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And Novel Pyrylium Salts for Use Therein curopaiscnes raieniamt European Patent Office © Publication number: 0 213 893 Office europ6en des brevets A2 bUKUPcAN PATENT APPLICATION Application number: 86306476.2 © int. ci.4: C 08 G 59/68 C 07 D 309/34 (§) Date of filing: 21.08.86 §) Priority: 02.09.85 IE 2158/85 © Applicant: LOCTITE (IRELAND) Ltd. Whitestown Industrial Estate Dublin 14(IE) *3) Date of publication of application : 11.03.87 Bulletin 87/11 © Inventor: Woods, JohnG. 138 Stillorgan Wood Upper Kilmacud Road Si) Designated Contracting States: County Dublin(IE) DE FR GB © Inventor: Rooney, JohnM. 64 Water Street South Glastonbury Connecticut 06073(US) © Representative: Merchant, James Ian et al, Elkington and Fife High Holborn House 52/54 High Holborn London WC1V6SHIGB) **) Photopolymensable compositions containing substituted pyrylium salts as photoinitlators; and novel pyrylium salts for use therein. [?) A photopolymerisable composition comprising (a) at least one material polymerisable by an acid- atalysed mechanism, and (b) a pyrylium salt having at least one phenyl substituent taring an electron donor group in the para- and/or ortho- iosition on the phenyl ring, and a hexafluoroantimonate or exafluoroarsenate counterion. Suitable electron donor groups include hydrocarbyloxy aarticularly alkoxy or alkenoxy), hydroxy, amide, phenoxy, liohydrocarbyl, thioaryl, and phenyl ester groups. The com- ositions have improved long term dark stability. Novel pyrylium salts are disclosed having at least one henyl substituent bearing an alkoxy or alkenoxy group in the era- and'or ortho- position on the phenyl ring and a hexa- uoroantimonate or hexafluoroarsenate counterion. Prefer- }d compounds are triarylpyrylium salts in which from one to uee of the phenyl groups has alkoxy or alkenoxy substi- jents in the para position on the phenyl groups in the 2, 6 ositions on the pyrylium ring. jyuun rnniing company Lia. 0213893 -l- Photopolymerisable compositions containing substituted pyrylium salts as photoinitiators ; and novel pyrylium salts for use therein This Invention relates to photopolymeri sable compositions 5 capable of polymerisation by an acid-catalysed mechanism under the influence of ultra-violet and/or visible light. The invention also relates to novel substituted pyrylium salts which are useful In catalysing such polymerisation reactions. The use of Lewis Acid catalysts in cationically polymeri sable 10 compositions is well known, as discussed in US Patent 4 058 400 Crivello, for example. The development of photocurable cationic systems is of great interest because they are not sensitive to oxygen and can be made up in one-package formulations which do not require mixing of ingredients or heat 15 at the point of use. US Patent 4 139 655 Tsao describes photo- curable compositions comprising an epoxy resin and a photo- decomposable thiopyrylium salt of the formula here K^, k*2 and K3 may De nyarogen, di^vi cum-aiumy 1 5 12 carbon atoms, 0 10 carbon atoms, cycloalkyl containing to ryl containing 6 to 12 carbon atoms and substituted erivatives thereof, M is a metal or metalloid, X is a halogen whole adical, a is a whole number from 1 to 10 and n is a umber from 1 to 3. Typical MXan" anions include BF4 , PFg the like. Among the thiopyrylium salts isFg , SbFg and lescribed therein as catalysts are 2,6-di phenyl -4-p- Kthoxyphenyl -thiopyrylium tetraf luoroborate , 2,6-diphenyl-4-p- nethoxyphenyl -thiopyrylium hexafluorophosphate , 2,4r6-tri-p- nethoxyphenyl -thiopyrylium tetraf luorborate and 2,4,6-tri-p- nethoxyphenyl -thiopyrylium hexafluorophosphate. JS Patent 4 405 765 Demmler et al describes a curable resin catalyst, composed of an epoxy resin, and a pyrylium salt as a rfith or without a metal chelate or metal salt as a co-catalyst. The pyrylium salt is of the formula IB rfhere R1 and Rb are identical and are each alky t or R2, R3 and R4 aralkyl, each of 1 to 8 carbon atoms, and alkyl, are identical or different and are each hydrogen or atoms or alkaryl or cycloalkyl, each of not more than 8 carbon naphthyl an unsubstltuted or alkyl substituted phenyl, , indenyl, indanyl or fluorenyl group or a heterocyclic is substituent containing one or two heteroatoms. X' a non- BF4 nucleophilic, weakly basic anion such as AsFs , SbFg , , CIO" preferably AsF" PFg , CF3SO3 or , . D21 3893 -3- JS Patent 4 474 868 Yamaoko et al describes a photo- polymerisation initiator composition comprising an organic peroxide and a pyrylium salt, thiapyryllum salt or seleno- pyrylium salt of the formula 5 wherein Rjt R2 and R3 each represents a hydrogen atom, an alkyl group, a haloalkyl group, an ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphthyl group, an alkyl phenyl group, an alkoxyphenyl group, a hydroxyphenyl 10 group, a halophenyl group, a nltrophenyl group, an aminophenyl group, a nitro group, an amino group or a hydroxy 1 group, X represents an oxygen atom, a sulfur atom or a selenium atom, and Y represents an anion functional group. Among the salts of formula 1 are 4-(4-butoxyphenyl )-2,6- 15 di phenyl pyrylium perchlorate; 2,6-bis (4-ethyl phenyl )-4-(4- methoxyphenyl )-pyrylium fluoroborate; 4-(4-butoxyphenyl )-2,6- bis (4-methoxyphenyl )-thiapyryli urn fluoroborate; 2,6-bis (4- ethyl phenyl )-4-(4-methoxyphenyl )-pyryli urn fluoroborate; 4- (4- butoxyphenyl ) -2, 6-d1 phenyl thiapyrylium perchlorate, fluoro- antimonate, fluorophosphate or fluoroborate; 2,4,6-tri (4-methoxyphenyl )thiapyryli urn perchlorate; and 2,6-bis (4- methoxyphenyl )-4-phenyl thiapyrylium fluoroborate. In a publication entitled "Photochemical ly initiated epoxide polymerisations" in Polymer Preprints, March 1982, 323-324, A. 25 Ledwith has reported that triarylpyrylium salts of the formula r h ) r Ar r = phenyl, p-toiyi are extremely eTTective pnotoimx.iai.orb iui L-jruuneAcuc polymerisation if the anion is SbFs-, whereas poor results were obtained for BF4- salts and PFs- salts. work the The present inventors have carried out further on use anion 5 of phenyl substituted pyrylium salts containing SbFe- have found that the as cationic photoinitiators. However they usefulness of these initiators is limited since the stability is in the dark of compositions containing these initiators poor. that if a phenyl 0 The present inventors have found surprisingly substituent bearing an electron donor group is present on the of pyrylium salt, then the long term dark stability a it photopolymeri sable composition is greatly increased, making useful for commercial applications. L5 The invention tnereTore provioes a piiuuupuijHKi isauic composition comprising acid-catalysed a) at least one material polymeri sable by an mechanism, and substituent b) a pyrylium salt having at least one phenyl ortho- 20 bearing an electron donor group in the para- and/or luoroantimonate or position on the phenyl ring, and a hexaf hexafluoroarsenate counterion. known The electron donor group may be selected from the range 021 3893 of such groups which can be substituted on a phenyl group, for example:- hydrocarbyloxy (-OR) hydroxy (-0H) 5 ami de (-NHCOCH3) - phenoxy (-0 Ar) thiohydrocarbyl (-SR) thioaryl (-SAr) phenyl ester (-OC0R) 10 wherein R represents hydrocarbyl and Ar represents aryl . The preferred electron donor group is hydrocarbyloxy, more particularly alkoxy or alkenoxy. This Invention also relates to novel pyrylium salts having at least one phenyl substituent bearing an alkoxy or alkenoxy 15 group 1n the para- and/or ortho- position on the phenyl ring and a hexafluoroantlmonate or hexaf 1 uoroarsenate counterion. The pyrylium salt may suitably be added in an amount from 0.01- 20%, preferably 0.1-10%, and more particularly 0.5-3%, by weight of the weight of the composition. 20 The pyrylium salt may be synthesised by known methods as described for example in US Patent 4,139,655 Tsao. This patent describes the preparation of 2, 4, 6-tri phenyl pyrylium salts by a coupling and cyclisatlon reaction of acetophenone and benzaldehyde. Pyrylium salts containing phenyl substituents 25 bearing hydrocarbyloxy electron donor groups can be prepared by this procedure using the corresponding hydrocarbyloxy substituted acetophenone and benzaldehyde derivatives. Examples of the syntheses of such derivatives are given below where the hydrocarbyloxy group is alkenoxy (Example 1) and alkoxy (Examples 2, 5, 6 and 7). )21 Similarly, pyrylium salts containing phenyl substituents bearing hydroxyl electron donor groups may be prepared using the corresponding hydroxy-substituted acetophenone and benzaldehyde derivatives. i Pyrylium salts containing phenyl substituents bearing acetamide electron donor groups may be prepared by treating mixtures of corresponding amine-substituted aromatic 1,3-dicarbonyl compounds and acetophenone derivatives with acetic anhydride by methods analogous to those outlined in "Comprehensive Organic LO Chemistry" by Barton and Ollis, Vol. 4, page 617 (Pergamon Press 1979). In this case, the anhydride functions as both a dehydrating/cycllsation and an acetyl ation reagent. Pyrylium salts containing phenyl substituents bearing a phenoxy electron donor group can be prepared by the base catalysed 15 addition of the corresponding phenoxy-substituted acetophenone to a substituted or unsubstituted 1,3-di phenyl prop-l-en-3-one to yield the corresponding 1,5 diketone intermediate. Cyclization and oxidation of the intermediate in the presence of acetic anhydride and ferric chloride yields the required 20 pyrylium salt. Thiohydrocarbyl and thioaryl groups may be introduced by reacting the corresponding thiohydrocarbyl and thioaryl substituted acetophenone and/or benzaldehyde by the method of Tsao referred to above. 25 Pyrylium salts containing phenyl groups bearing electron donor ester groups may be synthesised from the corresponding hydroxy phenyl (I.e. phenol) pyrylium salts by treatment with the required acid chloride. In the special case of phenyl acetate-substituted pyrylium salts, this may be achieved 30 by the treatment of mixtures of hydroxyphenyl -substituted 1,3-dicarbonyl compounds and acetophenone derivatives with acetic anhydride. In this case, the anhydride functions as both a dehydrating/cycl ization and acetylation reagent.
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