or more polymerizable com acrylamides, and Such block co-polymers and/or comb poly pounds having one or more unsaturated bonds copolymeriZ mers modified by post modification; polyethylenimines, able with these compounds and containing no acid group, can which for instance is crafted with polyesters; polyamines, be used. Such compounds can be obtained by copolymerizing which for instance is crafted with polyesters; and many kinds 50 one or more kinds of a low molecular compound having one of (modified) polyurethanes. or more acid groups and one or more polymerizable unsatur Polymeric dispersants may also be employed. Suitable ated bonds in the molecule with one or more polymerizable polymeric dispersants are, for example, BYK’s DISPER compounds having one or more unsaturated bonds copoly BYKR 101,115, 130, 140,160,161,162, 163, 164, 166, 168, merizable with these compounds and containing no acid 169,170, 171, 180,182, 2000, 2001, 2009, 2020, 2025, 2050, 55 group. Examples of acids groups are, a -COOH group, a 2090, 2091, 2095, 2096, 2150, Cibas Ciba R. EFKAR 4008, —SOH group, a -SONHCO— group, a phenolic hydroxy 4009, 4010, 4015,4046, 4047, 4050, 4055,4060,4080, 4300, group, a -SO2NH- group, and a —CO—NH-CO— 4310,4330, 4340, 4400, 4401, 4402,4403, 4406,4500, 4510, group. Among those, a high molecular compound having a 4520, 4530, 4540, 4550, 4560, Ajinomoto Fine Techno’s —COOH group is particularly preferred. PB(R711, 821,822,823, 824,827, Lubrizol's SOLSPERSE(R) 60 Examples of the polymerizable compounds having one or 1320, 13940, 17000, 20000, 21000, 24000, 26000, 27000, more —COOH groups and one or more polymerizable unsat 28000, 31845, 32500, 32550, 32600, 33500, 34750, 36000, urated bonds in a molecule are (meth)acrylic acid, 2-carboxy 36600, 37500, 39000, 41090, 44000, 53095 and combina ethyl (meth)acrylic acid, 2-carboxypropyl (meth)acrylic acid, tions thereof. crotonic acid, cinnamic acid, mono2-(meth)acryloyloxy It is preferred to use Ciba R. EFKA.R. 4046, 4047, 4060, 65 ethylsuccinate, mono 2-(meth)acryloyloxyethyladipate, 4300, 4310,4330, 4340, DISPERBYKR 161,162, 163, 164, mono 2-(meth)acryloyloxyethylphthalate, mono 2-(meth) 165, 166, 168, 169, 170, 2000, 2001, 2020, 2050,2090, 2091, acryloyloxyethylhexahydrophthalate, mono 2-(meth)acry US 8,507,726 B2 57 58 loyloxyethylmaleate, mono 2-(meth)acryloyloxypropyl of the polymerizable compounds having one or more Succinate, mono 2-(meth)acryloyloxypropyladipate, mono —SONHCO— groups and one or more polymerizable 2-(meth)acryloyloxypropylphthalate, mono 2-(meth) unsaturated bonds. acryloyloxypropylhexahydrophthalate, mono 2-(meth) Examples of polymerizable compounds having one or acryloyloxypropylmaleate, mono2-(meth) 5 more phenolic hydroxy groups and one or more polymeriZ acryloyloxybutylsuccinate, mono 2-(meth) able unsaturated bonds in a molecule include hydroxyphenyl acryloyloxybutyladipate, mono 2-(meth)acryloyloxybutyl (meth)-acrylamide, dihydroxyphenyl (meth)acrylamide, phthalate, mono 2-(meth)acryloyloxybutyl hydroxyphenyl-carbonyloxyethyl (meth)acrylate, hydrox yphenyloxyethyl (meth)acrylate, hydroxyphenylthioethyl hexahydrophthalate, mono 2-(meth)acryloyloxybutyl 0 (meth)acrylate, dihydroxyphenylcarbonyloxyethyl (meth) maleate, 3-(alkylcarbamoyl)acrylic acid, C.-chloroacrylic acrylate, dihydroxyphenyloxyethyl (meth)acrylate, and dihy acid, maleic acid, monoesterified maleic acid, fumaric acid, drooxy-phenylthioethyl (meth)acrylate. itaconic acid, citraconic acid, mesaconic acid, maleic anhy Examples of the polymerizable compound having one or dride, and ()-carboxypolycaprolactone mono(meth)acrylate. more —SONH- groups and one or more polymerizable Preferable examples of copolymers are copolymers of is unsaturated bonds in the molecule include compounds repre methyl (meth)acrylate and (meth)acrylic acid, copolymers of sented by formula (a) or (b): benzyl (meth)acrylate and (meth)acrylic acid, copolymers of methyl (meth)acrylate?, ethyl (meth)acrylate and (meth) CH2=CHAoo-Yoo-Aoo-SO2 NH-A (a) acrylic acid, copolymers of benzyl (meth)acrylate, (meth) acrylic acid and styrene, copolymers of benzyl (meth)acry- 20 CH2=CHAdoo-Y2oo-Asoo-NH-SO2-Asoo (b) late, (meth)acrylic acid and 2-hydroxyethyl (meth)acrylate, wherein Yoo and Yoo each represents —COO—, copolymers of methyl (meth)acrylate?, butyl (meth)acrylate, —CONAzoo-, or a single bond. Aloo and Aaoo each represents (meth)acrylic acid and styrene, copolymers of methyl (meth) H or CH, Aco and Asoo each represents C-C-alkylene acrylate, benzyl (meth)acrylate, (metha)crylic acid and optionally having a Substituent, cycloalkylene, arylene, or hydroxyphenyl (meth)acrylate, copolymers of methyl (meth) 25 aralkylene, or C-C alkylene into which an ether group and acrylate, (meth)acrylic acid and polymethyl (meth)acrylate a thioether group are inserted, cycloalkylene, arylene, or macromonomer, copolymers of benzyl (meth)acrylate, aralkylene; Asoo and Asoo each represents H, C-C2alkyl (meth)acrylic acid and polymethyl (meth)acrylate macro optionally having a substituent, a cycloalkyl group, an aryl monomer, copolymers of tetrahydrofurfuryl (meth)acrylate, group, or an aralkyl group; and Azoo represents H. styrene and (meth)acrylic acid, copolymers of methyl (meth) 30 C-C alkyl optionally having a substituent, a cycloalkyl acrylate, (meth)acrylic acid and polystyrene macromonomer, group, an aryl group, or an aralkyl group. copolymers of benzyl (meth)acrylate, (meth)acrylic acid and The polymerizable compounds having one or more polystyrene macromonomer, copolymers of benzyl (meth) —CO. NH CO— group and one or more polymerizable acrylate, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate unsaturated bond include maleimide and N-acryloyl-acryla and polystyrene macromonomer, copolymers of benzyl 35 mide. These polymerizable compounds become the high (meth)acrylate, (meth)acrylic acid, 2-hydroxypropyl (meth) molecular compounds comprising a —CO NH-CO— acrylate and polystyrene macromonomer, copolymers of ben group, in which a ring is formed together with a primary chain Zyl (meth)acrylate, (meth)acrylic acid, 2-hydroxy-3-phenox by polymerization. Further, a methacrylic acid derivative and ypropyl (meth)acrylate and polymethyl (meth)acrylate an acrylic acid derivative each having a —CO. NH CO macromonomer, copolymers of methyl (meth)acrylate, 40 group can be used as well. Such methacrylic acid derivatives (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate and poly and the acrylic acid derivatives include, for example, a meth styrene macromonomer, copolymers of benzyl (metha)cry acrylamide derivative Such as N-acetylmethacrylamide, late, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate and N-propionylmethacrylamide, N-butanoylmethacrylamide, polymethyl (meth)acrylate macromonomer, copolymers of N-pentanoylmethacrylamide, N-decanoylmethacrylamide, N-phenylmaleimide, benzyl (meth)acrylate, (meth)acrylic 45 N-dodecanoylmethacrylamide, N-benzoylmethacrylamide, acid and styrene, copolymers of benzyl (meth)acrylate, N-(p-methylbenzoyl)methacryl-amide, N-(p-chlorobenzoyl) (meth)acrylic acid, N-phenylmaleimide, mono-2-(meth) methacrylamide, N-(naphthyl-carbonyl)-methacrylamide, acryloyloxyethylsuccinate and styrene, copolymers of allyl N-(phenylacetyl)-methacryl-amide, and 4-methacryloylami (meth)acrylate, (meth)acrylic acid, N-phenylmaleimide, nophthalimide, and an acrylamide derivative having the same mono-2-(meth)acryloyloxyethylsuccinate and styrene, 50 Substituent as these. These polymerizable compounds poly copolymers of benzyl (meth)acrylate, (meth)acrylic acid, merize to be compounds having a -CO—NH-CO—group N-phenylmaleimide, glycerol mono(meth)acrylate and Sty in a side chain. rene, copolymers of benzyl (meth)acrylate, co-carboxypoly Examples of polymerizable compounds having one or caprolactone mono(meth)acrylate, (meth)acrylic acid, more polymerizable unsaturated bond and containing no acid N-phenylmaleimide, glycerol mono(meth)acrylate and Sty- 55 group include a compound having a polymerizable unsatur rene, and copolymers of benzyl (meth)acrylate, (meth)acrylic ated bond, selected from esters of (meth)acrylic acid, Such as acid, N-cyclohexylmaleimide and styrene. methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth) The term “(meth)acrylate” in the context of the present acrylate, butyl (meth)acrylate, tetrahydrofurfuryl (meth) application is meant to refer to the acrylate as well as to the acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, corresponding methacrylate. 60 hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, Vinylbenzenesulfonic acid and 2-(meth)acrylamide-2-me hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, thylpropanesulfonic acid are examples of the polymerizable dihydroxypropyl (meth)acrylate, allyl (meth)acrylate, cyclo compounds having one or more —SOH groups and one or hexyl (meth)acrylate, phenyl (meth)acrylate, methoxyphenyl more polymerizable unsaturated bonds. (meth)acrylate, methoxyethyl (meth)acrylate, phenoxyethyl N-methylsulfonyl (meth)acrylamide, N-ethylsulfonyl 65 (meth)acrylate, methoxydiethyleneglycol (meth)acrylate, (meth)acrylamide, N-phenylsulfonyl (meth)acrylamide, and methoxytriethyleneglycol (meth)acrylate, methoxypropyl N-(p-methylphenylsulfonyl) (meth)acrylamide are examples (meth)acrylate, methoxydipropyleneglycol (meth)acrylate, US 8,507,726 B2 59 60 isobornyl meth?acrylate), dicyclopentadienyl (meth)acrylate, acrylic acid copolymers, the itaconic acid copolymers, the 2-hydroxy-3-phenoxypropyl (meth)acrylate, tricyclo crotonic acid copolymers, the maleic anhydride copolymers, 5.2.1.0 decan-8-yl (meth)acrylate, aminoethyl (meth) for example, with styrene as a co-monomer, and maleic acid acrylate, N,N-dimethylaminoethyl (meth)acrylate, amino copolymers, and partially esterified maleic acid copolymers propyl (meth)acrylate, N,N-dimethylaminopropyl (meth) each described in, for example, JP 59-44615-B4 (the term acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth) “JP-B4' as used herein refers to an examined Japanese patent acrylate, 3,4-epoxybutyl (meth)acrylate, 6.7-epoxyheptyl publication), JP 54-34327-B4, JP 58-12577-B4, and JP (meth)acrylate; vinyl aromatic compounds, such as styrene, 54-25957-B4, JP 59-53836-A, JP 59-71048-A, JP C.-methylstyrene, vinyltoluene, p-chlorostyrene, polychlo 60-159743-A, JP 60-258539-A, JP 1-152449-A, JP rostyrene, fluorostyrene, bromostyrene, ethoxymethyl Sty 10 2-1994.03-A, and JP 2-1994.04-A, and which copolymers can rene, methoxystyrene, 4-methoxy-3-methystyrene, be further reacted with an amine, as e.g. disclosed in U.S. Pat. dimethoxystyrene, vinylbenzyl methyl ether, vinylbenzyl No. 5,650.263; further, a cellulose derivative having a car glycidyl ether, indene, 1-methylindene; vinyl or allyl esters, boxyl group on a side chain can be used, and particularly Such as vinyl acetate, vinyl propionate, vinyl butylate, vinyl preferred are copolymers of benzyl (meth)acrylate and pivalate, vinyl benzoate, vinyl trimethylacetate, vinyl diethy 15 (meth)acrylic acid and copolymers of benzyl (meth)acrylate, lacetate, vinyl barate, vinyl caproate, vinyl chloroacetate, (meth)acrylic acid and other monomers, for example as vinyl dichloroacetate, vinyl methoxyacetate, vinylbutoxyac described in U.S. Pat. No. 4,139,391, JP 59-44615-B4, JP etate, vinyl phenylacetate, vinyl acetate, vinyl acetoacetate, 60-159743-A and JP 60-258539-A. vinyl lactate, vinyl phenylbutylate, vinyl cyclohexylcarboxy Examples of solvent developable binder polymers are poly late, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlo (alkyl methacrylates), poly(alkyl acrylates), poly(benzyl robenzoate, vinyl naphthoate, allyl acetate, allyl propionate, methacrylate-co-hydroxyethylmethacrylate-co-methacrylic allyl butylate, allyl pivalate, allyl benzoate, allyl caproate, acid), poly(benzylmethacrylate-co-methacrylic acid); cellu allyl Stearate, allyl acetoacetate, allyl lactate; Vinyl or allyl lose esters and cellulose ethers, such as cellulose acetate, ethers, such as vinyl methyl ether, vinyl ethyl ether, vinyl cellulose acetobutyrate, methylcellulose, ethylcellulose; hexyl ether, vinyl octyl ether, vinyl ethylhexyl ether, vinyl 25 polyvinylbutyral, polyvinylformal, cyclized rubber, poly methoxyethyl ether, vinyl ethoxyethyl ether, vinyl chloroet ethers such as polyethylene oxide, polypropylene oxide and hyl ether, vinyl hydroxyethyl ether, vinyl ethylbutyl ether, polytetrahydrofuran, polystyrene, polycarbonate, polyure vinyl hydroxyethoxyethyl ether, vinyl dimethylaminoethyl thane, chlorinated polyolefins, polyvinyl chloride, vinyl chlo ether, vinyl diethylaminoethyl ether, vinyl butylaminoethyl ride/vinylidene copolymers, copolymers of vinylidene chlo ether, vinyl benzyl ether, vinyl tetrahydrofurfuryl ether, vinyl 30 ride with acrylonitrile, methyl methacrylate and vinyl acetate, phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers chloroethyl ether, vinyl dichlorophenyl ether, vinyl naphthyl such as polycaprolactam and poly(hexamethylene adipam ether, vinyl anthryl ether, allyl glycidyl ether; amide type ide), and polyesters such as poly(ethylene glycol terephta unsaturated compounds. Such as (meth)acrylamide, N.N- late) and poly(hexamethylene glycol Succinate) and polyim dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, 35 ide binder resins. N,N-dibutyl (meth)acrylamide, N,N-diethylhexyl (meth) The polyimide binder resin in the present invention can acrylamide, N,N-dicyclohexyl (meth)acrylamide, N.N- either be a solvent soluble polyimide or a polyimide precur diphenyl (meth)acrylamide, N-methyl-N-phenyl (meth)acry Sor, for example, a poly(amic acid). lamide, N-hydroxyethyl-N-methyl (meth)acrylamide, Preferred is a photopolymerizable composition, compris N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, 40 ing a binder polymer (e), in particular a photopolymerizable N-propyl (meth)acrylamide, N-butyl (meth)acrylamide, composition, comprising as a binder polymer (e)a copolymer N-hydroxyethyl (meth)-acrylamide, N-heptyl (meth)acryla of methacrylate and methacrylic acid. mide, N-octyl (meth)acrylamide, N-ethylhexyl (meth)-acry Interesting further are polymeric binder components as lamide, N-hydroxyethyl (meth)acrylamidecyclohexyl, described e.g. in JP 10-1711 19-A, in particular for use in N-benzyl (meth)acrylamide, N-phenyl (meth)acrylamide, 45 color filters. N-tolyl (meth)acrylamide, N-hydroxyphenyl (meth)acryla The photopolymerizable compositions can be used for mide, N-naphthyl (meth)acrylamide, N-phenylsulfonyl various purposes, for example as printing ink, e.g. Screen (meth)acrylamide, N-methylphenylsulfonyl (meth)acryla printing inks, inks for offset- or flexo printing, inkjet inks, mide and N-(meth)acryloylmorpholine, diacetone acryla inks for sheet-fed printing, electrophotography inks, intaglio mide, N-methylol acrylamide, N-butoxyacrylamide; poly 50 inks, as a clear finish, as a white or colored finish, for example olefin type compounds, such as butadiene, isoprene, for wood or metal, as powder coating, as a coating material, chloroprene and the like; (meth)acrylonitrile, methyl isopro inter alia for paper, wood, metal or plastic, as a daylight penyl ketone, maleimide, N-phenylmaleimide, N-meth curable coating for the marking of buildings and roadmark ylphenylmaleimide, N-methoxyphenylmaleimide, N-cyclo ing, for photographic reproduction techniques, for holo hexyl-maleimide, N-alkylmaleimide, maleic anhydride, 55 graphic recording materials, for image recording techniques polystyrene macromonomer, polymethyl (meth)acrylate or to produce printing plates, offset printing plates or flexo macromonomer, polybutyl (meth)acrylate macromonomer; printing plates, which can be developed with organic solvents crotonates, such as butylcrotonate, hexylcrotonate, glycerine or with aqueous alkalis, for producing masks for Screen print monocrotonate; and itaconates, such as dimethyl itaconate, ing, as dental filling compositions, as adhesives, as pressure diethyl itaconate, dibutyl itaconate; and maleates or fuma 60 sensitive adhesives, as laminating resins, as etch resists, Sol rates, such as dimethyl mareate, dibutyl fumarate. der resists, electroplating resists, or permanent resists, both There can be used as well hydroxystyrene homo- or co liquid and dry films, as photostructurable dielectric, for polymers or a novolak type phenol resin, for example, poly printed circuit boards and electronic circuits, as resists to (hydroxystyrene) and poly(hydroxystyrene-co-vinylcyclo manufacture color filters for a variety of display applications hexanol), a novolak resin, a cresol novolak resin, and a 65 or to generate structures in the manufacturing process of halogenated phenol novolak resin. More specifically, it plasma-display panels and electroluminescence displays, (as includes, for example, the methacrylic acid copolymers, the for example described in U.S. Pat. No. 5,853,446, EP863534, US 8,507,726 B2 61 62 JP 09-244230-A, JP10-62980-A, JP08-171863-A, U.S. Pat. Smooth film has formed, radiation-curing of the coating with No. 5,840.465, EP855731, JP05-271576-A, JP 05-67405-A) ultraviolet and/or visible light, using for example medium for the production of holographic data storage (HDS) mate pressure mercury lamps, metal halide lamps or Xenon lamps. rial, for the production of optical Switches, optical lattices A particular advantage of the radiation-curable powder coat (interference lattice), light circuits, for producing three-di ings over their heat-curable counterparts is that the flow time mensional articles by mass curing (UV curing in transparent after melting the powder particles can be delayed in order to moulds) or by the Stereolithography technique, as is ensure the formation of a smooth, high-gloss coating. In described, for example, in U.S. Pat. No. 4.575,330, to pro contrast to heat-curable systems, radiation-curable powder duce composite materials (for example styrenic polyesters, coatings can be formulated to melt at lower temperatures which may, if desired, contain glass fibres and/or other fibres 10 without the unwanted effect of shortening their lifetime. For and other auxiliaries) and other thick-layered compositions, this reason, they are also suitable as coatings for heat-sensi for coating or sealing electronic components and integrated tive Substrates, for example wood or plastics. In addition to circuits, or as coatings for optical fibres, or for producing the novel photoinitiator Systems, the powder coating formu optical lenses, e.g. contact lenses or Fresnel lenses. The com lations may also include UV absorbers. Appropriate positions according to the invention are further Suitable for 15 examples are listed above in sections 1.