Photoinitiators

Abstract: A photoinitiator complex has the formula (I): D⁺ is a cationic dye moiety. R¹ is a benzyl or substituted benzyl group, R², R³ and R⁴ are aryl or substituted aryl groups. The photoinitiator is capable of absorbing actinic radiation and producing free radicals.

Description: The present invention relates to a novel class of photoinitiators. U.S. Patents 4,772,541 and 4,772,530 to The Mead Corporation disclose a novel class of photoinitiators which are compounds consisting of an ionic photoreducible or photooxidizable dye and a counter ion which absorb light and generate a free radical. The preferred photoinitiators are complexes of a cationic dye and an alkyltriaryl borate anion. While the photoiniators disclosed therein are suitable for many applications we have sought to design photoinitiators which provide higher film speeds. The present invention arises out of this work. According to the present invention, we provide a photoinitiator complex of the formula (I): capable of absorbing actinic radiation and producing free radicals, D + being a cationic dye moiety; R 1 is a benzyl or substituted benzyl group, and R 2 , R 3 and R 4 are aryl or substituted aryl groups. The invention also extends to photohardenable compositions comprising a free radical polymerizable or crosslinkable compound and a photoinitiator complex as aforesaid, and also to photosensitive material comprising a support having a layer of such a photohardenable composition coated thereon. The characteristics of the basic borate anion may be altered to improve stability, speed of polymerization, and solubility by incorporating onto the benzyl and aryl rings various electron donating groups such as amino, dimethylamino, hydroxy, methoxy, t-butyl, or methyl; or various electron withdrawing groups such as phenyl, fluro, chloro, bromo, iodo, -COOH, -COOR where R is a lower alkyl group, methylcarbonyl, trifluoromethyl, cyano, methylsulfone, or nitro. Representative examples of the benzyl groups represented by R 1 include benzyl, tert-butylbenzyl, fluorobenzyl, chlorobenzyl, trifluoromethylbenzyl, methoxybenzyl, dimethylaminobenzyl and methylbenzyl. Representative examples of the aryl groups represented by R 1 , R 2 and R 3 include phenyl, naphthyl, anisyl, methylphenyl, dimethylphenyl, fluorophenyl, chlorophenyl, methoxyphenyl, tert-butylphenyl and di-tert-butylphenyl. Preferably D + is represented by the formula II: where y 1 and y 2 are the same or different and represent an oxygen atom, a sulfur atom, a selenium atom, a vinyl group, >C(CH 3 ) 2 , or >N-R 7 where R 7 is a short chain alkyl group; n is 0, 1, 2, or 3; z is 1 to 4; R 5 and R 6 are alkyl groups and preferably an alkyl group having at least 4 and preferably at least 7 carbon atoms; X is selected based on the desired absorption characteristics of the cationic dye-borate anion complex. X may be a hydrogen atom; an electron donating group such as amino, dimethylamino, hydroxy, methoxy, t-butyl, or methyl; or X may be an electron withdrawing group such as phenyl, fluoro, chloro, bromo, iodo, -COOH, -COOR where R is a lower alkyl group, methylcarbonyl, trifluoromethyl, cyano, methylsulfonyl, or nitro. We have shown that only a small amount of n-alkyl borate radicals in cyanine borate-initiated polymerization of acrylates escape the solvent cage to initiate polymerization. Recombination of the borate and cyanine radicals may be a significant factor in the loss of productive radicals. The benzyltriarylborates of the present invention provide a more stable radical for initiating free radical polymerization and should be less likely to recombine with the cyanine radical before diffusing from the solvent cage. Consequently, these cyanine-benzyltriarylborate photoinitiators should provide media with greater photographic speed than previous initiators which use n-butylborate or other less stable borate compounds. While our benzyltriarylborates show an increase in polvmerization speed over n-butylborate, they are still somewhat slow in a positive working system. However, they would be useful in a negative working or direct write system wherein polymerization is inhibited upon exposure to light. Methods useful in making our present photoinitiators, typical photohardenable compositions, and photosensitive materials are described in U.S. Patents 4,772,530 and 4,772,541. Useful dyes form photoreducible but dark stable complexes with borate anions and can be cationic methine, polymethine, triarylmethane, indoline, thiazine, xanthene, oxazine and acridine dyes. More specifically, the dyes may be cationic cyanine, carbocyanine, hemicyanine, rhodamine and azomethine dyes. The dyes should not contain groups which would neutralize or desensitize the complex or render the complex poorly dark stable. As a general rule, useful cationic dye-borate anion complexes must be identified empirically, however, potentially useful cationic dye and borate anion