US 20050048403A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0048403 A1 Kuroki (43) Pub. Date: Mar. 3, 2005

(54) PLANOGRAPHIC PRINTING PLATE (57) ABSTRACT MATERIAL AND PLANOGRAPHIC PRINTING PLATE PREPARING PROCESS Disclosed is a planographic printing plate material compris ing a hydrophilic support and provided thereon, a light (75) Inventor: Takaaki Kuroki, Tokyo (JP) sensitive layer and an overcoat layer in that order, Wherein the light sensitive layer contains (a) an alkali soluble poly Correspondence Address: mer, (b) a polymeriZable compound having an ethylenically FRISHAUF, HOLTZ, GOODMAN & CHICK, unsaturated bond, (c) a polymerization initiator, and (d) an PC anionic dye represented by the following formula (1), 767 THIRD AVENUE 25TH FLOOR NEW YORK, NY 10017-2023 (US) Formula (1) (73) Assignee: KONICA MINOLTA MEDICAL & GRAPHIC, INC., Tokyo (JP) (21) Appl. No.: 10/923,415 (22) Filed: Aug. 20, 2004 (30) Foreign Application Priority Data

Aug. 29, 2003 (JP) ...... JP2003-306272

Publication Classi?cation

(51) Int. Cl? ...... G03F 7/00 (52) US. Cl...... 430/300 US 2005/0048403 A1 Mar. 3, 2005

PLANOGRAPHIC PRINTING PLATE MATERIAL there is a method Which increases solubility of light sensitive AND PLANOGRAPHIC PRINTING PLATE layer. Typically, a resin having a high acid value or a PREPARING PROCESS photoinitiator system for accelerating reaction by heating has been studied. HoWever, satisfactory preheating latitude FIELD OF THE INVENTION has not yet obtained considering printing durability. Further, the above negative-Working photopolymeriZation type print [0001] The present invention relates to a planographic printing plate material With high sensitivity Which is capable ing plate material has problem in that sludge is likely to be produced in a developer, and does not have a satisfactory of being exposed With laser, and a process of preparing a planographic printing plate employing the same, and par running property. ticularly to a planographic printing plate material capable of being exposed With loW poWer laser, Which improves stor SUMMARY OF THE INVENTION age stability and preheating latitude, and minimizes sludge, [0006] An object of the invention is to provide a plano and a process of preparing a planographic printing plate graphic printing plate material providing high sensitivity, employing the same. high printing durability, and good preheating latitude, and a process of preparing a planographic printing plate employ BACKGROUND OF THE INVENTION ing the same. [0002] In recent years, as a printing plate for off-set printing, a large number of computer to plate (CTP) systems DETAILED DESCRIPTION OF THE have been developed and put into practical use, Which INVENTION imageWise exposes directly to a planographic printing plate material employing laser light based on digital image data to [0007] The present inventors have studied an extensive study. As a result, they have found that the preheating record an image on the material. As the CTP systems, there latitude is Widened by employing a speci?c anionic dye, are a silver salt system, a radical polymeriZation system and storage stability is greatly improved by employing eosin a thermal system, Which differ in characteristics. having a speci?c structure, and a combined use of a [0003] The radical polymeriZation system has character titanocene compound provides good preheating latitude as istics providing high sensitivity and high printing durability, Well as high sensitivity and printing durability, and com and is Widely applied in printing ?elds such neWspaper pleted the invention. Further, they have found that use of the printing. The general radical polymerization is disclosed in anionic dye in the invention provides a good running prop many literatures such as Japanese Patent O.P.I. Publication erty. No. 10-104835. A composition comprising an arene com [0008] The above object of the invention is attained by the pound as a polymeriZation initiator is disclosed in Japanese folloWing constitution. Patent O.P.I. Publication No. 1-152109. Japanese Patent Publication No. 2755723 discloses, as a composition pro [0009] 1. A planographic printing plate material compris viding high sensitivity and high printing durability, a pho ing a hydrophilic support and provided thereon, a light topolymeriZable composition Which comprises a polymer sensitive layer and an overcoat layer in that order, Wherein binder, a free-radical polymeriZable compound, a photore the light sensitive layer contains (a) an alkali soluble poly duction dye (photo-initiator), and a trihalomethyl compound mer, (b) a polymeriZable compound having an ethylenically and a metallocene compound as another photo-initiator, and unsaturated bond, (c) a polymeriZation initiator, and (d) an discloses in the examples a composition comprising an anionic dye represented by the folloWing formula (1), alcohol soluble eosin, a trihalomethyltriaZine, and a titanocene compound. Acomposition disclosed in this patent document provides excellent sensitivity and printing dura Formula (1) bility, Which is preferred, hoWever, a planographic printing plate material comprising the composition is greatly loWered in storage stability after long term storage, resulting in insuf?cient practical properties. [0004] The radical polymeriZation system generally employs a process comprising exposure, heat treatment, Water Washing, alkali development, and Water Washing in that order. This system is a preferred one to obtain high printing durability by completing the radical polymeriZation. HoWever, When printing plate materials having a different thickness Were processed, the printing plate materials are heated at preheating to different temperature due to the different thickness, producing problem of causing develop ment failure. As the countermeasure, an attempt has been made in Which arrangement of rollers in an automatic processing machine (automatic processor) or pre-determi [0010] Wherein R1 represents a substituted or unsubsti nation (provision) of preheating conditions to each plate tuted alkyl group having a carbon atom number of from 4 to 18, a cycloalkyl group having a carbon atom number of from thickness is examined. 4 to 18, or a substituted or unsubstituted aryl group having [0005] As an effective method to Widen the latitude as a carbon atom number of from 6 to 18; R2 through R11 printing plate materials to various preheating conditions, independently represent a hydrogen atom, a atom, a US 2005/0048403 A1 Mar. 3, 2005