-8. the production of medical equipment, auxiliaries or implants. The novel photocurable compositions are suitable, for Further, the compositions according to the invention are Suit example, as coating materials for Substrates of all kinds, for able for the preparation of gels with thermotropic properties, example wood, textiles, paper, ceramics, glass, plastics Such as for example described in DE19700064 and EP678534. as for example polyesters, polyethylene terephthalate, poly The novel photoinitiator mixtures may additionally be olefins or cellulose acetate, especially in the form of films, employed as initiators for emulsion polymerizations, pearl and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and polymerizations or Suspension polymerizations, as polymer GaAs, Sior SiO, to which it is for example intended to apply ization initiators for fixing ordered States of liquid-crystalline a protective layer or a printing ink, or by means of imagewise monomers and oligomers, or as initiators for fixing dyes on exposure, to generate an image. organic materials. 25 The novel radiation-sensitive compositions further find In coating materials, use is frequently made of mixtures of application as negative resists, having a very high sensitivity a prepolymer with polyunsaturated monomers, which may to light and being able to be developed in an aqueous alkaline additionally include a monounsaturated monomeras well. It medium without swelling. They are suitable for the produc is the prepolymer here which primarily dictates the properties tion of printing forms for relief printing, planographic print of the coating film, and by varying it the skilled worker is able 30 ing, photogravure or of screen printing forms, for the produc to influence the properties of the cured film. The polyunsatu tion of relief copies, for example for the production of texts in rated monomer functions as a crosslinking agent which ren braille, for the production of stamps, for use in chemical ders the film insoluble. The mono-unsaturated monomer milling or as a microresist in the production of integrated functions as a reactive diluent, which is used to reduce the circuits. The compositions further may be used as photopat viscosity without the need to employ a solvent. 35 ternable dielectric layer or coating, encapsulating material Unsaturated polyester resins are usually used in two-com and isolating coating in the production of computer chips, ponent systems together with a monounsaturated monomer, printed boards and other electric or electronic components. preferably with styrene. For photoresists, specific one-com The possible layer Supports, and the processing conditions of ponent systems are often used, for example polymaleimides, the coating Substrates, are just as varied. polychalcones or polyimides, as described in DE 2308830. 40 The novel composition also relates to a photosensitive The novel photoinitiator mixtures can also be used for the thermosetting resin composition and a method of forming a polymerization of radiation-curable powder coatings. The solder resist pattern by the use thereof, and more particularly powder coatings can be based on Solid resins and monomers relates to a novel photosensitive thermosetting resin compo containing reactive double bonds, for example maleates, sition useful as materials for the production of printed circuit vinyl ethers, acrylates, acrylamides and mixtures thereof. A 45 boards, the precision fabrication of metallic articles, the etch free-radically UV-curable powder coating can be formulated ing of glass and stone articles, the relief of plastic articles, and by mixing unsaturated polyester resins with solid acryla the preparation of printing plates and particularly useful as a mides (for example methyl methylacrylamidoglycolate) and solder resist for printed circuit boards and to a method of a novel free-radical photoinitiator, Such formulations being as forming a solder resist pattern by the steps of exposing a layer described, for example, in the paper “Radiation Curing of 50 of the resin composition selectively to an actinic ray through Powder Coating”. Conference Proceedings, Radtech Europe a photomask having a pattern and developing the unexposed 1993 by M. Wittig and Th. Gohmann. The powder coatings part of the layer. can also contain binders, as are described, for example, in DE The solder resist is a substance which is used during the 42285.14 and in EP 636669. soldering of a given part to a printed circuit board for the Free-radically UV-curable powder coatings can also be 55 purpose of preventing molten solder from adhering to irrel formulated by mixing unsaturated polyester resins with Solid evant portions and protecting circuits. It is, therefore, required acrylates, methacrylates or vinyl ethers and with a novel to possess Such properties as high adhesion, insulation resis photoinitiator (or photoinitiator mixture). The powder coat tance, resistance to soldering temperature, resistance to Sol ings may also comprise binders as are described, for example, vents, resistance to alkalis, resistance to acids, and resistance in DE 4228514 and in EP 636669. The UV-curable powder 60 to plating. coatings may additionally comprise white or coloured pig Because the photocurable compositions according to the ments. For example, preferably rutiletitanium dioxide can be invention have a good thermal stability and are sufficiently employed in concentrations of up to 50% by weight in order resistant to inhibition by oxygen, they are particularly Suit to give a cured powder coating of good hiding power. The able for the production of color filters or color mosaic sys procedure normally comprises electrostatic or tribostatic 65 tems, such as described, for example, in EP320264. Color spraying of the powder onto the Substrate, for example metal filters usually are employed in the manufacturing of flat panel or wood, melting of the powder by heating, and, after a displays such as LCD's, PDP (plasma panel display), EL US 8,507,726 B2 63 64 (electroluminessence) display, and projection systems, image diacetone alcohol, ethylene glycol monomethyl ether, ethyl sensors, CCD (charge coupled device), and CMOS (comple ene glycol monoethyl ether, ethylene glycol mono-n-butyl mentary metal oxide semiconductor) sensors for Scanner, ether, diethyleneglycol dimethyl ether, propyleneglycol digital camera and video camera. monomethyl ether acetate, ethyl-3-ethoxypropionate, The color filters usually are prepared by forming red, green methyl-3-methoxypropionate, n-butyl acetate, benzyl alco and blue pixels and a black matrix on a glass Substrate. In hol, acetone, methyl ethylketone, cyclopentanone, cyclohex these processes photocurable compositions according to the anone, 2-heptanone, 2-pentanone, epsilon-caprolactone, invention can be employed. A particularly preferred method gamma-butylolactone, dimethylformamide, dimethylacetoa of use comprises adding of the coloring matters, dyes and mide, hexamethylphosphoramide, ethyl lactate, methyl lac pigments of red, green and blue colors to the light-sensitive 10 resin composition of the present invention, coating of the tate, epsilon-caprolactam, and N-methyl-pyrrolidinone. The Substrate with the composition, drying of the coating with a concentration of the organic solvent which is miscible with short heat treatment, patternwise exposure of the coating to water is 0.1 to 30 weight%. actinic radiation and Subsequent development of the pattern Further, a publicly known Surface active agent can be in an aqueous alkaline developer solution and optionally a 15 added. The concentration of the Surface active agent is pref heat treatment. Thus, by Subsequently applying a red, green erably 0.001 to 10 weight%. and blue pigmented coating, in any desired order, on top of The developer solution can be used in all forms known to each other with this process a color filter layer with red, green the person skilled in the art, for example in form of a bath and blue color pixels can be produced. Solution, puddle, or a spraying solution. It is possible to put a In addition to a process in which the light-sensitive resin rinsing step after the development processing. composition is coated on a Substrate and dried, the light A final heat treatment is preferably carried out after the sensitive resin composition of the present invention can be development processing. Accordingly, a Support having a used as well for a layer transfer material. That is, the light layer which is photopolymerized by exposing (hereinafter sensitive resin composition is layer-wise provided directly on referred to as a photocured layer) is heated in an electric a temporary Support, preferably on a polyethylene terephtha 25 furnace and a drier, or the photocured layer is irradiated with late film, or on a polyethylene terephthalate film on which an an infrared lamp or heated on a hot plate. The heating tem oxygen-shielding layer and a peeling layer or the peeling perature and time depend on the composition used and the layer and the oxygen-shielding layer are provided. Usually, a thickness of the formed layer. In general, heating is preferably removable cover sheet made of a synthetic resin is laminated applied at about 120° C. to about 250° C., for about 5 to about thereon for a protection in handling. Further, there can be 30 60 minutes. applied as well a layer structure in which an alkali soluble The pigment which can be comprised in the composition thermoplastic resin layer and an intermediate layer are pro according to the present invention, including a pigmented vided on a temporary Support and further a light-sensitive color filter resist composition, is preferably a processed pig resin composition layer is provided thereon (JP5-173320-A). ment, for example a powdery or pasty product prepared by A metal Support, glass, ceramics or a synthetic resin film 35 finely dispersing a pigment into at least one resin selected can for example be used as a Support for a color filter. Glass from the group consisting of acrylic resin, vinyl chloride and a synthetic resin film, which is transparent, and have an vinyl acetate copolymer, maleic acid resin and ethyl cellulose excellent dimension stability is particularly preferred. resin. The thickness of the light-sensitive resin composition layer The red pigment for the color filter resist composition is usually 0.1 to 50 micrometers, in particular 0.5 to 5 40 comprises, for example, an anthraquinone type pigment micrometers. alone, a diketopyrolopyrole type pigment alone, a mixture of The development is carried out by washing out the areas them or a mixture consisting of at least one of them and a which were not polymerized with a suitable developing solu disazo type yellow pigment, an isoindoline type yellow pig tion. This process is repeated to form the image having plural ment or a pyrimidine type yellow pigment, in particular C. I. colors. 45 Pigment Red 177 alone, C. I. Pigment Red 254 alone, a A diluted aqueous solution of an alkaline Substance can be mixture of C. I. Pigment Red 177 and C. I. Pigment Red 254 used as a developing solution for the light-sensitive resin or a mixture consisting of at least one member of C. I. Pig composition of the present invention if the composition con ment Red 177 and C. I. Pigment Red 254, and C. I. Pigment tains alkali soluble resin or alkali soluble monomers or oli Yellow 83, C. I. Pigment Yellow 139, C. I. Pigment Yellow gomers, and further a developer Solution prepared by adding 50 150 or C. I. Pigment Yellow 215 (“CI” refers to the Color a small amount of a water-miscible organic solvent thereto is Index, known to the person skilled in the art and publicly included as well. available). Examples of suitable alkaline materials include alkali Further suitable examples for the pigment are C.I. Pigment metal hydroxides (for example, Sodium hydroxide and potas Red 9,97, 105, 122, 123, 144, 149, 168, 176, 179, 180, 185, sium hydroxide), alkali metal carbonates (for example, 55 202,207,209, 214, 220,221, 222, 242,244, 255,264,272 and Sodium carbonate and potassium carbonate), alkali metal abrominated diketopyrolopurole and C.I. PigmentYellow 12, bicarbonates (for example, sodium bicarbonate and potas 13, 14, 17, 20, 24, 31, 53, 55,93, 95, 109, 110, 128, 129, 138, sium bicarbonate), alkali metal silicates (for example, sodium 139, 150, 153, 154, 155, 166, 168, 185, 199, 213 and C.I. silicate and potassium silicate), alkali metal metasilicates (for Pigment Orange 43, 71 and 73. example, sodium metasilicate and potassium metasilicate), 60 Examples of the dyes for red color are C.I. Solvent Red 25, triethanolamine, diethanolamine, monoethanolamine, mor 27, 30, 35, 49, 83, 89, 100, 122, 138, 149, 150, 160, 179, 218, pholine, tetraalkylammonium hydroxides (for example, tet 230, C. I. Direct Red 20, 37, 39, 44, and C. I. Acid Red 6, 8, ramethylammoniumhydroxide), or trisodium phosphate. The 9, 13, 14, 18, 26, 27, 51, 52, 87, 88, 89,92, 94,97, 111, 114, concentration of the alkaline substance is 0.01 to 30 weight 115, 134, 145, 151,154, 180, 183, 184, 186, 198, C. I. Basic %, and pH is preferably 8 to 14. 65 Red 12, 13, C. I. Disperse Red 5, 7, 13, 17 and 58. The Red Suitable organic solvents which are miscible with water dyes can be used in combination with yellow and/or orange include methanol, ethanol. 2-propanol, 1-propanol, butanol, dyes. US 8,507,726 B2 65 66 The green pigment for the color filter resist composition The concentration of the pigment in the total Solid compo comprises for instance a halogenated phthalocyanine type nent (pigments of various colors and resin) is for example in pigment alone or its mixture with a disazo type yellow pig the range of 5% to 80% by weight, in particular in the range ment, an quinophthalone type yellow pigment or a metal of 20% to 65% by weight. complex, in particular C. I. Pigment Green 7 alone, C. I. The pigments in the color filter resist composition have preferably a mean particle diameter smaller than the wave Pigment Green 36 alone, C. I. Pigment Green 58 alone or a length of visible light (400 nm to 700 nm). Particularly pre mixture consisting of at least one member of C. I. Pigment ferred is a mean pigment diameter of <100 nm. Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58 and If necessary, the pigments may be stabilized in the photo C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I. 10 sensitive composition by pretreatment of the pigments with a Pigment Yellow 150 or C. I. Pigment Yellow 215. Other dispersant to improve the dispersion stability of the pigment suitable greenpigments are C.I.Pigment Green 15, 25 and 37. in the liquid formulation. Suitable additives are described Examples for suitable green dyes are C.I. Acid Green 3, 9, 16, above. C. I. Basic Green 1 and 4. 15 Preferably, the color filter resist composition according to Examples for suitable blue pigments for the color filter the present invention contains additionally at least one addi resist composition are phthalocyanine type pigments, used tion polymerizable monomeric compound as component (a). The ethylenically unsaturated compounds (a) in the color either alone or in combination with an dioxazine type violet filter resist composition include one or more olefinic double pigment, for instance, C. I. Pigment Blue 15:6 alone, a com bonds. They may be of low (monomeric) or high (oligomeric) bination of C. I. Pigment Blue 15:6 and C. I. Pigment Violet molecular mass. Examples of compounds containing a 23. Further examples for blue pigments are such of C. I. double bond are (meth)acrylic acid, (meth)acrylates, (meth) Pigment Blue 15:3, 15:4, 16, 22, 28 and 60 and sub-phthalo acrylonitrile, (meth)acrylamide, N-substituted (meth)acryla cyanine type pigments. Other Suitable pigments are C. I. mides, vinyl esters, vinyl ethers, styrenes and the like. Pigment Violet 14, 19,23,29, 32,37, 177 and C. I. Orange 73. 25 Examples of polyunsaturated compounds of relatively Examples for suitable blue dyes are C. I. Solvent Blue 25, high molecular mass (oligomers) are polyesters, polyure 49, 68,78,94, C.I. Direct Blue 25, 86,90, 108, C.I.Acid Blue thanes, polyethers and polyamides, which contain ethyleni 1, 7, 9, 15, 103,104,158, 161, C.I. Basic Blue 1, 3, 9, 25, and cally unsaturated carboxylates. C. I. Disperse Blue 198. Particularly suitable examples are esters of an ethyleni 30 cally unsaturated carboxylic acid with a polyol or polyep The pigment of the photopolymeric composition for black oxide described above. matrix preferably comprises at least one member selected Examples of esters based on polyols are trimethylolpro from the group consisting of carbon black, titanium black and pane tri(meth)acrylate, trimethylol-propane tri(acryloylox iron oxide. However, a mixture of other pigments which, in ypropyl)ether, trimethylolethane tri(meth)acrylate, ethylene total, give the black appearance, can also be used. For 35 glycol di-(meth)acrylate, diethylene glycol di(meth)acrylate, example, also C. I. Pigment Black 1, 7 and 31 can be used triethylene glycol di(meth)acrylate, tetra-ethylene glycol alone or in combination. di (meth)acrylate, tetramethylene glycol di(meth)acrylate, Other examples of the dyes used for color filter are C. I. neopentyl glycol di(meth)acrylate, pentaerythritol di(meth) Solvent Yellow 2, 5, 14, 15, 16, 19, 21, 33,56, 62,77, 83, 93, 40 acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate 162, 104, 105,114, 129, 130, 162, C. I. Disperse Yellow 3, 4, monooxalate, dipentaerythritol di(meth)acrylate, dipen 7, 31, 54, 61, 201, C. I. Direct Yellow 1, 11, 12, 28, C. I. Acid taerythritol tri(meth)acrylate, dipentaerythritol tetra(meth) Yellow 1, 3, 11, 17, 23, 38, 40, 42, 76, 98, C. I. Basic Yellow acrylate, dipentaerythritol penta(meth)acrylate, dipen 1, C. I. Solvent Violet 13,33, 45,46, C. I. Disperse Violet 22, 45 taerythritol hexa(meth)acrylate, dipentaerythritol penta 24, 26, 28, C. I. Acid Violet 49, C. I. Basic Violet 2, 7, 10, C. (meth)acrylate mono(2-hydroxyethyl)ether, I. Solvent Orange 1, 2, 5, 6, 37, 45, 62.99. C. I. Acid Orange tripentaerythritol octa(meth)acrylate, 1,3-butanediol 1, 7, 8, 10, 20, 24, 28,33, 56, 74, C. I. Direct Orange 1, C. I. di (meth)acrylate, 1,4-butanediol diitaconate, hexanediol Disperse Orange 5, C. I. Direct Brown 6,58,95, 101,173, C. di (meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, Sor I. Acid Brown 14, C. I. Solvent Black 3, 5, 7, 27, 28, 29, 35, 50 bitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol 45 and 46. penta(meth)acrylate, Sorbitol hexacmeth)acrylate, oligoester In Some special cases of manufacturing color filters, (meth)acrylates, glycerol di(meth)acrylate and tri(meth)acry complementary colors, yellow, magenta, cyan and optionally late, di(meth)acrylates of polyethylene glycol with a molecu green, are used instead of red, green and blue. As yellow for 55 lar weight of from 200 to 1500, pentaerythritol diitaconate, this type of color filters, the abovementioned yellow pigments dipentaerythritol trisitaconate, dipentaerythritol pentaitacon and dyes can be employed. Examples of the colorants Suitable ate, dipentaerythritol hexaitaconate, ethylene glycolditacon for magenta color are C. I. Pigment Red 122, 144, 146, 169, ate, propylene glycol ditaconate, 1,3-butanediol ditaconate, 177, C. I. Pigment Violet 19 and 23. Examples of cyan color 1,4-butanediol diitaconate, tetramethylene glycol ditacon are aluminum phthalocyanine pigments, titanium phthalo 60 ate, Sorbitol tetraitaconate, ethylene glycol dicrotonate, tet cyanine pigments, cobalt phthalocyanine pigments, and tin ramethylene glycol dicrotonate, pentaerythritol dicrotonate, phthalocyanine pigments. ethylene glycol dimaleate, tiethylene glycol dimaleate, pen For any color, combinations of more than two pigments can taerythritol dimaleate, sorbitol tetramaleate, or mixtures also be used. Especially suitable in color filter applications 65 thereof. are powdery processed pigments prepared by finely dispers Other examples are pentaerythritol and dipentaerythritol ing the above mentioned pigments into a resin. derivatives shown in the following formula (XII) and (XIII): US 8,507,726 B2 67 68
(XII) Roo-(Mo)0-O-(CH2 CH-O-(Mo)0-Roo Roo-(Mo)0-O-CH-C-CH-O-CH-C-CH2-(Mo)o-Roo Roo-(Mo)0-O-CH2 CH-O-(Mo)0-Roo (XIII) CH-O-(Mo)0-Roo Roo-(Mo)0-O-CH-C-CH-O-(Mo)0-Roo, CH-O-(Mo)0-Roo wherein 15 basic acid anhydride with a product of the reaction of phenol Mo is —(CH2CH2O)— or —CH2CH(CH)O , or cresol novolac epoxy resin and an unsaturated monocar Roo is —COCH=CH or —COC(CH)—CH, boxylic acid. p0 is 0 to 6 (total of p0: 3-24), and q0 is 0 to 6 (total of q0: Other examples are the products from the polycondensa 2-16). tion reaction and/or addition reaction of the compound of Typical examples of component (a) based on polyepoxides formula (XIV) with one or more abovementioned polybasic are 2.2-bis(4-(2-hydroxy-3-acryloxy)propoxyphenylpro- acid anhydrides.
(XIV) R300 R300 ic---o-c-f-c-o-tes-on-pi ==X-- ==X-to-vs-o-c-b-c-d---ch pi R200 R200 R400 R400 pane, 2,2-bis(4-(2-hydroxy-3-acryloxy) wherein Yo is propoxyethoxyphenylpropane, 9.9-bis(4-(2-hydroxy-3- acryloxy)propoxyphenylfluorene, 9.9-bis(4-(2-hydroxy- 35 3-acryl-Oxy)propoxyethoxyphenylfluorine, and reaction O acrylicproducts acid. of epoxy resins based on novolacs with (meth) C H3Cy/ CH3, Hy/ H Polyethers obtained from the reaction of the polyols or 1N, 1N polyepoxides with the unsaturated compounds with a 0 hydroxy group Such as 2-hydroxyethyl (meth)acrylate, vinyl CF3 CF, H3C CH3, O , 3 O alcohol can also be used as component (a). / s | O Also suitable as components (a) are the amides of identical 1N 1 n 1 N. 1 N. or different, unsaturated carboxylic acids with aromatic, V / cycloaliphatic- and aliphatic- polyamines having preferably 2 45 1NV/ to 6, especially 2 to 4, amino groups. s Other examples are unsaturated urethanes derived from a polyisocyanate and an unsaturated compound having a Roo is hydrogen or methyl, hydroxy group or from a polyisocyanate, a polyol and an so Roo and Rao independently of each other are hydrogen, unsaturated compound having a hydroxy group. methyl, Cl, or Br. Mo is substituted or unsubstituted alky Other examples are polyesters, polyamides, or polyure- lene having 1 to 10 carbon atoms, X is 0 to 5, and y is 1 to thanes having ethylenically unsaturated groups in the chain. 10. Examples of Such compounds as component (a) are Other suitable polymers with acrylate or methacrylate described in JP2002-206014A, JP2004-69754A, JP2004 groups in the side chains are, for example, solvent soluble or 55 30224.5A, JP2005-77451 A, JP2005-316449A, JP2005 alkaline soluble polyimide precursors, for example poly 338328A and JP3754O65B2. (amic acid ester) compounds, having the photopolymerizable Polymers or oligomers as abovementioned have for side groups either attached to the back-bone or to the ester example a molecular weight of about 1,000 to 1,000,000, groups in the molecule, i.e. according to EP 624826. Such preferably 2,000 to 200,000 and an acid value of about 10 to oligomers or polymers can be formulated optionally with 60 200 mg KOH/g, preferably 20 to 180 mg KOH/g. reactive diluents, like polyfunctional (meth)acrylates in order A preferred photopolymerizable composition comprises as to prepare highly sensitive polyimide precursor resists. component (a) a compound having at least two ethylenically Further examples of the componenta) are also the above- unsaturated bonds and at least one carboxylic acid group in mentioned polymers or oligomers having at least one car- the molecule, in particular a reaction product obtained by boxyl function and at least two ethylenically unsaturated 65 adding an epoxy group containing unsaturated compound to groups within the molecular structure, such as a resin a part of the carboxyl groups of a carboxylic acid group obtained by the reaction of a saturated or unsaturated poly- containing polymer or a reaction product of the compound US 8,507,726 B2 69 70 shown below with one or more polybasic acid anhydrides. urated bonds in a molecule and the polymerizable compounds Further preferred components (a) comprise a compound having one or more polymerizable unsaturated bond and con obtained from the reaction of a compound of the formula taining no acid group described above can be used for the (XIV) with one or more polybasic acid anhydrides. organic polymer binder. Further examples are the above-mentioned reaction prod The weight-average molecular weight of the binders is ucts obtained by adding an epoxy group containing unsatur preferably 500 to 1,000,000, e.g. 3,000 to 1,000,000, more ated compound to a part of the carboxyl groups of a carboxy preferably 5,000 to 400,000. lic acid group containing polymer. These compounds may be used singly or as a mixture of Concrete examples of the compounds are, for example a two or more kinds. The content of the binder in the light reaction product of a copolymer of styrene, C.-methylstyrene 10 sensitive resin composition is preferably 10 to 95 weight %, and acrylic acid or a copolymer of methyl methacrylate and more preferably 15 to 90 weight% based on the whole solid acrylic acid with 3,4-epoxycyclohexylmethyl (meth)acrylate. matterS. Unsaturated compounds having a hydroxy group Such as Examples for color filter resists, the composition of such 2-hydroxyethyl (meth)acrylate and glycerol mono(meth) resists and the processing conditions are given by T. Kudo et acrylate can be used instead of the above mentioned epoxy 15 al., Jpn. J. Appl. Phys. Vol. 37 (1998) 3594; T. Kudo et al., J. group containing unsaturated compounds as the reactant for Photopolym. Sci. Technol. Vol 9 (1996) 109; K. Kobayashi, carboxylic acid group containing polymers. Solid State Technol. November 1992, p. S15-S18; U.S. Pat. Other examples are half esters of anhydride containing Nos. 5,368,976; 5,800,952; 5,882,843; 5,879,855; 5,866,298; polymers, for example reaction products of a copolymer of 5,863,678; JP 06-230212A; EP320264; JP 09-269410A; JP maleic anhydride and one or more other polymerizable com 10-221843A, JP 01-090516A: JP 10-171119A, U.S. Pat. pounds with (meth)acrylates having an alcoholic hydroxy Nos. 5,821,016, 5,847,015, 5,882,843, 5,719,008, group Such as 2-hydroxyethyl (meth)acrylate or having an EP881541, or EP902327. epoxy group for example such as the compounds described in The photoinitiator mixtures of the present invention can be the formula (V-1)-(V-15). used in color filter resists, for example, Such as those given as Reaction products of polymers having alcoholic hydroxy 25 examples above, or can partially or fully replace the known groups such as copolymers of 2-hydroxyethyl (meth)acry photoinitiators in Such resists. It is understood by a person late, (meth)acrylic acid, benzy methacylate and styrene, with skilled in the art that the use of the new photoinitiator mix (meth)acrylic acid or (meth)acrylchloride can also be used as tures of the present invention is not limited to the specific component (a). binder resins, crosslinkers and formulations of the color filter Other examples are reaction products of a polyester with 30 resist examples given hereinbefore but can be used in con terminal unsaturated groups, which is obtained from the reac junction with any radically polymerizable component in tion of a dibasic acid anhydride and a compound having at combination with a dye or color pigment or latent pigment to least two epoxy groups followed by further reaction with an form a photosensitive color filter ink or color filter resist. unsaturated compound, with a polybasic acid anhydride. The photosensitive compositions of the present invention, Further examples are resins obtained by the reaction of a 35 as already stated above, are also suitable for the preparation of saturated or unsaturated polybasic acid anhydride with a reac the black matrix of color filters. Said black matrix composi tion product obtained by adding epoxy group containing tion for example comprises (meth)acrylic compound to all of the carboxyl groups of a a photoinitiator mixture of the present invention, carboxylic acid containing polymeras mentioned above. an organic binder, in particular an organic binder, which is The photopolymerizable compounds can be used alone or 40 an epoxy acrylate resin having carboxyl groups, in any desired mixtures. a black coloring material, In a color filter resist composition the whole amount of the a polymer dispersant, in particular a polymer dispersant monomers contained in the photo-polymerizable composi containing basic functional groups, tion is preferably 5 to 80% by weight, in particular 10 to 70% a photopolymerizable monomer. by weight based on the whole solid contents of the composi 45 The person skilled in the art is familiar with such formu tion, i.e. the amount of all components without the solvent(s). lations. Examples of suitable black matrix compositions and As the binder used in the color filter resist composition, the components (other than the photoinitiator) as described which is soluble in an alkaline aqueous solution and insoluble above are given in JP Patent No. 375.4065, the disclosure of in water, for example, a homopolymer of a polymerizable which hereby is incorporated by reference. compound having one or more acid groups and one or more 50 It is obvious to those skilled in the art, that the photosen polymerizable unsaturated bonds in the molecule, or a sitive compositions of the present invention can be used for copolymer of two or more kinds thereof, and a copolymer of generating red, green and blue color pixels and a black matrix, one or more polymerizable compounds having one or more for the manufacture of a color filter, regardless of the above unsaturated bonds copolymerizable with these compounds described differences in processing, regardless, of additional and containing no acid group, can be used. As described 55 layers which can be applied and regardless of differences in above, Such compounds can be obtained by copolymerizing the design of the color filter. The use of a composition accord one or more kinds of a low molecular compound having one ing to the present invention to form colored elements shall not or more acid groups and one or more polymerizable unsatur be regarded as limited by different designs and manufacturing ated bonds in the molecule with one or more polymerizable processes of Such color filters. compounds having one or more unsaturated bonds copoly 60 The photoinitiator mixtures and the corresponding photo merizable with these compounds and containing no acid curable compositions of the present invention are in particular group as described above. A high molecular compound hav suited for the preparation of red, green and blue color filters. ing a -COOH group as acid group is particularly preferred. They may also be employed in the black matrix of a color Preferable examples of copolymers are copolymers of filter. (meth)acrylate and (meth)acrylic acid as described above. 