substituted or unsubstituted alkyl group having a carbon [0020] 10. The planographic printing plate material of atom number of from 1 to 6, a cycloalkyl group having a item 9 above, Wherein the light sensitive layer further carbon atom number of from 4 to 6, a substituted or contains a polyhalogenated compound as the polymeriZation unsubstituted aryl group having a carbon atom number of initiator. from 6 to 18 or —N(R12) (R13) in Which R12 and R13 independently represent a substituted or unsubstituted alkyl [0021] 11. The planographic printing plate material of group having a carbon atom number of from 1 to 6, a item 10 above, Wherein the polyhalogenated compound is a cycloalkyl group having a carbon atom number of from 4 to polyhalomethylsulfone, a polyhalomethyl oXadiaZole, or a 6, or a substituted or unsubstituted aryl group having a compound having a polyhaloacetyl structure represented by carbon atom number of from 6 to 18; and Y+ represents a the folloWing formula (2), hydrogen ion, an alkali metal ion or an onium ion. R21—CX2— (c:o) _R22 Formula (2) [0011] 2. The planographic printing plate material of item [0022] Wherein R21 represents a hydrogen atom, a bromine 1 above, Wherein the light sensitive layer contains a metal atom, a chlorine atom, an alkyl group, an aryl group, an acyl locene compound as the polymeriZation initiator. group, an alkylsulfonyl group, an arylsulfonyl group or a [0012] 3. The planographic printing plate material of item cyano group; R22 represents a hydrogen atom or a monova 2 above, Wherein the light sensitive layer further contains a lent organic substituent, provided that R21 and R22 may polyhalogenated compound as the polymeriZation initiator. combine With each other to form a ring; and X represents a bromine atom or a chlorine atom. [0013] 4. The planographic printing plate material of item 3 above, Wherein the polyhalogenated compound is a poly [0023] 12. The planographic printing plate material of any halomethylsulfone, a polyhalomethyl oXadiaZole, or a com one of items 8 through 11 above, Wherein the alkali soluble pound having a polyhaloacetyl structure represented by the polymer has a Weight average molecular Weight of from folloWing formula (2), 15,000 to 500,000, and an acid value of from 30 to 200. R21—CX2— (c:o) _R22 Formula (2) [0024] 13. The planographic printing plate material of any one of items 8 through 12 above, Wherein the alkali soluble [0014] Wherein R21 represents a hydrogen atom, a bromine polymer has repeating a monomer unit having an ethyleni atom, a chlorine atom, an alkyl group, an aryl group, an acyl cally unsaturated bond in an amount of from 5 to 50 mol % group, an alkylsulfonyl group, an arylsulfonyl group or a in the molecule. cyano group; R22 represents a hydrogen atom or a monova lent organic substituent, provided that R21 and R22 may [0025] 14. The planographic printing plate material of any combine With each other to form a ring; and X represents a one of items 8 through 13 above, Wherein the polymeriZable bromine atom or a chlorine atom. compound having an ethylenically unsaturated bond is a polyfunctional acrylate having an amido bond and a sec [0015] 5. The planographic printing plate material of any ondary or tertiary amino group in the molecule. one of items 1 through 4 above, Wherein the alkali soluble polymer has a Weight average molecular Weight of from [0026] 15. A process of preparing a planographic printing 15,000 to 500,000, and an acid value of from 30 to 200. plate, the process comprising the steps of imageWise eXpos ing the planographic printing plate material of any one of [0016] 6. The planographic printing plate material of any items 1 through 14 above, employing a laser With an one of items 1 through 5 above, Wherein the alkali soluble emission Wavelength of from 400 to 600 nm; heating the polymer has a repeating monomer unit having an ethyleni resulting eXposed material at a temperature of from 80 to cally unsaturated bond in an amount of from 5 to 50 mol % 150° C. for 3 to 30 seconds; and developing the heated in the molecule. material With an alkali developer having a pH of from 10 to [0017] 7. The planographic printing plate material of any 12.5. one of items 1 through 6 above, Wherein the polymeriZable compound having an ethylenically unsaturated bond is a [0027] Next, the light sensitive layer, the overcoat layer, the hydrophilic support, and various additives, Which con polyfunctional acrylate having an amido bond and a sec stitute the planographic printing plate material of the inven ondary or tertiary amino group in the molecule. tion, and an image formation process and a developing [0018] 8. A planographic printing plate material compris process Will be explained. ing a hydrophilic support and provided thereon, a light sensitive layer and an overcoat layer in that order, Wherein [0028] the light sensitive layer contains (a) an alkali soluble poly [0029] The light sensitive composition in the invention mer, (b) a polymeriZable compound having an ethylenically contains (a) an alkali soluble polymer, (b) a polymeriZable unsaturated bond, (c) a polymeriZation initiator, and (d) an compound (hereinafter also referred to as an ethylenically anionic dye having an acidic group, a basic group or a unsaturated compound) having an ethylenically unsaturated hydroXyl group, each group reacting With a reactive com bond, (c) a polymeriZation initiator (hereinafter also referred pound to be modi?ed With a substituted or unsubstituted to as an initiator), and (d) an anionic dye represented by alkyl group, a substituted or unsubstituted cycloalkyl group formula (1) above. or an unsubstituted aryl group, Wherein the reactive com pound has an SP value of from 15 to 26 [Mpal/z]. [0030] (Anionic Dye) [0019] 9. The planographic printing plate material of item [0031] The present invention is characteriZed in that a 8 above, Wherein the light sensitive layer contains a metal Xanthene dye represented by formula (1) above is used as a locene compound as the polymeriZation initiator. photoinitiator. US 2005/0048403 A1 Mar. 3, 2005

[0032] In formula (1), the substituted or unsubstituted alkyl or cycloalkyl group having a carbon atom number of -continued from 4 to 18 represented by R1 above has a carbon atom 1-4 number of preferably from 4 to 10. The substituted or unsubstituted aryl group having a carbon atom number of from 6 to 18 represented by R1 above has a carbon atom number of preferably from 6 to 12. R1 is especially prefer Br Br \ ably a substituted or unsubstituted alkyl group having a carbon atom number of from 4 to 10. KO 0 0

[0033] Examples of R1 include butyl, heXyl, cycloheXyl, Br Br octyl, decyl, dodecyl, and phenyl. Of these, R1 is preferably butyl, heXyl, cycloheXyl, or octyl. R2 through R11 indepen dently represent preferably a hydrogen atom or a halogen 1-5 atom (especially preferably a brornine atorn). Y“ is prefer ably a hydrogen ion or an alkali metal ion (i.e., sodium or potassium ion). coocnzqczns)3 Br Br [0034] Typical examples of a dye represented by formula \ (1) Will be listed beloW, but the invention is not speci?cally lirnited thereto. KO 0 0

Br Br

1-1 1-6

COOC8H17 I COO(CH2)7CF3 Br Br \ Br Br \

KO 0 0 KO 0 0 Br Br Br Br 1-2

1-7

COOC8H17 OZN \ I N02 I COOC8H17 Br \ Br NaO O 0

Br Br 'O O 0 1-3 Br Br

(CeH5)35+

Br Br [0035] The anionic dye in item 8 above having in the molecule an acidic group, a basic group or a hydroXyl group \ Q refers to a dye having in the molecule having an acidic group KO 0 0 (a knoWn acidic substituent such as a carboXyl group, a sulfo group or a phosphonic acid group), a basic group (a knoWn Br Br basic substituent such as an amino group) or a hydroXyl group (such as alcoholic or phenolic hydroXyl). The acidic group, basic group or hydroXyl group of the anionic dye above is rnodi?ed to a substituted or unsubstituted alkyl US 2005/0048403 A1 Mar. 3, 2005

group, a cycloalkyl group or a substituted or unsubstituted [0044] Of these, polymers having a hydroxyl group or a aryl group on reaction With a compound capable of reacting carboxyl group are preferably used, and polymers having a With the acidic group, basic group or hydroxyl group. The carboxyl group are more preferably used. compound capable of reacting With the acidic group, basic group or hydroxyl group has an SP value of from 15 to 26 [0045] Of these, a vinyl copolymer is preferably used [Mpaml Which is obtained by copolymeriZation of an acryl monomer, and more preferred is a copolymer containing (a) a carboxyl [0036] As the compound capable of reacting With an group-containing monomer unit and (b) an alkyl (meth)acry acidic group, a basic group or a hydroxyl group, there is a late unit as the copolymeriZation component. hydroxyl group-containing compound, a cyclic ether such as an epoxy group-containing compound, a vinyl ether, or an [0046] Examples of the carboxyl group-containing mono amino group-containing compound, each being capable of mer include an ot,[3-unsaturated carboxylic acid, for reacting With an acidic group; a hydroxyl group-containing example, acrylic acid, methacrylic acid, maleic acid, maleic compound, an isocyanate group-containing compound or an anhydride, itaconic acid, itaconic anhydride or a carboxylic acidic group-containing compound, each being capable of acid such as a half ester of phthalic acid With 2-hy droxymethacrylic acid. reacting With a basic group; or an acidic group-containing compound or an isocyanate group-containing compound, [0047] Examples of the alkyl (meth)acrylate include an each being capable of reacting With a hydroxyl group. unsubstituted alkyl ester such as methyl(meth)acrylate, eth yl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acry [0037] An SP value of these compounds is preferably from late, amyl(meth)acrylate, hexyl(meth)acrylate, heptyl 15 to 26 [Mpal/z]. HoWever, preferred SP value is as folloWs (meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, according to kinds of the substituent the compounds have. decyl(meth)acrylate, undecyl(meth)acrylate, or dodecyl [0038] An SP value of a carboxyl group-containing com (meth)acrylate; a cyclic alkyl ester such as cyclohexyl pound is preferably from 15 to 26 [Mpal/z]. An SP value of (meth)acrylate; and a substituted alkyl ester such as benZyl an alcoholic hydroxyl group-containing compound is pref (meth)acrylate, 2-chloroethyl (meth)acrylate, N,N-dimethy erably from 15 to 26 [Mpal/z], and more preferably from 20 laminoethyl (meth)acrylate, or glycidyl (meth)acrylate. to 26 [Mpal/z]. An SP value of a phenolic hydroxyl group containing compound is preferably from 15 to 25 [Mpal/z]. [0048] As another monomer unit, a monomer unit derived An SP value of an amino group-containing compound is from the monomer described in the folloWing items (1) preferably from 15 to 26 [Mpal/z]. through (14) can be used. [0039] As the compounds falling Within the scope [0049] (1) A monomer having an aromatic hydroxy group, described above, among compounds described in “Polymer for example, 0-, (p- or m-) hydroxystyrene, or o-, (p- or m-) Handbook, Fourth Edition”, VII, p. 675 et seq., compounds hydroxyphenylacrylate; can be suitably used Which have a group (for example, R1 of [0050] (2) Amonomer having an aliphatic hydroxy group, formula reacting With the acidic group, basic group or for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl meth hydroxyl group to be substituted With a substituted or acrylate, N-methylolacrylamide, N-methylolmethacryla unsubstituted alkyl group, a substituted or unsubstituted mide, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacry cycloalkyl group or an unsubstituted aryl group. late, 5-hydroxypentyl acrylate, 5-hydroxypentyl [0040] Examples of alcoholic hydroxyl group-containing methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl compounds having an SP value of from 15 to 26 [Mpa1/2] methacrylate, N-(2-hydroxyethyl)acrylamide, N-(2-hy include propanol, isopropanol, butanol, isobutanol, cyclo droxyethyl)methacrylamide, or hydroxyethyl vinyl ether; hexanol, pentanol, 2-ethyl-1-butanol, 1,3-dimethyl-1-bu [0051] (3) Amonomer having an aminosulfonyl group, for tanol, 1-octanol, 2-octanol, decanol, undecanol, dodecanol, example, m- or p-aminosulfonylphenyl methacrylate, m- or tridecyl alcohol, oleyl alcohol, allyl alcohol, 3-chloropro p-aminosulfonylphenyl acrylate, N-(p-aminosulfonylphe panol, benZyl alcohol, and diacetone alcohol. Alcoholic nyl) methacrylamide, or N-(p-aminosulfonylphenyl)acryla hydroxyl group-containing compounds having an SP value mide; of preferably from 20 to 26 [Mpa1/2] are propanol, isopro panol, butanol, isobutanol, cyclohexanol, pentanol, 2-ethyl [0052] (4) A monomer having a sulfonamido group, for 1-butanol, 1-octanol, 2-octanol, decanol, undecanol, allyl example, N-(p-toluenesulfonyl)acrylamide, or N-(p-tolu alcohol, 3-chloropropanol, benZyl alcohol, and diacetone enesulfonyl)methacrylamide; alcohol. [0053] (5) An acrylamide or methacrylamide, for example, acrylamide, methacrylamide, N-ethylacrylamide, N-hexy [0041] (Alkali Soluble Polymer) lacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, [0042] In the invention, the alkali soluble polymer refers N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, to a polymer having an acid value and is preferably a N-4-hydroxyphenylacrylamide, or N-4-hydroxyphenyl copolymer having various structures described later. methacrylamide; [0043] As the copolymer, a polyacrylate resin, a polyvi [0054] (6) A monomer having a ?uorinated alkyl group, nylbutyral resin, a resin, a resin, a for example, tri?uoromethyl acrylate, tri?uoromethyl meth resin, an epoxy resin, a phenol resin, a polycar acrylate, tetra?uoropropyl methacrylate, hexa?uoropropyl bonate resin, a resin, a polyvinyl formal methacrylate, octa?uoropentyl acrylate, octa?uoropentyl resin, a shellac resin, or another natural resin is preferably methacrylate, heptadeca?uorodecyl methacrylate, heptade used. These resins can be used as an admixture of tWo or ca?uorodecyl methacrylate, or N-butyl-N-(2-acryloxyethyl more thereof. )heptadeca?uorooctylsulfonamide; US 2005/0048403 A1 Mar. 3, 2005