65 The photo-sensitive composition of the present invention Examples of the polymerizable compounds having one or can suitably be used for forming a color filter but will not be more —COOH groups and one or more polymerizable unsat limited to this application. It is useful as well for example for US 8,507,726 B2 71 72 a recording material, a resist material, a protective layer, a above, having a maximum absorption at a UV wavelength in dielectric layer, an optical film Such as overcoat film, anti the range of 340-450 nm, wherein the refractive index con reflective film, anti-glare film, hard coat, prism sheet, retar trast adjusted sensitivity is greater than 3x10'An/(mJ/cm). dation film, alignment film and sealant in display applications Photocuring further is of great importance for printing and display elements, a paint, and a printing ink. 5 The photosensitive compositions according to the inven applications, since the drying time of the ink is a critical factor tion are also suitable for manufacturing interlayer insulating for the production rate of graphic products, and should be in layers or dielectric layers in a liquid crystal display, and more the order of fractions of seconds. UV-curable inks are par particularly in a reflection type liquid crystal display includ ticularly important for Screen printing, offset inks, ink-jet ing an active matrix type display having a thin film transistor 10 inks, flexographic printing inks, intaglio inks, electrophoto (TFT) as a Switching device, and a passive matrix type with graphic inks, sheetfed inks, overprint varnishes or primers. out a Switching device. Subject of the invention therefore also is a photopolymer The photosensitive compositions according to the inven izable composition as described above, which is a printing tion can further be used for manufacturing spacers, which ink, in particular an offset printing ink. control a cell gap of the liquid crystal part in liquid crystal 15 display panels. As already mentioned above, the novel photoinitiator mix The photocurable compositions according to the invention tures are highly suitable also for producing printing plates e.g. are suitable for producing spacers for liquid crystal displays flexo printing plates or offset printing plates. This application (as described above) because of their high sensitivity. uses, for example, mixtures of Soluble linear polyamides or The photosensitive compositions according to the inven styrenefbutadiene and/or styrenefisoprene rubber, polyacry tion are also Suitable for manufacturing microlens arrays used lates or polymethyl methacrylates containing carboxyl in liquid crystal display panels, image sensors and the like. groups, polyvinyl alcohols or urethane acrylates with photo Because the photocurable compositions according to the polymerizable monomers, for example acrylamides and/or invention have low yellowing properties, both thermally and methacrylamides, or acrylates and/or methacrylates, and a photochemically, they are suitable for the production of 25 photoinitiator. Films and plates of these systems (wet or dry) microlens arrays as described above. are exposed over the negative (or positive) of the printed The novel radiation-sensitive compositions are also Suit original, and the uncured parts are subsequently washed out able for photo-lithographic steps used in the production pro using an appropriate solvent or aqueous solutions. cess of plasma display panels (PDP), particularly for the imaging forming process of barrier rib, phosphor layer and 30 Printing inks are known to the person skilled in the art, are electrodes. used widely in the art and are described in the literature. The compositions according to the invention also find They are, for example, pigmented printing inks and print application for the production of one- or more-layered mate ing inks coloured with dyes. rials for the image recording or image reproduction (copies, A printing ink is, for example, a liquid or paste-form dis reprography), which may be mono- or polychromatic. Fur 35 persion that comprises colorants (pigments or dyes), binders thermore the materials are Suitable for color proofing sys tems. In this technology formulations containing microcap and also optionally solvents and/or optionally water and addi Sules can be applied and for the image production the tives. In a liquid printing ink, the binder and, if applicable, the radiation curing can be followed by a thermal treatment. Such additives are generally dissolved in a solvent. Customary systems and technologies and their applications are for 40 viscosities in the Brookfield viscometer are, for example, example disclosed in U.S. Pat. No. 5,376,459. from 20 to 5000 mPa's, for example from 20 to 1000 mPa's, The photoinitiator mixtures are also Suitable as photoini for liquid printing inks. For paste-form printing inks, the tiators in the holographic data storage application. Said pho values range, for example, from 1 to 100 Pas, preferably from toinitiators generate radicals and initiate polymerization of 5 to 50 Pas. The person skilled in the art will be familiar with monomer upon irradiation with blue laser radiation, Suitable 45 the ingredients and compositions of printing inks. Suitable for holographic data storage. The wavelength range of the pigments, like the printing ink formulations customary in the blue laser is 390-420 nm, preferably 400-410 nm and particu art, are generally known and widely described. larly 405 nm. Holographic storage systems (holographic Printing inks comprise pigments advantageously in a con recording media) are for example used to record and to centration of, for example, from 0.01 to 40% by weight, retrieve a large amount of data with fast access time. The 50 preferably from 1 to 25% by weight, especially from 5 to 10% photoinitiator mixtures of the invention are for example in particular suitable for systems as described for example in by weight, based on the total weight of the printing ink. WOO3FO21358. The printing inks can be used, for example, for intaglio It was found that the photoinitiator mixtures of the present printing, gravure printing, flexographic printing, screen print invention combine high reactivity with low absorbance at 405 55 ing, offset printing, lithography or continuous or dropwise nm and are suitable for this application. Dyes and sensitizers ink-jet printing on material pretreated in accordance with the can also be added to the formulations. Suitable dyes and process of the invention using generally known formulations, sensitizers for blue laser radiation are for example couma for example inpublishing, packaging or shipping, in logistics, rines, Xanthones, thioxanthones and benzophenones. in advertising, in security printing or in the field of office It was found that the photoinitiator mixtures allow photo 60 equipment. polymerization of monomers in thick layers, such as required for holographic data storage, with high sensitivity and yield Suitable printing inks are both solvent-based printing inks recording layers which are sensitive to blue laser radiation. and water-based printing inks. Of interest are, for example, The photoinitiator mixtures are in particular suitable for the printing inks based on aqueous acrylate. Such inks are to be preparation of optical articles (for example optical 65 understood as including polymers or copolymers that are waveguides) or holographic recording media e.g. comprising obtained by polymerisation of at least one monomer contain a polymer and an organic photoinitiator mixture as described ing a group US 8,507,726 B2 74 the solventless acrylate polymers can be mixed with so-called reactive diluents, for example vinyl-group-containing mono mers. Further Suitable binder components are epoxy-group containing compounds. O- - - - or HC The printing ink compositions may also comprise as addi tional component, for example, an agent having a water retaining action (humectant), e.g. polyhydric alcohols, poly and that are dissolved in water or a water-containing organic alkylene glycols, which renders the compositions especially solvent. Suitable organic solvents are water-miscible solvents Suitable for ink-jet printing. 10 It will be understood that the printing inks may comprise customarily used by the person skilled in the art, for example further auxiliaries, such as are customary especially for alcohols, such as methanol, ethanol and isomers of propanol, (aqueous) ink-jet inks and in the printing and coating indus butanol and pentanol, ethylene glycol and ethers thereof. Such tries, for example preservatives (such as glutardialdehyde as ethylene glycol methyl ether and ethylene glycol ethyl and/or tetramethylolacetyleneurea, anti-oxidants, degassers/ ether, and ketones, such as acetone, ethyl methyl ketone or 15 defoamers, viscosity regulators, flow improvers, anti-settling cyclo, for example isopropanol. Water and alcohols are pre agents, gloss improvers, lubricants, adhesion promoters, anti ferred. skin agents, matting agents, emulsifiers, stabilisers, hydro Suitable printing inks comprise, for example, as binder phobic agents, light stabilisers, handle improvers and anti primarily an acrylate polymer or copolymer and the solventis statics. When such agents are present in the compositions, selected, for example, from the group consisting of water, their total amount is generally s1% by weight, based on the C-Calcohols, ethylene glycol, 2-(C-Calkoxy)-ethanol, weight of the preparation. acetone, ethyl methyl ketone and any mixtures thereof. Printing inks suitable in process step d2) include, for In addition to the binder, the printing inks may also com example, those comprising a dye (with a total content of dyes prise customary additives known to the person skilled in the of e.g. from 1 to 35% by weight, based on the total weight of art in customary concentrations. 25 the ink). For intaglio or flexographic printing, a printing ink is usu Dyes Suitable for colouring such printing inks are known to ally prepared by dilution of a printing ink concentrate and can the person skilled in the art and are widely available commer then be used in accordance with methods known perse. cially, e.g. from Ciba Spezialitätenchemie AG, Basel. The printing inks may, for example, also comprise alkyd Such printing inks may comprise organic solvents, e.g. systems that dry oxidatively. 30 water-miscible organic solvents, for example C-Calcohols, The printing inks are dried in a known manner customary amides, ketones or ketone alcohols, ethers, nitrogen-contain in the art, optionally with heating of the coating. ing heterocyclic compounds, polyalkylene glycols, A Suitable aqueous printing ink composition comprises, C-Calkylene glycols and thioglycols, further polyols, e.g. for example, a pigment or a combination of pigments, a glycerol and C-C alkyl ethers of polyhydric alcohols, usu dispersant and a binder. 35 ally in an amount of from 2 to 30% by weight, based on the Dispersants that come into consideration include, for total weight of the printing ink. example, customary dispersants, such as water-soluble dis The printing inks may also, for example, comprise solubi persants based on one or more arylsulfonic acid/formalde lisers, e.g. 6-caprolactam. hyde condensation products or on one or more water-soluble The printing inks may, interalia for the purpose of adjust oxalkylated phenols, non-ionic dispersants or polymeric 40 ing the Viscosity, comprise thickeners of natural or synthetic acids. origin. Examples of thickeners include commercially avail The arylsulfonic acid/formaldehyde condensation prod able alginate thickeners, starch ethers or locust bean flour ucts are obtainable, for example, by Sulfonation of aromatic ethers. The printing inks comprise Such thickeners e.g. in an compounds. Such as naphthalene itself or naphthalene-con amount of from 0.01 to 2% by weight, based on the total taining mixtures, and Subsequent condensation of the result 45 weight of the printing ink. ing arylsulfonic acids with formaldehyde. Such dispersants It is also possible for the printing inks to comprise buffer are known and are described, for example, in U.S. Pat. No. Substances, for example borax, borate, phosphate, polyphos 5,186.846 und DE-A-197 27767. Suitable oxalkylated phe phate or citrate, in amounts of e.g. from 0.1 to 3% by weight, nols are likewise known and are described, for example, in in order to establish a pH value of e.g. from 4 to 9, especially U.S. Pat. No. 4,218,218 und DE-A-197 27 767. Suitable 50 from 5 to 8.5. non-ionic dispersants are, for example, alkylene oxide As further additives, such printing inks may comprise Sur adducts, polymerisation products of vinylpyrrolidone, vinyl factants or humectants. Surfactants that come into consider acetate or vinyl alcohol and co- or ter-polymers of vinyl ation include commercially available anionic and non-ionic pyrrolidone with vinyl acetate and/or vinyl alcohol. It is also Surfactants. Humectants that come into consideration possible, for example, to use polymeric acids which act both 55 include, for example, urea or a mixture of Sodium lactate as dispersants and as binders. (advantageously in the form of a 50 to 60% aqueous solution) Examples of suitable binder components that may be men and glycerol and/or propylene glycol in amounts of e.g. from tioned include (meth-)acrylate-group-containing, vinyl 0.1 to 30% by weight, especially from 2 to 30% by weight, in group-containing and/or, depending on the intended applica the printing inks. tion, epoxy-group-containing monomers, prepolymers and 60 Furthermore, the printing inks may also comprise custom polymers and mixtures thereof. Further examples are ary additives, for example foam-reducing agents or especially melamine acrylates and silicone acrylates. The acrylate com substances that inhibit the growth of fungi and/or bacteria. pounds may also be non-ionically modified (e.g. provided Such additives are usually used in amounts of from 0.01 to 1% with amino groups) or ionically modified (e.g. provided with by weight, based on the total weight of the printing ink. acid groups or ammonium groups) and used in the form of 65 The printing inks may also be prepared in customary man aqueous dispersions or emulsions (e.g. EP-A-704469, EP-A- ner by mixing the individual components together, for 12339). Furthermore, in order to obtain the desired viscosity example in the desired amount of water. US 8,507,726 B2 75 76 As already mentioned, depending upon the nature of the late, pentaerythritol propoxylate tetraacrylate, neopentylgly use, it may be necessary for e.g. the Viscosity or other physical col ethoxylate diacrylate, neopentylglycol propoxylate dia properties of the printing ink, especially those properties crylate. which influence the affinity of the printing ink for the sub Nonlimiting examples of higher molecular weight (oligo strate in question, to be adapted accordingly. meric) polyunsaturated compounds (also known as prepoly The printing inks are also Suitable, for example, for use in mers) are esters of ethylenically unsaturated mono- or poly recording systems of the kind in which a printing ink is functional carboxylic acids and polyols or polyepoxides, and expressed from a small opening in the form of droplets which polymers having ethylenically unsaturated groups in the are directed towards a Substrate on which an image is formed. chain or in side groups, e.g. unsaturated polyesters, polya 10 mides and polyurethanes and copolymers thereof, alkyd res Suitable substrates are, for example, textile fibre materials, ins; polybutadiene and butadiene copolymers, polyisoprene paper, plastics or aluminium foils pretreated by the process and isoprene copolymers, polymers and copolymers having according to the invention. Suitable recording systems are (meth)acrylic groups in side chains such as methacrylated e.g. commercially available ink-jet printers. urethanes and also mixtures of one or more Such polymers. Preference is given to printing processes in which aqueous 