[0055] (7) A vinyl ether, for example, ethyl vinyl ether, meter is a neutraliZing point, and the acid value is obtained 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl from an amount of potassium hydroxide necessary to reach ether, octyl vinyl ether, or phenyl vinyl ether; the neutraliZing point. [0056] (8) A vinyl ester, for example, vinyl acetate, vinyl [0070] An alkali soluble polymer having a polymeriZable chroloacetate, vinyl butyrate, or vinyl benZoate; unsaturated group can be synthesiZed according to a con ventional method Without any limitations. [0057] (9) Astyrene, for example, styrene, methylstyrene, or chloromethystyrene; [0071] For example, a method can be used Which reacts the carboxyl group described later With a glycidyl group, or [0058] (10) A vinyl ketone, for example, methyl vinyl reacts a hydroxyl group With an isocyanate group. ketone, ethyl vinyl ketone, propyl vinyl ketone, or phenyl [0072] Typically, the alkali soluble polymer is a reaction vinyl ketone; product obtained by reacting a copolymer having a carboxyl [0059] (11) An ole?n, for example, ethylene, propylene, group-containing monomer unit With an aliphatic epoxy isobutylene, butadiene, or isoprene; containing unsaturated compound such as allyl glycidyl ether, glycidyl (meth)acrylate, ot-ethylglycidyl (meth)acry [0060] (12) N-vinylpyrrolidone, N-vinylcarbaZole, or late, glycidyl crotonate, glycidyl isocrotonate, crotonyl gly N-vinylpyridine, cidyl ether, itaconic acid monoalkylmonoglycidyl ester, fumaric acid monoalkylmonoglycidyl ester, or maleic acid [0061] (13) A monomer having a cyano group, for monoalkylmonoglycidyl ester; or an alicyclic epoxy-con example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, taining unsaturated compound such as 3,4-epoxycyclohexy 2-methyl-3-butene nitrile, 2-cyanoethyl acrylate, or o-, m- or lmethyl (meth)acrylate. In the invention, When an amount of p-cyanostyrene; the carboxyl group reacted With the epoxy-containing unsat [0062] (14) A monomer having an amino group, for urated compound is represented in terms of mol %, The example, N,N-diethylaminoethyl methacrylate, N,N-dim amount is preferably from 5 to 50 mol %, and more ethylaminoethyl acrylate, N,N-dimethylaminoethyl meth preferably from 10 to 30 mol % in vieW of sensitivity and acrylate, polybutadiene urethane acrylate, N,N-dimethy printing durability. laminopropyl acrylamide, N,N-dimethylacrylamide, [0073] Reaction of a copolymer having a carboxyl group acryloylmorpholine, N-isopropylacrylamide, or N,N-diethy containing monomer unit With an epoxy-containing unsat lacrylamide. urated compound is carried out for example, at 80 to 120° C. [0063] Further another monomer may be copolymeriZed for 1 to 50 hours. The reaction product can be synthesiZed With the above monomers. according to a conventional polymeriZation method, for example, a method described in literatures such as W. R. [0064] As the polymer is also preferred an unsaturated Sorenson & T. W. Cambell “Kobunshi Gosei Jikkenho” bond-containing copolymer Which is obtained by reacting a published by TOKYO KAGAKU DOHJIN, or Japanese carboxyl group contained in the above vinyl copolymer Patent O.P.I. Publication Nos. 10-315598 and 11-271963, or molecule With for example, a compound having a (meth a method similar to the above. )acryloyl group and an epoxy group. [0074] The content of the alkali soluble polymer in the [0065] Examples of the compound having a (meth)acry light sensitive layer is preferably from 10 to 90% by Weight, loyl group and an epoxy group in the molecule include more preferably from 15 to 70% by Weight, and still more glycidyl acrylate, glycidyl methacrylate and an epoxy preferably from 20 to 50% by Weight. group-containing unsaturated compound disclosed in J apa [0075] Examples of the copolymer having a carboxyl nese Patent O.P.I. Publication No. 11-27196. group-containing monomer unit described above include a copolymer having at least one selected from units derived [0066] Of the above alkali soluble polymers, those giving from the folloWing monomers (1) through (17): an acid value of from 30 to 200 are preferred. Of these, those further having a Weight average molecular Weight of from [0076] (1) A monomer having an aromatic hydroxy group; 15,000 to 500,000 are especially preferred. [0077] (2) Amonomer having an aliphatic hydroxy group; [0067] Of the above polymers, those having a polymeriZ (3) A monomer having an aminosulfonyl group; able unsaturated group are preferred, and those having 5 to [0078] 50 mol % of the polymeriZable unsaturated group as a [0079] (4) A monomer having a sulfonamido group; repeating unit are especially preferred. [0080] (5) An ot,[3-unsaturated carboxylic acid; [0068] In the invention, the Weight average molecular (6) A substituted or unsubstituted alkyl acrylate; Weight of the polymers is measured by gel permeation [0081] chromatography (GPC). [0082] (7) A substituted or unsubstituted alkyl acrylate; [0069] In the invention, the acid value refers to the number [0083] (8) Acrylamide or methacrylamide; of mg of potassium hydroxide (KOH) necessary to neutral (9) A monomer having a ?uorinated alkyl group; iZe 1 g of the compound described above. The acid value can [0084] be determined as folloWs: A sample is diluted With methyl [0085] (10) A vinyl ether; cellosolve by a factor of 50, and the resulting solution is titrated With a 0.1 mol/liter potassium hydroxide solution. [0086] (11) A vinyl ester; In?ection point of the pH curve obtained according to a pH [0087] (12) A styrene; US 2005/0048403 A1 Mar. 3, 2005

[0088] (13) A vinyl ketone; dimethylethyl)-5-hydroxymethyl-5-ethyl-1,3-dioxane dia crylate, tricyclodecanedimethylol acrylate, [0089] (14) An ole?n; tricyclodecanedimethylol acrylate-e-caprolactone adduct or [0090] (15) N-vinylpyrrolidone, N-vinylcarbaZole, or 1,6-hexanediol diglycidylether diacrylate; a dimethacrylate, N-vinylpyridine; diitaconate, dicrotonate or dimaleate alternative of the above diacrylate; a polyfunctional acrylate such as trimethylolpro [0091] (16) A monomer having a cyano group; and pane triacrylate, ditrimethylolpropane tetraacrylate, trim [0092] (17) A monomer having an amino group. ethylolethane triacrylate, pentaerythritol triacrylate, pen taerythritol tetraacrylate, dipentaerythritol tetraacrylate, [0093] Typical examples thereof include a monofunctional dipentaerythritol pentaacrylate, dipentaerythritol hexacry acrylate such as 2-ethylhexyl acrylate, 2-hydroxypropyl late, dipentaerythritol hexacrylate-e-caprolactone adduct, acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phe pyrrogallol triacrylate, propionic acid dipentaerythritol tria noxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydro crylate, propionic acid dipentaerythritol tetraacrylate or furfuryl-oxyethyl acrylate, tetrahydrofurfuryloxyhexan hydroxypivalylaldehyde modi?ed dimethylolpropane tria orideacrylate, an ester of 1,3-dioxane-e-caprolactone adduct crylate; a methacrylate, itaconate, crotonate or maleate alter With acrylic acid, or 1,3-dioxolane acrylate; a methacrylate, native of the above polyfunctional acrylate. itaconate, crotonate or maleate alternative of the above acrylate; a bifunctional acrylate such as ethyleneglycol [0098] Prepolymers can be used, and the prepolymers can diacrylate, triethyleneglycol diacrylate, pentaerythritol dia be used singly, in combination, or as an admixture thereof crylate, hydroquinone diacrylate, resorcin diacrylate, hex With the above described monomers and/or oligomers. anediol diacrylate, neopentyl glycol diacrylate, tripropylene [0099] Examples of the prepolymer include polyester glycol diacrylate, hydroxypivalic acid neopentyl glycol dia (meth)acrylate obtained by incorporating (meth)acrylic acid crylate, neopentyl glycol diacrylate, diacrylate of in a polyester of a polybasic acid such as adipic acid, hydroxypivalic acid neopentyl glycol-e-caprolactone trimellitic acid, maleic acid, phthalic acid, terephthalic acid, adduct, 2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl hymic acid, malonic acid, succinic acid, glutaric acid, ita 5-ethyl-1,3-dioxane diacrylate, tricyclodecanedimethylol conic acid, pyromellitic acid, fumalic acid, pimelic acid, acrylate, tricyclodecanedimethylol acrylate-e-caprolactone sebatic acid, dodecanic acid or tetrahydrophthalic acid With adduct or 1,6-hexanediol diglycidylether diacrylate; a a polyol such as ethylene glycol, ethylene glycol, diethylene dimethacrylate, diitaconate, dicrotonate or dimaleate alter glycol, propylene oxide, 1,4-butane diol, triethylene glycol, native of the above diacrylate; a polyfunctional acrylate such tetraethylene glycol, glycol, grycerin, trim as trimethylolpropane triacrylate, ditrimethylolpropane tet ethylol propane, pentaerythritol, sorbitol, 1,6-hexanediol or raacrylate, trimethylolethane triacrylate, pentaerythritol tria 1,2,6-hexanetriol; an epoxyacrylate such as bisphenol crylate, pentaerythritol tetraacrylate, dipentaerythritol tet A.epichlorhydrin.(meth)acrylic acid or phenol novol raacrylate, dipentaerythritol pentaacrylate, dipentaerythritol ak.epichlorhydrin.(meth)acrylic acid obtained by incorpo hexacrylate, dipentaerythritol hexacrylate-e-caprolactone rating (meth)acrylic acid in an epoxy resin; an urethane adduct, pyrrogallol triacrylate, propionic acid dipentaeryth acrylate such as ethylene glycol.adipic ritol triacrylate, propionic acid dipentaerythritol tetraacry acid.tolylenediisocyanate.2-hydroxyethylacrylate, polyeth late or hydroxypivalylaldehyde modi?ed dimethylolpropane ylene glycol.tolylenediisocyanate.2-hydroxyethylacrylate, triacrylate; a methacrylate, itaconate, crotonate or maleate hydroxyethylphthalyl methacrylate.xylenediisocyanate, 1,2 alternative of the above polyfunctional acrylate. polybutadieneglycol.tolylenediisocyanate.2-hydroxyethy [0094] (Ethylenically Unsaturated Compound) lacrylate or trimethylolpropane.propylene glycol.tolylenedi isocyanate.2-hydroxyethylacrylate, obtained by [0095] As the ethylenically unsaturated compound in the incorporating (meth)acrylic acid in an urethane resin; a invention, a compound having a monofunctional or poly silicone acrylate such as polysiloxane acrylate, or polysi functional ethylenically unsaturated group is suitably used. loxane.diisocyanate.2-hydroxyethylacrylate; an alkyd modi [0096] The ethylenically unsaturated compound in the ?ed acrylate obtained by incorporating a methacroyl group invention is preferably a polyfunctional acrylate having an in an oil modi?ed alkyd resin; and a spiran resin acrylate. amido bond and a primary or secondary amino group. [0100] The light sensitive layer in the light sensitive layer [0097] Typical examples of the ethylenically unsaturated of the planographic printing plate material of the invention compound include a monofunctional acrylate such as 2-eth may contain a monomer such as a phosphaZene monomer, ylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acry triethylene glycol, an E0 modi?ed isocyanuric acid diacry late, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, late, an E0 modi?ed isocyanuric acid triacrylate, dimethy nonylphenoxyethyl acrylate, tetrahydrofurfuryl-oxyethyl loltricyclodecane diacrylate, trimethylolpropane acrylate acrylate, tetrahydrofurfuryloxyhexanorideacrylate, an ester benZoate, an alkylene glycol acrylate, or a urethane modi?ed of 1,3-dioxane-e-caprolactone adduct With acrylic acid, or acrylate, or an addition polymeriZable oligomer or prepoly 1,3-dioxolane acrylate; a methacrylate, itaconate, crotonate mer having a structural unit derived from the above mono or maleate alternative of the above acrylate; a bifunctional mer. acrylate such as ethyleneglycol diacrylate, triethyleneglycol [0101] The ethylenically unsaturated compound used in diacrylate, pentaerythritol diacrylate, hydroquinone diacry the invention is a phosphate compound having at least one late, resorcin diacrylate, hexanediol diacrylate, neopentyl (meth)acryloyl group. The phosphate compound is a com glycol diacrylate, tripropylene glycol diacrylate, hydrox pound having a (meth)acryloyl group in Which at least one ypivalic acid neopentyl glycol diacrylate, neopentyl glycol hydroxyl group of phosphoric acid is esteri?ed. The ethyl adipate diacrylate, diacrylate of hydroxypivalic acid neo enically unsaturated compound used in the invention is not pentyl glycol-e-caprolactone adduct, 2- (2-hydroxy-1,1 limited, as long as it has a (meth)acryloyl group. US 2005/0048403 A1 Mar. 3, 2005