15 Examples of Suitable mono- or poly-functional unsatur printing inks are used. ated carboxylic acids are acrylic acid, methacrylic acid, cro Suitable monomers in particular for ink-jet printing inks, tonic acid, itaconic acid, cinnamic acid, maleic acid, fumaric include those compounds which have at least one carbon acid, itaconic acid, and unsaturated fatty acids Such as lino carbon unsaturated bond. Non limiting examples of Such lenic acid and oleic acid. Acrylic and methacrylic acid are OOCS a preferred. (meth)acrylic acid and salts thereof (meth)acrylic acid esters It is also possible, however, to use saturated di- or poly Such as alkylesters e.g. methyl, ethyl, 2-chloroethyl, N-dim carboxylic acids in admixture with unsaturated carboxylic ethylaminoethyl. n-butyl, isobutyl-, pentyl, hexyl, cyclo acids. Examples of Suitable Saturated di- or poly-carboxylic hexyl, 2-ethylhexyl, octyl, isobornyl 2-exobornylesters: acids include, for example, tetrachlorophthalic acid, tetrabro phenyl, benzyl-, and o-, m- and p-hydroxyphenyl esters; 25 mophthalic acid, phthalic anhydride, adipic acid, tetrahydro hydroxyalkylesters e.g. 2-hydroxyethyl, 2-hydroxypropyl. phthalic acid, isophthalic acid, terepthalic acid, trimellitic 4-hydroxybutyl, 3,4-dihydroxybutyl or glycerol 1,2,3-pro acid, heptane-dicarboxylic acid, sebacic acid, dodecanedicar panetriolesters; epoxyalkylesters e.g. glycidyl, 2,3-epoxy boxylic acid, hexahydrophthalic acid, etc. butyl, 3,4-epoxy butyl, 2,3-epoxycyclohexyl, 10, 11-ep Suitable polyols are aromatic and, especially, aliphatic and oxyundecyl esters; (meth)acrylamides, N-substituted (meth) 30 cycloaliphatic polyols. Examples of aromatic polyols are acrylamides, C.2. N-methylolacrylamide, hydroquinone, 4,4'-dihydroxydiphenyl, 2.2-di(4-hydrox N-methylolmethacrylamide, N-ethylacrylamide, N-ethyl yphenyl)propane, and novolaks and resols. Examples of poly methacrylamide, N-hexylacrylamide, N-hexylmethacryla epoxides are those based on the said polyols, especially the mide, N-cyclohexylacrylamide, N-cyclohexylmethacryla aromatic polyols and epichlorohydrin. Also Suitable as poly mide-, N-hydroxy-ethylacrylamide, N-phenylacrylamide, 35 ols are polymers and copolymers that contain hydroxyl N-phenylmethacrylamide, N-benzylacrylamide, N-benzyl groups in the polymer chain or in side groups, e.g. polyvinyl metacrylamide, N-nitrophenylacrylamide, N-nitrophenyl alcohol and copolymers thereof or polymethacrylic acid methacrylamide, N-ethyl-N-phenylacrylamide, N-ethyl-N- hydroxyalkyl esters or copolymers thereof. Further suitable phenylmethacrylamide, N-(4-hydroxyphenyl)acrylamide, polyols are oligoesters having hydroxyl terminal groups. and N-(4-hydroxyphenyl)methacrylamide, IBMAA 40 Examples of aliphatic and cycloaliphatic polyols include (N-isobutoxymethyl acrylamide), (meth)acryl-nitriles: alkylenediols having preferably from 2 to 12 carbon atoms, unsaturated acid anhydrides such as itaconic anhydride, Such as ethylene glycol, 1.2- or 1,3-propanediol. 1.2-, 1.3- or maleic anhydride, 2,3-dimethyl maleic anhydride, and 1,4-butanediol, pentanediol, hexanediol, octanediol, dode 2-chloromaleic anhydride, unsaturated acid esters such as canediol, diethylene glycol, triethylene glycol, polyethylene maleic acid esters, phthalic acid esters, itaconic acid esters, 45 glycols having molecular weights of preferably from 200 to methylene Succinic acid esters; 1500, 1,3-cyclopentanediol, 1.2-, 1.3- or 1,4-cyclohex styrenes. Such as methyl styrene, chloromethyl styrene, and anediol. 1,4-dihydroxymethylcyclohexane, glycerol, tris(B- o-, m-, and p-hydroxystyrene, divinylbenzene: vinyl chloride hydroxyethyl)amine, trimethylolethane, trimethylolpropane, and vinylidene chloride; vinyl ethers such as isobutyl vinyl pentaerythritol, dipentaerythritol and sorbitol. ether, ethyl vinylether, 2-chloroethyl vinylether, hydroxy 50 The polyols may be partially or fully esterified by one or by ethyl vinylether, propyl vinylether, butyl vinylether, isobutyl different unsaturated carboxylic acid(s), it being possible for vinyl ether, octyl vinylether and phenyl vinylether, vinyl and the free hydroxyl groups in partial esters to be modified, for allyl esters such as vinyl acetate, vinyl acrylate, vinyl chlo example etherified, or esterified by other carboxylic acids. roacetate, vinyl butyrate and vinyl benzoate, divinyl Succi Preferred in ink-jet ink formulations are: (meth)acrylated nate, diallyl phthalate, triallyl phosphate; isocyanurates Such 55 epoxy esters; (meth)acrylated poly-esters or vinyl-ether as triallyl isocyanurate and tris(2-acryloylethyl)isocyanurate; group-containing polyesters, (meth)acrylated polyurethanes, N-vinylheterocyclic compounds, N-vinylpyrrolidone or suit polyethers and polyols. ably substituted vinylpyrrolidones, N-vinylcarbazol, N-vi A preferred component used in UV-curable inkjet are acry nylcaprolactam or Suitably Substituted vinylcaprolactames, lates which have been modified by reaction with primary or 4-vinyl-pyridine. 60 secondary amines, as described, for example, in U.S. Pat. No. Typical examples for esters are the ones as given herein 3,844,916, EP280222, U.S. Pat. Nos. 5,482,649 or 5,734,002. before. Such amine-modified acrylates are also termed aminoacry The following esters of alkoxylated polyols are also suit lates. It is known that in the presence of aminoacrylates UV able: glycerol ethoxylate triacrylate, glycerol propoxylate curable systems show an increased curing performance. They triacrylate, trimethylolpropane ethoxylate triacrylate, trim 65 are useful to overcome the oxygen inhibition typically ethylolpropane propoxylate triacrylate, pentaerythritol observed for radical induced polymerization reactions, espe ethoxylate tetraacrylate, pentaerythritol propoxylate triacry cially for low viscous systems like UV-curable inkjet. Ami US 8,507,726 B2 77 78 noacrylates are obtainable, for example, under the name small (0.005 to 15 um) to permit free flow of the ink at the EBECRYL 80, EBECRYL 81, EBECRYL 83, EBECRYL ejecting nozzles. The pigment particles should preferably be P115, EBECRYL 7100 from UCB Chemicals, under the 0.005 to 1 um. name Laromer PO 83F. Laromer PO 84F, Laromer PO 94F Very fine dispersions of pigments and their preparation are from BASF, under the name PHOTOMER 4775 F, PHO disclosed in e.g. U.S. Pat. No. 5,538,548. TOMER 4967 F from Cognis or under the name CN501, The inks preferably comprise a total content of colorant of CN503, CN550 from Cray Valley or under the tradename 1 to 35% by weight, in particular 1 to 30% by weight, and Genomer 5275 from Rahn AG. preferably 1 to 20% by weight, based on the total weight of These aminoacrylates are in particular Suitable as compo ink. A limit of 2.5% by weight, in particular 5% by weight, 10 and preferably 7.5% by weight, is preferred here as the lower nent (a) for compositions comprising a photoinitiator mixture limit. consisting of at least one compound of the formula I and at Suitable colorants are for example pure pigment powders least one benzophenone compound (BK) or at least one thiox such as Cyan IRGALITER Blue GLO (Ciba Inc.) or pigment anthone compound (TX) as defined above. preparations such as MICROLITH-pigment preparations. It will be clear that mixtures of all these cited monomers, 15 Inkjet inks may include a variety of further additives such prepolymers, polymers and oligomers can be used in the ink as for example Surfactants, biocides, buffering agents, anti compositions comprising the novel photoinitiator mixture mold agents, pH adjustment agents, electric conductivity according to the present invention. adjustment agents, chelating agents, anti-rusting agents, The amount of the photopolymerizable monomer, oligo polymerisation inhibitors, light stabilizers, and the like. Such mer or prepolymer in this connection is for example 10 to 80 additives may be included in the inkjet inks in any effective wt %, preferably 10 to 60 wt %. amount, as desired. The inks comprising the photoinitiator mixtures of the Compositions according to the present invention may fur present invention may besides to radically polymerizable ther contain organic solvents, for example, ketones, ethers components also comprise cationic-curable compositions and esters, such as methyl ethyl ketone, isobutyl methyl having a low viscosity which comprise at least one aliphatic 25 ketone, cyclopentanone, cyclohexanone, N-methylpyrroli or aromatic epoxide, at least one polyol or polyvinyl polyols done, dioxane, tetrahydrofuran, 2-methoxy-ethanol, as mentioned above, and at least one cation-generating pho 2-ethoxyethanol. 1-methoxy-2-propanol. 1,2-dimethoxy toinitiator. A number of these epoxides are well known in the ethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypro art and are commercially available. pionate or 1-Isopropyl-2,2-dimethyltrimethylendiisobu Photoinitiators that can be used in the cationic photocur 30 tyrate available as TXIB from Eastman. able compositions are, for example, aryl iodonium salts and The reactive diluent in the ultraviolet ray curable ink and aryl sulfonium salts. the ultraviolet ray curable ink composition is a monomer Emphasized are such hybrid systems that contain cationi which has at least one double bond reactive group at the cally and radically polymerisable and photopolymerisable molecule terminal. Examples thereof are monofunctional raw materials. Examples of cationically polymerisable sys 35 caprolactone acrylate, tridecyl acrylate, isodecyl acrylate, tems include cyclic ethers, especially epoxides and oxetanes, isooctyl acrylate, isomiristyl acrylate, isostearyl acrylate, and also vinyl ethers and hydroxy-containing compounds. 2-ethylhexyl-diglycol acrylate, 2-hydroxybutyl acrylate, Lactone compounds and cyclic thioethers as well as vinyl 2-acryloyloxyethylhexahydrophthalic acid, neopentylglycol thioethers can also be used. Further examples include amino acrylic acid benzoic acid ester, isoamylacylate, lauryl acry plastics or phenolic resole resins. These are especially 40 late, Stearyl acrylate, butoxyethyl acylate, ethoxy-diethylene melamine, urea, epoxy, phenolic, acrylic, polyester and alkyd glycol acrylate, methoxy-triethylene glycol acrylate, meth resins, but especially mixtures of acrylic, polyester or alkyd oxy-polyethylene glycol acrylate, methoxydipropylenegly resins with a melamine resin. Radiation curable resins contain col acrylate, phenoxyethyl acrylate, phenoxy-polyethylene ethylenically unsaturated compounds, especially (meth)acry glycol acrylate, nonylphenol ethylene oxide adduct acrylate, late resins. 45 tetrahydrofurfuryl acrylate, isobonyl acrylate, 2-hydroxy Furthermore interesting are hybrid systems that are photo ethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phe polymerized in a first stage and then crosslinked through noxypropyl acrylate, 2-acryloyloxyethyl Succinic acid, thermal post-treatment in a second stage. Such hybrid sys 2-acryloyloxyethyl-phthalic acid and 2-acryloyloxyethyl-2- tems comprise an unsaturated compound in mixtures with hydroxyethylphthalic acid; difunctional hydroxypivalic acid non-photopolymerizable film-forming components. These 50 neopenthylglycol diacrylate, polytetramethylene glycol dia may, for example, be physically drying polymers or solutions crylate, trimethylol propane acrylic acid benzoic acid ester, thereof in organic solvents, for example nitrocellulose or diethylene glycol diacrylate, triethylene glycol diacrylate, cellulose acetobutyrate. However, they may also be chemi tripropylene glycol diacrylate, tetraethylene glycol diacry cally or thermally curable resins, for example polyisocyan late, polyethylene glycol (200) diacrylate, polyethylene gly ates, polyepoxides or melamine resins. 55 col (400) diacrylate, polyethylene glycol (600) diacrylate, Other compositions Suitable as for example ink-jet inks are polyethylene glycol (1000) diacrylate, polypropylene (400) dual cure compositions, which are cured first by heat and diacrylate, polypropylene (700) diacrylate, neopentylglycol subsequently by UV or electron irradiation, or vice versa, and diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacry whose components contain ethylenic double bonds as late, 1.6-hexanediol diacrylate, 1.9-nonanediol diacrylate, described above capable to react on irradiation with UV light 60 dimethylol-tricyclodecane diacrylate, bisphenol A ethylene in presence of a photoinitiator, in the context of the invention oxide adduct diacrylate and bisphenol A propyleneoxide the novel photoinitiator mixture as described above. adduct diacrylate; trifunctional trimethylolpropane triacry Inkjet inks for example contain a colorant. A wide variety late, ethylene oxide modified trimethyl propane triacrylate, of organic and inorganic dyes and pigments, alone or in ethylene oxide modified trimethylolpropane triacrylate, pen combination may be selected for use in inkjet ink composi 65 taerythritol triacrylate, tris(2-hydroxyethyl)isocyanurate tri tions; the person skilled in the art is familiar with the appro arylate and propoxylated glyceril triacrylate; tetrafunctional priate coice. The pigment particles should be sufficiently pentaditrimethylol propane tetraacrylate, ethoxylated pen US 8,507,726 B2 79 80 taerythritol tetraacrylate, pentaerythritol tetraacrylate; pen pipes, containers, etc. Further examples of moulding, impreg tafunctional dipentaerythritol hydroxypentaacrylate; and nating and coating compositions are UP resin gel coats for hexa-functional dipentaerythritol hexaacrylate; and modifi mouldings containing glass fibres (GRP). Such as corrugated cations thereof. These can be used alone or in a combination. sheets and paper laminates. Paper laminates may be based on The amount of the reactive diluent is, for example, 40-80 urea resins or melamine resins. Prior to production of the wt %, 10 to 90 wt %, preferably 20 to 80 wt %. laminate, the gel coat is produced on a Support (for example Anotherfield where photocuring is employed is the coating a film). The novel photocurable compositions can also be of metals, in the case, for example, of the coating of metal used for casting resins or for embedding articles, for example plates and tubes, cans or bottle caps, and the photocuring of electronic components, etc. polymer coatings, for example of floor or wall coverings 10 The compositions and compounds according to the inven based on PVC. tion can be used for the production of holographies, Examples of the photocuring of paper coatings are the waveguides, optical Switches wherein advantage is taken of colourless varnishing of labels, record sleeves and book cov the development of a difference in the index of refraction CS. between irradiated and unirradiated areas. The photoinitiators of the present invention are also suit 15 The use of photocurable compositions for imaging tech able for use in UV-curable adhesives; e.g. in the preparation niques and for the optical production of information carriers of pressure-sensitive adhesives, laminating adhesives, hot is also important. In Such applications, as already described melt adhesives, moisture-cure adhesives, silane reactive above, the layer (wet or dry) applied to the support is irradi adhesives or silane reactive sealants and the like, and related ated imagewise, e.g. through a photomask, with UV or visible applications. Said adhesives can be hot melt adhesives as well light, and the unexposed areas of the layer are removed by waterborne or solvent borne adhesives, liquid solventless treatment with a developer. Application of the photocurable adhesives or 2-part reactive adhesives. In particular suitable layer to metal can also be carried out by electrodeposition. are pressure-sensitive adhesives (PSA), for example uv-cur The exposed areas are polymeric through crosslinking and able hot melt pressure sensitive adhesives. Said adhesives for are therefore insoluble and remain on the Support. Appropri example comprise at least one rubber component, at least one 25 ate colouration produces visible images. Where the Support is resin component as tackyfier and at least one oil component, a metallized layer, the metal can, following exposure and for example in the weight ratio 30:50:20. Suitable tackyfiers development, be etched away at the unexposed areas or rein are natural or synthetic resins. The person skilled in the art is forced by electroplating. In this way it is possible to produce aware of Suitable corresponding compounds as well as of electronic circuits and photoresists. When used in image suitable oil components or rubbers. 