[0102] Besides the above compounds, compounds dis ring group; a is an integer of from 0 to 4; b is 0 or 1; c is an closed in Japanese Patent O.P.I. Publication Nos. integer of from 1 to 3; m1 is an integer of from 2 to 4; and 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, n1 is an integer of from 1 to m1, provided that plural groups 62-187092, 63-67189, and 1-244891, compounds described having the same de?nition may be the same or different. on pages 286 to 294 of “11290 Chemical Compounds” edited by Kagakukogyo Nipposha, and compounds [0107] In formula (I), examples of the alkyl group repre sented by R4 include a methyl group, an ethyl group, a described on pages 11 to 65 of “UV'EB Koka Handbook (Materials)” edited by Kobunshi Kankokai can be suitably propyl group, a butyl group, a pentyl group, an iso-pentyl used. Of these compounds, compounds having tWo or more group, a 2-ethylhexyl group, an octyl group, a decyl group, acryl or methacryl groups in the molecule are preferable, and an n-dodecyl group, an n-tetradecyl group, an n-pentradecyl those having a molecular Weight of not more than 10,000, group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, and an n-docosadecyl group. and preferably not more than 5,000 are more preferable. [0108] Examples of the hydroxyalkyl group represented [0103] The compound having an amido bond and a sec by R4 include a hydroxymethyl group, a hydroxyethyl ondary or tertiary amino group in the molecule preferably group, a hydroxypropyl group, and a hydroxypentyl group. used in the invention is a compound represented by the folloWing formula (I): [0109] Examples of the aryl group represented by R4 include a phenyl group, and a naphthyl group. [0110] Examples of the alkyl group represented by R1 or R2 are the same as those denoted in R4 above. [0111] Examples of the alkoxy group represented by R1 or R2 include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and a propoxyethyl group. [0112] The divalent linkage group having a carbon atom number of from 2 to 12 represented by X1 is a divalent [0104] Wherein Q1 represents saturated hydrocarbon group having a carbon atom number of from 2 to 12 or an arylene group having a carbon atom number of from 6 to 12. Examples of the divalent saturated hydrocarbon group having a carbon atom number of from 2 to 12 represented by X1 include an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octam ethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a cyclohexylene group (e.g., a 1,6-cyclohexanediyl [0105] R4 represents an alkyl group, a hydroxy alkyl group), and a cyclopentylene group (e.g., a 1,5-cyclopen group, or an aryl group; R1 and R2 independently represent tanediyl group). a hydrogen atom, an alkyl group, or an alkoxyalkyl group; R3 represents a hydrogen atom, a methyl group, or a methyl [0113] Examples of the arylene group having a carbon group; X1 represents a divalent linkage group having a atom number of from 6 to 12 represented by X1 include a carbon atom number of from 2 to 12; X2 represents a phenylene group, and a naphthylene group. divalent linkage group, a trivalent linkage group, a tetrava [0114] Examples of the divalent group represented by X2 lent linkage group, or include the same as those denoted in the divalent linkage having a carbon atom number of from 2 to 12 represented by X1. Examples of the divalent group represented by X2 further include those in Which up to ?ve methylene groups of the divalent saturated hydrocarbon group above are replaced by oxygen atoms. [0115] Examples of the trivalent group represented by X2 include an ethanetriyl group, a propanetriyl group, a butan [0106] in Which Z represents a hydrogen atom, an alkyl etriyl group, a pentanetriyl group, a hexanetriyl group, a group, an alkenyl group, an aryl group, a halogen atom, an heptanetriyl group, a octanetriyl group, a nonanetriyl group, alkoxy group, or a heterocyclic group, p is an integer of from a decanetriyl group, an undecanetriyl group, a dodecanetriyl 1 to 4, and q is an integer of from 1 to 3; D1 and D2 group, a cyclohexanetriyl group, a cyclopentanetriyl group, independently represent a divalent linkage group having a a benZenetriyl group and a naphthalenetriyl group. carbon atom number of from 1 to 5; E represents an divalent group having a carbon atom number of from 2 to 12, an [02116] Examples of the tetravalent group represented by aliphatic group having a 5- to 7-membered heterocyclic ring X include a propanediylidene group, a 1,3-propanediyl-2 containing one or tWo kinds of the atom selected from the ylidene group, a butanediylidene group, a pentanediylidene group consisting of a nitrogen atom, an oxygen atom and a group, a hexanediylidene group, a heptanediylidene group, sulfur atom, an arylene group having a carbon atom number an octanediylidene group, a nonanediylidene group, a of from 6 to 12, or a 5- or 6-membered aromatic heterocyclic decanediylidene group, an undecanediylidene group, a US 2005/0048403 A1 Mar. 3, 2005

dodecanediylidene group, a cyclohexanediylidene group, a [0124] In the aliphatic group having a 5- to 7-membered cyclopentanediylidene group, a benZenetetrayl group and a heterocyclic ring containing one or tWo kinds of the atom naphthalenetetrayl group. selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, represented by E, the 5- to [0117] Examples of the alkyl group represented by Z 7-membered heterocyclic ring is, for example, pyridine, include a methyl group, an ethyl group, a propyl group, a furan, pyrrole, pyraZole, imidaZole, oxaZole, thiaZole, pyri butyl group, a pentyl group, an isopentyl group, a 2-ethyl midine, pyridaZine, pyran, thiophene, isoxaZole, pyrroline, hexyl group, an octyl group and a decyl group. imidaZoline, pyraZolidine, pyraZoline, piperidine, pipera [0118] Examples of the alkenyl group represented by Z Zine, morpholine, or quinuclidine. include a 2-propenyl group, a butenyl group, a 1-methyl-3 [0125] Examples of the aliphatic group include a divalent propenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group having a carbon atom number of from 2 to 12 having group, and a 4-hexenyl group. Examples of the aryl group the heterocyclic ring described above. The divalent group represented by Z include a phenyl group, a m-chlorophenyl described above is the same as those denoted above in the group, a tolyl group, and a naphthyl group. divalent linkage group having a carbon atom number of [0119] Examples of the halogen atom represented by Z from 2 to 12 represented by X1. include a ?uorine atom, a chlorine atom, a bromine atom and [0126] Examples of the arylene group having a carbon an iodine atom. atom number of from 2 to 12 represented by E include a [0120] Examples of the alkoxy group represented by Z phenylene group and a naphthylene group. include a methoxy group, an ethoxy group, a propoxy group, [0127] Examples of the heterocyclic ring of the 5- or and a butoxy group. 6-membered aromatic heterocyclic ring group represented by E include rings such as furan, pyrrole, pyraZole, imida [0121] Examples of the heterocyclic group represented by Zole, oxaZole, thiaZole, 1,2,3-oxaZole, 1,2,3-triaZole, 1,2,4 Z include a pyridyl group, a pyrrolyl group, a 2-methylpyr triaZole, 1,3,4-thiadiaZole, pyridine, pyridaZine, pyrimidine, rolyl group, an indolyl group, an imidaZolyl group, a furyl pyraZine, s-triaZine, benZofuran, indole, benZothiophene, group, a thiaZolyl group, and a pyrimidinyl group. benZimidaZole, benZothiaZole, purine, quinoline, and iso [0122] Examples of the divalent group having a carbon quinoline. atom number of from 1 to 5 represented by D1 or D2 include [0128] Each of the substituents denoted in formula (I) a methylene group, a trimethylene group, a tetramethylene above may further have a substituent. group, a propylene group, an ethylethylene group, a pen [0129] The compound represented by formula (I) above tamethylene group, and a cyclopentylene group. can be synthesiZed by a knoWn method, for example a [0123] The divalent group having a carbon atom number method described in Japanese Patent No. 2509288. of from 2 to 12 by E is the same as those denoted above in [0130] Exempli?ed compounds of the compound repre the divalent linkage group having a carbon atom number of sented by formula (I) Will be listed beloW, but the present from 2 to 12 represented by X1. invention is not limited thereto.