30 forming materials the novel photoinitiators provide excellent The pre-polymerized adhesives containing the isocyan performance in generating so called printout images, ates, for example in blocked form, can for example be pro whereby a color change is induced due to irradiation. To form cessed at high temperature and coated onto the Substrate Such print-out images different dyes and/or their leuco form following the hotmelt process, afterwards full cure is are used and examples for Such print out image systems can achieved by an additional curing step involving the blocked 35 be fount e.g. in WO96/41240, EP706091, EP511403, U.S. isocyanates, which is realized by photoactivation of the pho Pat. Nos. 3,579,339 and 4,622,286. tolatent catalyst. The novel photoinitiator mixture is also suitable for a pho The compounds according to the invention may also be topatternable composition for forming a dielectric layer of a used as initiators for emulsion, bead or Suspension polymeri multilayer layer circuit board produced by a sequential build sation processes or as initiators of polymerisation for the 40 up process. fixing of orientation states of liquid-crystalline monomers The invention, as described above, provides compositions and oligomers, or as initiators for the fixing of dyes on organic for producing pigmented and non-pigmented paints and var materials. nishes, powder coatings, printing inks, printing plates, adhe Also of interest is the use of the novel photoinitiators for sives, pressure-sensitive adhesives, dental compositions, gel curing shaped articles made from composite compositions. 45 coats, photoresists for electronics, electroplating resist, etch The composite compound consists of a self-supporting resist, both liquid and dry films, Solder resist, as resists to matrix material, for example a glass fibre fabric, or alterna manufacture color filters for a variety of display applications, tively, for example, plant fibres cf. K.-P. Mieck, T. Reuss to generate structures in the manufacturing processes of mann in Kunststoffe 85 (1995), 366-370), which is impreg plasma-display panels (e.g. barrier rib, phosphor layer, elec nated with the photocuring formulation. Shaped parts 50 trode), electroluminescence displays and LCD (e.g. inter comprising composite compounds, when produced using the layer insulating layer, spacers, microlens array), for holo novel compounds, attain a high level of mechanical stability graphic data storage (HDS), as composition for encapsulating and resistance. The novel compounds can also be employed electrical and electronic components, for producing magnetic as photocuring agents in moulding, impregnating and coating recording materials, micromechanical parts, waveguides, compositions as are described, for example, in EP7086. 55 optical Switches, plating masks, etch masks, colour proofing Examples of such compositions are gel coat resins, which are systems, glass fibre cable coatings, screen printing stencils, Subject to stringent requirements regarding curing activity for producing three-dimensional objects by means of stere and yellowing resistance, and fibre-reinforced mouldings, for olithography, and as image recording material, for holo example, light diffusing panels which are planar or have graphic recordings, microelectronic circuits, decolorizing lengthwise or crosswise corrugation. Techniques for produc 60 materials, decolorizing materials for image recording mate ing Such mouldings, such as hand lay-up, spray lay-up, cen rials, for image recording materials using microcapsules, as a trifugal casting or filament winding, are described, for photoresist material used for forming dielectric layers in a example, by P. H. Selden in “Glasfaserverstärkte Kunstst sequential build-up layer of a printed circuit board. offe', page 610, Springer Verlag Berlin-Heidelberg-New Substrates used for photographic information recordings York 1967. Examples of articles which can be produced by 65 include, for example, films of polyester, cellulose acetate or these techniques are boats, fibre board or chipboard panels polymer-coated papers; Substrates for offset printing formes with a double-sided coating of glass fibre-reinforced plastic, are specially treated aluminium, Substrates for producing US 8,507,726 B2 81 82 printed circuits are copper-clad laminates, and Substrates for exposure at 248 nm and ArF excimer lasers for exposure at producing integrated circuits are, for example, silicon wafers. 193 nm are also suitable. Lasers in the visible region can also The layer thickness of the photosensitive layer for photo be employed. graphic materials and offset printing forms is generally from The term “imagewise' exposure includes both, exposure about 0.5um to 10um, while for printed circuits it is from 0.1 5 through a photomask comprising a predetermined pattern, for um to about 100 um. Following the coating of the substrates, example a slide, a chromium mask, a stencil mask or a reticle, the solvent is removed, generally by drying, to leave a coat of as well as exposure by means of a laser or light beam, which the photoresist on the substrate. for example is moved under computer control over the Surface Coating of the Substrates can be carried out by applying to 10 of the coated Substrate and in this way produces an image. the Substrate a liquid composition, a solution or a Suspension. Suitable UV laser exposure systems for the purpose are, for The choice of solvents and the concentration depend princi example, provided by Etec and Orbotech (DP-100TM pally on the type of composition and on the coating technique. DIRECT IMAGING SYSTEM). Other examples of laser light sources are, for example excimer lasers, such as F2 The solvent should be inert, i.e. it should not undergo a 15 excimer lasers at 157 nm exposure, KrF excimer lasers for chemical reaction with the components and should be able to exposure at 248 nm and ArF excimer lasers for exposure at be removed again, after coating, in the course of drying. 193 nm. Further suitable are solid state UV lasers (e.g. Examples of suitable solvents are ketones, ethers and esters, Gemini from ManiaBarco, DI-2050 from PENTAX) and vio Such as methyl ethyl ketone, isobutyl methyl ketone, cyclo let laser diodes with 405 nm output (DI-2080, DI-PDP from pentanone, cyclohexanone, N-methylpyrrolidone, dioxane, PENTAX). Lasers in the visible region can also be employed. tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, And the computer-controlled irradiation can also be achieved 1-methoxy-2-propanol. 1,2-dimethoxyethane, ethyl acetate, by electron beams. It is also possible to use masks made of n-butyl acetate, ethyl 3-ethoxypropionate, 2-methoxypropy liquid crystals that can be addressed pixel by pixel to generate lacetate, methyl-3-methoxypropionate, 2-heptanone, 2-pen 25 digital images, as is, for example, described by A. Bertsch, J. tanone, and ethyl lactate. Y. Jezequel, J. C. Andre in Journal of Photochemistry and The solution is applied uniformly to a substrate by means Photobiology A: Chemistry 1997, 107, p. 275-281 and by of known coating techniques, for example by printing, spin K.-P. Nicolay in Offset Printing 1997, 6, p. 34-37. coating, dip coating, knife coating, curtain coating, brushing, 30 Following the imagewise exposure of the material and spraying, especially by electrostatic spraying, and reverse prior to development, it may be advantageous to carry out roll coating, and also by means of electrophoretic deposition. thermal treatment for a short time. After the development a It is also possible to apply the photosensitive layer to a tem thermal post bake can be performed to harden the composi porary, flexible support and then to coat the final substrate, for tion and to remove all traces of solvents. The temperatures example a copper-clad circuit board, or a glass Substrate by 35 employed are generally 50-250° C., preferably 80-220° C.: transferring the layer via lamination. the duration of the thermal treatment is in general between 0.25 and 60 minutes. The quantity applied (coat thickness) and the nature of the The photocurable composition may additionally be used in substrate (layer support) are dependent on the desired field of a process for producing printing plates or photoresists as is application. The range of coat thicknesses generally com 40 described, for example, in DE4013358. In such a process the prises values from about 0.1 um to more than 100 um, for composition is exposed for a short time to visible light with a example 0.1 um to 1 cm, preferably 0.5um to 1000 um. wavelength of at least 400 nm, without a mask, prior to, Following the coating of the substrates, the solvent is simultaneously with or following imagewise irradiation. removed, generally by drying, to leave an essentially dry 45 After the exposure and, if implemented, thermal treatment, resist film of the photoresist on the substrate. the unexposed areas of the photosensitive coating are The photosensitivity of the novel compositions can extend removed with a developer in a manner known perse. in general from about 150 nm to 600 nm, for example 190-600 As already mentioned, the novel compositions can be nm, (UV-vis region). Suitable radiation is present, for developed by aqueous alkalis or organic solvents. Particularly example, in Sunlight or light from artificial light sources. 50 Suitable aqueous-alkaline developer solutions are aqueous Consequently, a large number of very different types of light Solutions of tetraalkylammonium hydroxides or of alkali Sources are employed. Both point Sources and arrays ("lamp metal silicates, phosphates, hydroxides and carbonates. carpets') are Suitable. Examples are carbon arc lamps, Xenon Minor quantities of wetting agents and/or organic solvents arc lamps, low-, medium-, high- and Super high-pressure 55 may also be added, if desired, to these solutions. Examples of mercury lamps, possibly with metal halide dopes (metal typical organic solvents, which may be added to the developer halogen lamps), microwave-stimulated metal vapour lamps, liquids in Small quantities, are cyclohexanone, 2-ethoxyetha excimer lamps, Superactinic fluorescent tubes, fluorescent nol, toluene, acetone and mixtures of Such solvents. Depend lamps, argon incandescent lamps, electronic flashlights, pho ing on the Substrate also solvents, e.g. organic solvents, can be tographic flood lamps, light emitting diodes (LED), electron 60 used as developer, or, as mentioned above mixtures of aque beams and X-rays. The distance between the lamp and the ous alkalis with such solvents. Particularly useful solvents for Substrate to be exposed in accordance with the invention may Solvent development include methanol, ethanol. 2-propanol, vary depending on the intended application and the type and 1-propanol, butanol, diacetone alcohol, ethylene glycol output of lamp, and may be, for example, from 1 cm to 150 65 monomethyl ether, ethylene glycol monoethyl ether, ethylene cm. Laser light sources, for example excimer lasers, such as glycol mono-n-butyl ether, diethyleneglycol dimethyl ether, F excimer lasers at 157 nm exposure, KrF excimer lasers for propyleneglycol monomethyl ether acetate, ethyl-3-ethox US 8,507,726 B2 83 84 ypropionate, methyl-3-methoxypropionate, n-butyl acetate, atoms are referred to in the following examples without any benzyl alcohol, acetone, methyl ethyl ketone, cyclopen mention of specific isomers, the n-isomers are meant in each tanone, cyclohexanone, 2-heptanone, 2-pentanone, epsilon CaSC. caprolactone, gamma-butylolactone, dimethylformamide, dimethylacetamide, hexamethyl-phosphoramide, ethyl lac EXAMPLE 1. tate, methyl lactate, epsilon-caprolactam, and N-methyl-pyr Synthesis of rolidinone. Optionally, water can be added to these solvents up to a level at which still a clear solution is obtained and at which sufficient solubility of the unexposed areas of the light 10 sensitive composition is maintained. O The invention therefore also provides a process for the -o-c-ch photopolymerization of compounds containing ethylenically C C-CH unsaturated double bonds, i.e. monomeric, oligomeric or 15 polymeric compounds containing at least one ethylenically N unsaturated double bond, which comprises adding to these compounds at least one photoinitiator mixture as described CH above and irradiating the resulting composition with electro magnetic radiation, in particular light of the wavelength 150 to 600 nm, in particular 190-600 nm, with electron beam, or with X-rays. tic-c= In other words, adding to these compounds compounds HC-C-O containing ethylenically unsaturated double bonds at least 25 one photoinitiator mixture as described above and irradiating O the resulting composition with electromagnetic radiation, in particular light of the wavelength 150 to 600 nm, in particular compound of formula I; R=R CH, R, phenyl substi 190-600 nm, with electron beam, or with X-rays. 30 tuted by CH The invention further provides a coated substrate which is coated on at least one surface with a composition as described 1.a. 1-(4-(4-Acetyl-phenyl)-4-(3-methyl-benzoyl)- above, and describes a process for the photographic produc phenyl-amino-phenyl)-ethanone tion of relief images, in which a coated Substrate is subjected to imagewise exposure and then the unexposed portions are 35 To triphenylamine (5.00 g) in CHCl2(80 mL) are added removed with a developer. Imagewise exposure may be AlCl(2.89 g) and m-toluoyl chloride (3.15g) at 0°C. After effected by irradiating through a mask or by means of a laser stirring overnight at room temperature, AlCls (5.98 g) and or electron beam as already described above. Of particular acetyl chloride (3.36 g) are further added at 0°C. After the advantage in this context is the laser beam exposure already mixture is stirred at room temperature overnight, the reaction 40 mixture is poured into ice-water, and the crude product is mentioned above. extracted twice with CHC1. The combined organic layer is A further subject of the invention is a cured coating washed with H2O and brine, dried over MgSO, and concen obtained by applying a composition according to claim 4 to a trated to give the product. The structure of the product, which Substrate and irradiating said coated Substrate with electro is obtained as a yellow solid, is confirmed by the "H-NMR magnetic radiation in the range from 150 to 600 nm, or with 45 spectrum (CDC1). 8 ppm): 2.44 (s.3H), 2.59 (s. 6H), 7.16 electron beam or with X-rays. 7.25 (m, 6H), 7.34-7.42 (m, 2H), 7.58 (d. 1H), 7.63 (s, 1H), The examples which follow illustrate the invention in more 7.79 (d. 2H), 7.92 (d, 4H). detail. Parts and percentages are, as in the remainder of the description and in the claims, by weight, unless stated other 1.b. 1-4-(4-1-(Acetoxyimino)-ethyl-phenyl-4- wise. Where alkyl radicals having more than three carbon 50 (3-methyl-benzoyl)-phenyl-amino)-phenyl-etha atoms are referred to in the following examples without any none oxime O-acetate mention of specific isomers, the n-isomers are meant in each The ketone 1.a is transformed to the corresponding oxime CaSC. acetate 1.b, which is isolated as a yellow solid, according to The photoinitiator mixtures of the invention have a good 55 the procedure described in WO02-100903. The structure is thermal stability, low volatility, good storage stability and confirmed by the 'H-NMR spectrum (CDCl3). Ó ppm): 2.27 high solubility, and are also Suitable for photopolymerisa (s, 6H), 2.38 (s, 6H), 2.43 (s.3H), 7.11 (d. 2H), 7.16 (d. 4H), tions in the presence of air (oxygen). Further, they cause only 7.34-7.40 (m, 2H), 7.56 (d. 2H), 7.61 (s, 1H), 7.70 (d, 4H), low yellowing in the compositions after photopolymeriza 7.75 (d. 2H). tion, as well as an excellent resolution in resist applications, in 60 particular color filters and high curing speeds in particular in EXAMPLES 2-12 printing ink applications. The examples which follow illustrate the invention in more The compounds of examples 2-12 are prepared according detail. Parts and percentages are, as in the remainder of the 65 to the method as given in example 1 employing the appropri description and in the claims, by weight, unless stated other ate educts. The compounds and their physical data are listed wise. Where alkyl radicals having more than three carbon in table 1 below.