R2

Compound No. R4 Q1 m a R1 R2 b X1 X2 c R3 11

1-1 _ / 3 1 H H 0 —C2H4 1 cH3 3 \

1-2 _ / 3 1 cH3 H 0 —C2H4 1 cH3 3 \

1-3 C2H4OH / 3 1 H H 0 _ C2H4 1 cH3 2 \

1-4 _ / 3 1 H H 1 *1C2H4 1 cH3 3 N\

US 2005/0048403 A1 Mar. 3, 2005 10

-continued zwoloipgiodwoig?fgiobwk

#0 0% _ QYOJOJLQQLELQNWAEQQLLOYQ

[-18 l?g 1M0 TR O

QYOWOJLQQLELJWAEQQLNOYQO O

US 2005/0048403 A1 Mar. 3, 2005 13

-continued I-28

O

O NHWEiO/VOWKK O T giOA/Ow/kO O O O

[0132] An ethylenically unsaturated compound repre 7-membered cycloalkylene group, an arylene group having sented by the following formula (II) is also preferred. a carbon atom number of from 6 to 12, or a 5- or 7-mem bered heterocyclic group; d and e independently represent an integer of from 1 to 4; g is an integer of from 2 to 4; and f is an integer of from 1 to g, provided that plural groups having the same de?nition may be the same or different. Formula (II) R5 [0135] In formula (II), When (g-f) is tWo or more, plural R8’s may be the same or different. It is preferred that g and f are the same. When R8 is an alkyl group, or a hydroXyalkyl group, R8 has a carbon atom number of preferably from 2 to 8, more preferably from 2 to 4. When R8 is an aryl group, R8 is preferably monocyclic or bicyclic, and more preferably monocyclic. The aryl groups include those having a sub stituent such as an alkyl group, an alkoXy group or a halogen atom. [0133] Wherein Q2 represents [0136] When R5 and R6 independently represent an alkyl group, or an alkoXy group, R5 and R6 independently has a carbon atom number of preferably from 1 to 5. R7 is preferably a methyl group. [0137] D3 and D4 may be the same or different, and D3 and D4 are preferably 6-member saturated heterocyclic groups having tWo nitrogen atoms, respectively. [0138] When G is the saturated hydrocarbon group, G has a carbon atom number of preferably from 2 to 6. When G is the arylene group, G is preferably phenylene, When G is the cycloalkylene group, G is preferably cycloheXylene group, and When G is the heterocyclic group, G is preferably a 5 or 6-membered heterocyclic group containing a nitrogen atom or a sulfur atom. [0134] R8 represents an alkyl group, a hydroXyalkyl [0139] In order to prepare a compound of formula (II) in group, or an aryl group; R5 and R6 independently represent Which Q2 is N, and g and f are the same, for eXample, a hydrogen atom, an alkyl group, or an alkoxyalkyl group; glycidylacrylate or hydroXyacrylate is reacted With alky and R7 represents a hydrogen atom, a methyl group, or a lamine. Other compounds can be prepared in the same Was methyl group; D3 and D4 independently represent a divalent as above. saturated hydrocarbon group having a carbon atom number of from 1 to 5; G represents a saturated hydrocarbon group [0140] EXempli?ed compounds of the compound repre having a carbon atom number of from 2 to 12, a 5- to sented by formula (II) Will be listed beloW.

US 2005/0048403 A1 Mar. 3, 2005 15

[0141] The light sensitive layer of the planographic print 2,4,6-tri?uorophenyl, bis(cyclopentadienyl)-Ti-bis-2,6 ing plate material of the invention contains the above di?uorophenyl, bis(cyclopentadienyl)-Ti-bis-2,4 ethylenically unsaturated compound in an amount of pref di?uorophenyl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6 erably from 5 to 99% by Weight, more preferably from 10 to penta?uorophenyl, bis(methylcyclopentadienyl)-Ti-bis-2,3, 99% by Weight, and still more preferably from 20 to 97% by 5,6-tetra?uorophenyl, bis(methylcyclopentadienyl)-Ti-bis Weight. 2,4-di?uorophenyl (IRUGACURE 727L, produced by Ciba Specialty Co., Ltd.), bis(cyclopentadienyl)-bis(2,6-di?uoro [0142] (Binder) 3-(pyr-1-yl)phenyl) titanium (IRUGACURE 784, produced [0143] As the binder used in the light sensitive layer of the by Ciba Specialty Co., Ltd.), bis(cyclopentadienyl)-bis(2,4, planographic printing plate material of the invention, a 6-tri?uoro-3-(pyr-1-yl)phenyl) titanium, and bis(cyclopen polymer With a Weight average molecular Weight of from tadienyl)-bis(2,4,6-tri?uoro-3-(2,5-dimethylpyr-1-yl)phe 15,000 to 500,000 and With an acid value of 30 to 200 is nyl) titanium. preferably used, Which has the ethylenically unsaturated bond as contained in the ethylenically unsaturated com [0150] (Polyhalogenated Compound) pound described above. KnoWn polymers having no ethyl [0151] Examples of the polyhalogenated compound enically unsaturated bond can be used singly or in combi include carbon tetrachloride, phenyltribromomethylphenyl nation With the above-described polymer. sulfone, phenyl trichloromethyl ketone, and compounds [0144] (Polymerization Initiator) Examples of the poly described in Japanese Patent O.P.I. Publication No. meriZation initiator include a metallocene compound such as 53-133428, Japanese Patent Publication Nos. 57-1819 and ferrocene or titanocene, a triarylsulfonium compound, a 57-6096, and US. Pat. No. 3,615,455. Of these, polyhalom diaryliodonium compound, polyhalogenated compound, a ethylsulfone, polyhalomethyloxaZole, or a polyhaloacetyl bisimidaZole compound, a benZoin derivative, and an compound is preferred. N-phenylglycine derivative. In the invention, a metallocene [0152] As the polyhaloacetyl compound, polyhaloacetyla compound or a polyhalogenated compound is preferred. mide compound is preferred. For example, a polyhaloacetyl [0145] (Metallocene Compound) compound represented by formula (2) and preferably a compound (polyhaloacetylamide compound) represented by [0146] The “metallocene” is a bicyclopentadienyl com formula (3) are cited. plex, (C5H5)2M, Which is comprised of tWo cyclopentadiene rings and a transition metal. Typical examples thereof R21—CX2—(C:O) —R22 Formula (2) include ferrocene (C5H5)2Fe, and (C5H5)2M, in Which M is [0153] Wherein R21 represents a hydrogen atom, a chlorine Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os or Ir. atom, a bromine atom, an alkyl group, an aryl group, an acyl [0147] The cyclopentadiene ring of the metallocene does group, an alkylsulfonyl group, an arylsulfonyl group or a not exhibit nonsaturability, but aromaticity like a benZene cyano group; R22 represents a hydrogen atom or a monova ring. The cyclopentadiene ring is susceptible to electrophilic lent substituent, provided that R21 and R22 may combine substitution as in aromatic compounds, and can be acylated, With each other to form a ring; and X represents a chlorine alkylated, sulfonated or methacrylated. atom or a bromine atom. [0148] Typical examples of the titanocene compound pref CX3—(C:O) —Y—R23 Formula (3) erably used Will be explained beloW. [0154] Wherein R23 represents a monovalent substituent; Y represents —O— or —NR24—, in Which R24 represents a [0149] Examples of the titanocene compound include hydrogen atom or an alkyl group, provided that R23 and R24 those disclosed in Japanese Patent O.P.I. Publication Nos. may combine With each other to form a ring; and X 6341483 and 2-291. Preferred examples of the titanocene compound include bis(cyclopentadienyl)-Ti-dichloride, bis represents a chlorine atom or a bromine atom. (cyclopentadienyl)-Ti-bisphenyl, bis(cyclopentadienyl)-Ti [0155] Typical examples of the compound represented by bis-2,3,4,5,6-penta?uorophenyl, bis(cyclopentadienyl)-Ti formula (2) or (3) Will be listed beloW, but the invention is bis-2,3,5,6-tetra?uorophenyl, bis(cyclopentadienyl)-Ti-bis not limited thereto.

BRl BRZ Br Br Br MB. O Br