US 8,507,726 B2 95 96 0.7 wt.-% silicone additive (DC57, provided by Dow Corn a fabric is stretched is placed on the printed sample and ing) rotated once around its own axis under a pressure of 220 16.0 wt.-%pigment (IRGALITE(RBlue GLO, provided by g/cm in the course of 10 seconds. If visible damage to Ciba Inc.) the sample is caused by this procedure, the printing ink The formulations to be tested are applied using a Prufbau 5 has not been sufficiently through cured; machine onto a corona treated polymeric white foil. The or by rubbing the surface with a Tela tissue. In this test, the samples are exposed to a medium pressure mercury lamp or a transfer of the ink from the exposed surface to the tissue gallium-doted lamp with a power ranging from 80 to 200 characterizes a poor curing of the ink surface. W/cm under air or nitrogen at different belt speeds. Reactivity is measured by the cure speed defined as the Polymerization efficiency is assessed using: 10 maximum belt speed required to get a proper cure at a con either a REL complete curing tester immediately after the stant light intensity. irradiation. In this test, an aluminum cylinder over which The following compounds are used in the examples:
BP-1 O O CH3 | -o-c-ch C C C-CH ( ) ( )
N
He-c= HC-C-O | O
oxime HK-1 ()---on". CH3 BP-2
C
O O with x = 2-20 HK-2 BPO-1 fits H. CH3 HOHCHC C CHCH-OH O O H CH3 CH3 H3C C-HP
CH3 2
HK-3 MPO-1 ()--O CH
CH US 8,507,726 B2
-continued KS-1 ()--()--()----(it, )—cit CH3 EDB O CH
CHO21su l \ V CH3 mixture-1: 5 parts BPO-1 mixture-2: liquid blend of 17 parts MPO-1 2,4,6-trimethylbenzoylphenylphosphine oxide 78 parts HK-1 alpha hydroxyketone 2,4,6-trimethylbenzophenone 4-methylbenzophenone (= ESACURE(R) KTO46)
Example A1 Example A4 2O Mixtures with Compounds of the Formula (HK) Mixture with Compound of the Formula (BPO) TABLE A1 Cure speed measured by REL of HK-2 and blend HK-2 oxime in TABLE A4 the presence of HK-1 in a blue flexo ink; Gallium lamp, cold mirrors, 25 150 Wen under nitrogen, white PEC foil corona treated Cure speed measured by REL of BPO-1 and blend BPO-1 foxime in a blue flexo ink; Hg lamp, cold mirrors, 80 W/cm under air, white 4% HK-1 + Photoinitiator Cure speed (m/min) PEC foil 4% HK-2 140 Photoinitiator Curing speed (m/min) 4% blend HK-2/oxime (ratio 92:8) 160 30 490 BPO-1 90 4% Blend BPO-1 foxime (ratio 92:8) 120 Example A2 Example A5 Mixture with Compounds of the Formula (HK) and 35 p (BP) Mixture with Compound of the Formula (HK) and (MPO) TABLE A2 40 Cure speed measured by REL of HK-3/BP-1 and a blend TABLE A5 HK-3/BP-1/oxime in a blue flexo ink; Hg lamp, cold mirrors, 200 W/cm under nitrogen 700 ppm O2, white PEC foil corona treated Cure speed measured by REL of MPO-1 and blend MPO-1 foxime in a blue flexo ink; Ga lamp, cold mirrors, 150 W/cm Cure speed under nitrogen, white PEC foil corona treated Photoinitiator (m/min) 45 4% HK-1 + Photoinitiator Cure speed (m/min) 5% HK-3/BP-1 (ratio 1:1) 8O 5% blend HK-3/BP-1 (ratio 1:1)/oxime (ratio 92:8) 150 4% MPO-1 40 4% Blend MPO-1/oxime (ratio 92:8) 60 Example A3 50 Example A6 Mixture with Compounds of the Formula (BP) Mixture with Compound of the Formula (HK) and 55 TABLE A3 (BPO) Cure speed measured by REL and rubbing of BP-2 and blend BP-2.foxime with 2% EDB in a blue flexo ink; Hg lamp, cold mirrors, 200 W/cm TABLE A6 under air, white PEC foil 60 Cure speed measured by REL of BPO-1 and blend BPO-1 foxime Cure speed Cure speed with HK-1 in a blue flexo ink; Ga lamp, cold mirrors, 200 W/cm under (m/min) (m/min) inert atmosphere Photoinitiator REL Tissue Rub 4% HK-1 + Photoinitiator Cure speed (m/min) 10% BP-2 and 2% EDB 50 30 10% of a blend BP-2/oxime (92/8) 1OO-110 50 490 BPO-1 8O and 2% EDB 65 4% Blend BPO-1 foxime (ratio 92.5:7.5) 120 US 8,507,726 B2 99 100 Example A7 TABLE A9-continued LED characteristics: Loctite (R) CureJetTM 405 LED, Typical Output: Mixture with Compound of the Formula (KS) 1.1 Watt/cm2, Substrate placed at 23 mm distance from the lamp. Spectral Output Range is 390-420 nm with primary peak at 405 nm 5 TABLE A7 Photoinitiator UV Fixture time (s) 1.0% mixture-2 4.5 Cure speed measured by REL of KS-1 and blend KS-1 foxime with 1.0% mixture-2 3.0 and without EDB in a blue flexo ink; Hg lamp, cold mirrors, 200 W/cm 0.1% oxime under air, white PEC 10 Curing speed As all examples clearly demonstrate, the addition of a Photoinitiator (m/min) REL Small amount of the oxime ester compound of formula I 4% KS-1 50 enhances the performance of the photoinitiators of the for 4% Blend KS-1 foxime (ratio 92:8) 70 mulae (HK), (MPO), (BPO), (BP) and (KS) considerably. 4% KS-1 - 2%. EDB 110 15 The invention claimed is: 4% of a blend KS-1/oxime (ratio 92:8) + 2% EDB 140-150 1. Photoinitiator mixture comprising (i) at least one compound selected from the group consist ing of alpha-hydroxy ketones, monoacylphosphine Example A8 oxides, bisacylphosphine oxides, ketosulfones, benzil ketals, benzoin ether, phenylglyoxylates, borates and Mixture with Compound of the Formula (BPO), titanocenes; and Curing Via LED (ii) at least one compound of the formula (I) and (I)
25 (I) TABLE A8 R7 Cure speed measured by rubbing of BPO-1 and BPO-1 foxime (92:8) in a blue flexo ink; LED characteristics: Loctite (R) CureJetTM 405 LED, o=t^ Ro Typical Output: 1.1 Watt/cm, substrate placed at 23 mm distance Xy. from the lamp. Spectral Output Range is 390-420 nm with primary 30 Rs peak at 405 nm, white PVC foil. R 21 i. Photoinitiator Curing time (s) O C 3% BPO-1 35 3% Blend BPO-1 foxime, ratio 92.8 30 2% Blend BPO-1 foxime, ratio 92.8 35 35 J---(\ /) \{ W CE - R R (I) Example A9 R; 40 OC R9 Curing of an Adhesive Formulation Rs x^4 A UV curable acrylic adhesive formulation is prepared R 2 i. comprising = 9 C=O, 50% aliphatic urethane acrylate (Ebecryl 270 from Cytec), 45 25% isobornyl acrylate (IBOA), O J---- \ A \ /)---- 25% trimethylolpropane triacrylate (TMPTA), and R R" photoinitiator as indicated in the table A9 One drop of adhesive is applied to a glass slide, then cov 50 wherein ered at an angle of approx 45° with a second glass slide and R and R' independently of one another are hydrogen, subsequently irradiated with the UV LED source at a constant C-C scycloalkyl or C-C alkyl which is unsubstituted distance of 150 mm. Determined is the fixture time. The or Substituted by one or more halogen, phenyl and/or fixture time is defined as the time of UV exposure needed to CN; or prevent two bonded glass slides from relative movement 55 R and R' are C-Calkenyl; or under light shear pressure. R and R', are phenyl which is unsubstituted or substituted by one or more C-Calkyl, halogen, CN, OR, SR TABLE A9 and/or NRSR; or RandR' are C-Calkoxy, benzyloxy; or phenoxy which LED characteristics: Loctite (R) CureJetTM 405 LED, Typical Output: 60 1.1 Watt/cm2, Substrate placed at 23 mm distance from the lamp. is unsubstituted or substituted by one or more Spectral Output Range is 390-420 nm with primary peak at 405 nm C-Calkyl and/or halogen; R and R' independently of one another are hydrogen; Photoinitiator UV Fixture time (s) unsubstituted C-Coalkyl or C-Coalkyl substituted by 1.0% mixture-1 7.0 one or more halogen, OR, SR C-Coheteroaryl, 1.0% mixture-1 S.O 65 Cs-Cophenoxycarbonyl, 0.1% oxime C-Coheteroaryloxycarbonyl, NRR, COOR, CONRR, US 8,507,726 B2 101 102 or each of which is substituted by C-Calkoxycarbonyl optionally interrupted by one or more O and/or option R20 ally substituted by one or more hydroxyl groups; or each of which is substituted by OR, SR SOR, SOR 5 and/or NRR: phenyl and/or by phenyl which is substituted by OR, SR M2 is a direct bond, cyclohexylene or C-Coalkylene or and/or NRR, wherein the unsubstituted or substituted C-Coalkylene-X—, which C-Coalkylene or C-Coalkyl optionally contains one or more C-C mul C-Coalkylene-X— is optionally interrupted by one or tiple bonds; or R and R' are NRSR more O and/or optionally substituted by one or more 10 halogen, OR, phenyl or phenyl substituted by OR SR and/or NRs R. or M is phenylene, naphthylene orphe O nylene-X—, each of which is unsubstituted or substi N-O-C-R tuted by one or more C-Calkyl, phenyl, halogen, OR, SR and/or NRR, or M is C-Coalkylene-C(O)— 15 X-, C-Coalkylene-X—C(O)—, phenylene-C(O)— X- or C-Coalkylene-phenylene-X—; or C-Cocycloalkyl; M is a direct bond, cyclohexylene, C-Coalkylene or or are C-Coalkyl which is interrupted by one or more O C-Coalkylene-X—, which C-Coalkylene or and which optionally is substituted by one or more halo C-Coalkylene-X—is optionally interrupted by one or gen, OR, phenyland/or phenyl substituted by OR, SR more O and/or optionally substituted by one or more and/or NRSR; or halogen, OR, phenyl or phenyl substituted by OR SR RandR' are phenyl which is unsubstituted or substituted and/or NRSR; or by one or more C-Calkyl, phenyl, halogen, OR, SR M is phenylene, naphthylene or phenylene-X—, each of and/or NRSR; or 25 which is unsubstituted or substituted by one or more R and Rare C-Coalkanoyl or benzoyl which is unsub C-Calkyl, phenyl, halogen, OR, SR and/or NRSR; stituted or substituted by one or more C-Calkyl, phe O nyl, OR, SR and/or NRR; or M is C-Coalkylene-C(O)—X—, C-Coalkylene-X—C R and Rare C-C alkoxycarbonyl which is optionally (O)—, phenylene-C(O)—X—, C-Coalkylene-phe interrupted by one or more O and/or optionally substi 30 nylene-X— or phenylene-(CO)-phenylene; tuted by one or more hydroxyl groups; or X is O, S or NRs: R and Rare phenoxycarbonyl which is unsubstituted or X is O, S, SO or SO: Substituted by C-Calkyl, halogen, phenyl, OR, SR X is a direct bond, C-Coalkylene which optionally is and/or NRSR; or interrupted by O, CO or NRs, and which uninterrupted R and Rare CN, CONRR, NO, S(O), C-Calkyl: 35 or interrupted C-Coalkylene is unsubstituted or Substi S(O)-phenyl which optionally is substituted by tuted by one or more halogen, OR, COOR, NRR, C-Calkyl or SO C-Calkyl, or are SOO-phenyl C-Coheteroaryl, C-Coheteroaryl-(CO)O, which optionally is substituted by C-C alkyl: C-Coheteroaryl-S, CONRR, or are diphenyl phosphinoyl or di-(C-Calkoxy)-phosphi noyl; or 40 R and Rare R20 (A) 45 phenyl or by phenyl Substituted by halogen, C-Coalkyl, C-Chaloalkyl, SR, OR, or NRSR, and -M-CH-C-Ari, which unsubstituted or substituted, interrupted or non (B) interrupted C-Coalkylene optionally contains one or more C C multiple bonds; FRV C I y NR. O 50 R is hydrogen, C-Coalkyl or phenyl-C-C-alkyl; or -M \ X R is C-Coalkyl which is substituted by OH, SH, —CN, MYR, C-Calkenoxy, OCHCHCN, OCHCH(CO)O(C- C Calkyl). O(CO)—(C-C alkyl). O(CO)-phenyl, (CO) O (C) OH and/or (CO)O(C-C alkyl); or Rs | 55 R is C-Coalkyl which is interrupted by one or more O; or R is (CHCHO), H. (CHCHO)(CO)—(C-C alkyl). \ N1 N1 NR C-Csalkanoyl, C-Calkenyl, C-Calkenoyl or -Ms Cs-Cocycloalkyl which optionally is interrupted by O. 4N O S, CO, NRs; or 60 R is benzoyl which is unsubstituted or substituted by one m is 1 or 2; or more C-Calkyl, halogen, OH and/or C-Calkoxy: Ars is phenyl, naphthyl or coumarinyl, each of which is O Substituted once or more times by halogen, C-C alkyl, R is phenyl, naphthyl or C-Coheteroaryl, each of which C-C scycloalkyl, benzyl and/or phenoxycarbonyl; or is unsubstituted or substituted by halogen, OH, each of which is substituted by phenyl or by phenyl 65 C-Calkyl, C-Calkoxy, CN, NO phenyl-C- which is substituted by one or more OR, SR and/or Calkyloxy, phenoxy, C-C alkylsulfanyl, phenylsul NRR: fanyl, N(C-C alkyl), diphenylamino and/or US 8,507,726 B2 103 104 R" has one of the meanings as given for R; R" O R" has one of the meanings as given for R. R, is hydrogen, C-Coalkyl, C-Calkyl which is Substi tuted by halogen, phenyl, OH, SH, CN, C-Calkenoxy, OCHCHCN, OCHCH(CO)O(C-C alkyl). n is 1-20; O(CO)–(C-C alkyl), O(CO)-phenyl, (CO)OH or R is hydrogen, C-Coalkyl, C-Calkenyl, (CO)O(C-C alkyl); or Cs-Cocycloalkyl, phenyl-C-C-alkyl, wherein the R is C-C alkyl which is interrupted by one or more O; or C-Coalkyl, C-Calkenyl, Cs-Cocycloalkyl, phenyl R, is (CH2CH2O), H., (CHCHO)(CO)—(C-Calkyl). C-C alkyl optionally is interrupted by O, S, CO, NRs: 10 C-Calkenyl or C-C scycloalkyl; or O R, is phenyl, biphenylyl, naphthyl or C-Coheteroaryl, R is C-Calkyl which is substituted by OH, SH, CN, each of which optionally is substituted by one or more C-Calkenoxy, OCHCHCN, OCHCH(CO)O(C- C-Coalkyl, halogen, C-Chaloalkyl, CN, NO, OR, Calkyl). O(CO)—(C-C alkyl). O(CO)-phenyl, (CO) OH or (CO)O(C-C alkyl); or 15 SR SOR SOR or NRR, wherein the substituents Rais (CH2CH2O), H., (CH2CH2O)(CO)—(C-Calkyl). OR, SR or NRSR optionally form 5- or 6-membered C-Calkanoyl, C-Calkenyl, C-Calkenoyl; or rings via the radicals R. R. Rs and/or R with one of the R is benzoyl which is unsubstituted or substituted by one carbon atoms of the phenyl, biphenylyl, naphthyl or or more C-Calkyl, halogen, —OH, C-C alkoxy or C-Coheteroaryl ring; C-C alkylsulfanyl; or Rs and Ro and R's and R' independently of each other are R is phenyl, naphthyl or C-Coheteroaryl, each of which hydrogen, C-C alkyl which optionally is substituted is unsubstituted or substituted by halogen, C-C alkyl, by one or more halogen, phenyl, CN, OH, SH, C-Calkoxy, CN, NO, phenyl-C-C-alkyloxy, phe C-Calkoxy, (CO)OH or (CO)O(C-C alkyl); or noxy, C-C alkylsulfanyl, phenylsulfanyl, N(C- Rs and R. and R's and R's are phenyl which optionally is Calkyl), diphenylamino, (CO)O(C-Calkyl). 25 Substituted by one or more C-Calkyl, halogen, CN, (CO)—C-Calkyl, (CO)N(C-Calkyl) or OR, SR or NRR; or Rs and Ro and R's and Ro are halogen, CN, OR, SR, SOR, SOR or NRSR, wherein the substituents OR, R" O SR or NRR optionally form 5- or 6-membered rings 30 via the radicals R. R. Rs and/or R with one of the carbonatoms of the phenyl or with the substituent R, or one of the carbonatoms of the naphthylene or phenylene Rs and R independently of each other are hydrogen, group of M, or C-Coalkyl, C-Chydroxyalkyl, C-Coalkoxyalkyl, Rs and R and R's and R's together are C-Calkenyl, Cs-Cocycloalkyl, phenyl-C-C-alkyl, 35 C-Calkanoyl, C-Calkenoyl, benzoyl; or Rs and R are phenyl, naphthyl or C-Coheteroaryl, each R10 R11 R12 R3 R14 R15 O of which is unsubstituted or substituted by C-C alkyl, benzoyl or C-Calkoxy; or -CEC-CEC- or - CEC-C-O-; Rs and R together with the N-atom to which they are 40 attached form a 5- or 6-membered saturated or unsatur Rio R, R2 and R independently of one another are ated ring which optionally is interrupted by O.S or NR, hydrogen, C-C alkyl which optionally is substituted and which ring is unsubstituted or substituted by one or by one or more halogen, phenyl, CN, OH, SH, more C-Coalkyl, C-Coalkoxy, =O, SR, OR or C-Calkoxy, (CO)OH or (CO)O(C-C alkyl); or NR7Rs (CO)R, NO, halogen, C-Chaloalkyl, CN, 45 Rio R, R2 and R are phenyl which optionally is Sub phenyl, stituted by one or more C-Calkyl, halogen, CN, OR, SR or NRR; or Rio R, R2 and Rs are halogen, CN, OR, SR or R" O NRR: 50 Ra and Rs independently of each other are hydrogen, C-C alkyl which optionally is substituted by one or more halogen, phenyl, CN, OH, SH, C-Calkoxy, (CO) or by Cs-Cocycloalkyl which optionally is interrupted OH or (CO)O(C-C alkyl); or R and Rs are phenyl by O, S, CO or NR; or which optionally is substituted by one or more Rs and R together with the N-atom to which they are 55 C-Calkyl, halogen, CN, OR, SR or NRSR; attached form a heteroaromatic ring system, which het R, and Rs independently of each other are hydrogen, eroaromatic ring system is unsubstituted or Substituted C-Coalkyl, C-Chaloalkyl, C-Clocycloalkyl or phe by one or more C-Coalkyl, C-Chaloalkyl, nyl; or C-Coalkoxy, =O, SR, OR, NR7Rs (CO)R. R7 and Rs together with N-atom to which they are 60 attached form a 5- or 6-membered saturated or unsatur ated ring, which optionally is interrupted by O. S or R" O NR; or R, and Rs independently of one another are C-C alkylene or C-Csalkenylene which is attached to 65 one of the C-atoms of the phenyl or naphthyl ring to halogen, NO, CN, phenyl or by C-Cocycloalkyl which the NRRs is attached, wherein said which optionally is interrupted by O, S, CO or NR; C-C alkylene or C-Calkenylene optionally is inter US 8,507,726 B2 105 106 rupted by O, CO or NR, and to which C-C alkylene or phenyl-C-C alkyl, Cs-Cocycloalkyl which optionally C-Calkenylene optionally a benzene ring is con is interrupted by O.S or CO, or is phenyl. densed; 2. A photoinititator mixture according to claim 1, wherein Ro is hydrogen, OH, C-Coalkyl, C-Chaloalkyl, the component (i) comprises an alpha-hydroxy ketone, C-Coalkyl which is interrupted by O, CO or NR 5 monoacylphosphine oxide, bisacylphosphine oxide, ketosul Cs-Cocycloalkyl which optionally is interrupted by O. fone or benzil ketal. S, CO or NR, or is phenyl, naphthyl, phenyl-C- 3. Photoinitiator mixture according to claim 1, wherein the Calkyl, SR, OR or NR7Rs: compounds of the formula I and (I) Ro is COOR, CONRR (CO)R; RandR are C-C alkyl; or Ro has one of the meanings as given for Rs and Re: 10 R and R' independently of one another are unsubstituted R is COOR, CONRR (CO)R; C-Coalkyl or C-Coalkyl substituted by COOR or or R has one of the meanings as given for Rs: R is hydrogen, C-Coalkyl, C-Coalkenyl, Cs-Cocycloalkyl which optionally is interrupted by O. S, CO or NRs, or is C-Cocycloalkenyl; or is 15 C-Coalkyl which is Substituted by one or more halo R20 gen, SR, OR, COOR, NRSR, C-Coheteroaryl, C-Coheteroaryl-(CO)O, CONRR, X is O: R is C-Coalkyl, C-Csalkanoyl orphenyl-C-C-alkyl, or R is C-Cocycloalkyl which optionally is interrupted by O: R20 R is C-Coalkyl, C-Csalkanoyl phenyl-C-C-alkyl or C-Coheteroaryl; or R is phenyl which is unsubstituted or phenyl; or R2 is C-Coalkyl which is interrupted by 25 or substituted by C-Coalkyl, halogen or one or more O and/or optionally is substituted by one or more halogen, SR, OR, COOR, NRR, R" O C-Coheteroaryl, C-Coheteroaryl-(CO)O, | CONRR, -CEN-O-C-R"; 30 Rs and Reindependently one another are hydrogen, phenyl or C-Coalkyl, or Rs and R together with the N-atom to R20 which they are attached form a heteroaromatic ring sys 35 tem, in particular carbazolyl, or phenyl: R, is phenyl, naphthyl or C-Coheteroaryl, each of which O R is phenyl, naphthyl, coumarinyl or optionally is substituted by one or more C-Calkyl, C-Coheteroaryl, each of which optionally is substi halogen, CN, OR, SR, or NRs Re: tuted by one or more C-C alkyl, phenyl, halogen, Rs and R are hydrogen; C-Chaloalkyl, CN, NO, SR, OR, NRSR or by 40 Ro is (CO)R; and Cs-Cocycloalkyl which optionally is interrupted by O. R is (CO)R. CO or NRs: 4. A photopolymerizable composition comprising or R is C-Coalkanoyl, or benzoyl which is unsubsti (a) at least one ethylenically unsaturated photopolymeriz tuted or Substituted by one or more C-Calkyl, halogen, able compound and phenyl, SR, OR or NRR: 45 (b) a photoinitiator mixture as defined in claim 1. or R2 is C-C alkoxycarbonyl which optionally is inter 5. A photopolymerizable composition comprising rupted by one or more O and/or optionally is substituted (a) at least one ethylenically unsaturated photopolymeriz by one or more OH: able aminoacrylate compound or at least one ethyleni or R is phenoxycarbonyl which is unsubstituted or Sub cally unsaturated photopolymerizable acrylate and a stituted by one or more C-Calkyl, C-Chaloalkyl, 50 halogen, phenyl, SR, OR or NRSR; H-donor and or R is NRsR: (b1) a photoinitiator mixture consisting of at least one or R forms a ring with one of the C-atoms of the phenyl compound of the formula I or I" as defined in claim 1 and ring to which the group a benzophenone compound or a thioxanthone com 55 pound; and optionally (d) other additives. O 6. A photopolymerizable composition according to claim 4, wherein the component (a) is a resin obtained by the reac N-O-C-R tion of a Saturated or unsaturated polybasic acid anhydride 60 with a product of the reaction of an epoxy resin and an unsaturated monocarboxylic acid. 7. A photopolymerizable composition according to claim is attached, wherein said formed ring is unsubstituted or 4, additionally to the photoinitiator (b) comprising at least one Substituted; further photoinitiator (c), and/or other additives (d). R has one of the meanings as given for R, and 65 8. A photopolymerizable composition according to claim 5 Ra is hydrogen, C-Coalkyl, C-Chaloalkyl, as further additive (d) comprising a pigment or a mixture of C-Coalkyl which is interrupted by O. S or CO, or is pigments. US 8,507,726 B2 107 108 9. A photopolymerizable composition according to claim 5 direct imaging system, as a photoresist material used for as further additive (d) comprising a dispersant or a mixture of forming dielectric layers in a sequential build-up layer of a dispersants. printed circuit board. 10. A photopolymerizable composition according to claim 14. A method of using a composition according to claim 4 4, comprising 0.01 to 25% by weight of the photoinitiator (b). for producing pigmented and nonpigmented paints and var or the photoinitiators (b) and (c), based on the solid compo nishes, powder coatings, printing inks, printing plates, adhe sition. sives, pressure sensitive adhesives, dental compositions, gel 11. A photopolymerizable composition according to claim coats, photoresists for electronics, electroplating resists, etch 4, which is a printing ink. resists, both liquid and dry films, Solder resists, resists to 12. A process for the photopolymerization of compounds 10 containing ethylenically unsaturated double bonds, which manufacture color filters for a variety of display applications, comprises irradiating a composition according to claim 4 resists to generate structures in the manufacturing processes with electromagnetic radiation in the range from 150 to 600 of plasma-display panels, electroluminescence displays and nm, or with electron beam or with X-rays. LCD, spacers for LCD, for holographic data storage (HDS). 13. A process according to claim 12 for producing pig 15 as composition for encapsulating electrical and electronic mented and nonpigmented paints and varnishes, powder coat components, for producing magnetic recording materials, ings, printing inks, printing plates, adhesives, pressure sensi micromechanical parts, waveguides, optical Switches, plating tive adhesives, dental compositions, gel coats, photoresists masks, etch masks, colour proofing systems, glass fibre cable for electronics, electroplating resists, etch resists, both liquid coatings, screen printing stencils, for producing three-dimen and dry films, solder resists, resists to manufacture color sional objects by means of stereolithography, as image filters for a variety of display applications, resists to generate recording material, for holographic recordings, microelec structures in the manufacturing processes of plasma-display tronic circuits, decolorizing materials, decolorizing materials panels, electroluminescence displays and LCD, spacers for for image recording materials, for image recording materials LCD, for holographic data storage (HDS), as composition for using microcapsules, as a photoresist material for a UV and encapsulating electrical and electronic components, for pro 25 visible laser direct imaging system, as a photoresist material ducing magnetic recording materials, micromechanical parts, used for forming dielectric layers in a sequential build-up waveguides, optical Switches, plating masks, etch masks, layer of a printed circuit board. colour proofing systems, glass fibre cable coatings, screen 15. A coated substrate which is coated on at least one printing stencils, for producing three-dimensional objects by Surface with a composition according to claim 4. means of stereolithography, as image recording material, for 30 16. Cured coating obtained by applying a composition holographic recordings, microelectronic circuits, decoloriz according to claim 4 to a substrate and irradiating said coated ing materials, decolorizing materials for image recording Substrate with electromagnetic radiation in the range from materials, for image recording materials using microcap 150 to 600 nm, or with electron beam or with X-rays. sules, as a photoresist material for a UV and visible laser k k k k k