combinations can be identified by reference to the Weller equation (Rehm, D. and Weller, A., Isr. J. Chem. (1970), 8, 259-271), which can be simplified as follows. ΔG=E ox -E red -E hv where ΔG is the change in the Gibbs free energy, E ox is the oxidation potential of the borate anion, E red is the reduction potential of the caticnic dye, and E hv is the energy of light used to excite the dye. Useful complexes will have a negative free energy change. Similarly, the difference between the reduction potential of the dye and the oxidation potential of the borate must be negative for the complex to be dark-stable, i.e., E ox -E red >0. As indicated, Eq. 1 is a simplification and it does not absolutely predict whether a complex will be useful or not. There are a number of other factors which will influence this determination. One such factor is the effect of the monomer on the complex. It is also known that if the Weller equation produces too negative a value, deviations from the equation are possible. Furthermore, the Weller equation only predicts electron transfer, it does not predict whether a particular dye complex is an efficient initiator of polymerization. The equation is a useful first approximation. The most typical example of a free radical addition polymerizable or crosslinkable compound useful in our photohardenable compositions is an ethylenically unsaturated compound and, more specifically, a polyethylenically unsaturated compound. These compounds include both monomers having one or more ethylenically unsaturated groups, such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation. Such compounds are well known in the art and include acrylic and methacrylic esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol; and acrylate or methacrylate terminated epoxy resins and acrylate or methacrylate terminated polyesters. Representative examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylol-propane triacrylate (TMPTA), pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentacrylate (DPHPA), hexanediol-1,6-dimethacrylate, and diethyleneglycol dimethacrylate. The cationic dye-borate anion complex is suitably used in an amount up to about 1% by weight based on the weight of the photopolymerizable or crosslinkable species in the photohardenable composition. Preferably, the cationic dye-borate anion complex is used in an amount of about 0.2% to 0.5% by weight. While the cationic dye-borate anion complex can be used alone as the initiator, film speeds still tend to be somewhat low and oxygen inhibition is observed. We have found that it is preferable to use the complex in combination with an autoxidizer, particularly N,N-dialkylanilines. An autoxidizer is a compound which is capable of consuming oxygen in a free radical chain process. Representative examples of N,N-dialkylanilines useful in our photohardenable compositions are 4-cyano-N, N-dimethylaniline, 4-acetyl-N,N-dimethylaniline, 4-bromo-N, N-dimethylaniline, ethyl 4-(N,N-dimethylamino) benzoate, 3-chloro-N,N-dimethylaniline, 4-chloro-N,N-dimethylaniline, 3-ethoxy-N,N-dimethylaniline, 4-fluoro-N,N-dimethylaniline, 4-methyl-N,N-dimethylthioaniline, 4-amino-N,N-dimethylaniline, 3-hydroxy-N,N-dimethylaniline, N,N,N',N'-tetramethyl-1,4-dianiline and 4-acetamido-N,N-dimethylaniline, Preferred N,N-diialkylanilines are 2,6-diisopropyl-N,N-dimethylaniline, 2,6-diethyl-N,N-dimethylaniline, N,N,2,4,6-pentamethylaniline (PMA) and p-t-butyl-N,N-dimethylaniline. The autoxidizers are preferably used in concentrations of about 4-5% by weight. Thiols and disulfides also appear to enhance film speed although the mechanism is not clear. Particularly preferred thiols are selected from mercaptobenzoxazoles, mercaptotetrazines, mercaptotriazines and mercaptobenzothiazoles. Representative examples include 2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-mercapto-1-methylimidazole, 2-mercapto-5-methylthio-1,3,4-thiadiazole, 5-n-butylthio-2-mercapto-1,3,4-thiadiazole, 4-methoxybenzenethiol, 1-phenyl-1H-tetrazole-5-thiol, 4-phenyl-4H-1,2,4-triazole-3-thiol, 2-mercaptobenzimidazole, pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptoproprionate), trimethylolpropane tris(mercapto-acetate), 4-acetamidothiophenol, mercaptosuccinic acid, dodecanethiol, 2-mercaptopyridine, 4-mercaptopyridine, 2-mercapto-3H-quinazoline, and 2-mercaptothiazoline. Disulphides as described in our copending Patent Application 90302540.1 (Publication No: EP-A-0387087) are also useful. The photohardenable compositions may be used to prepare photocurable resists, photoadhesives, photocurable coatings and photocurable inks. They may also be microencapsulated and used in the full color panchromatic imaging system described in U.S. Patent 4,772,541. A preferred method for microencapsulating the composition is described in our European Patent Application 88311479.5 (Publication No: EP-A-0319337). A preferred developer material is described in U.S. Patent 4,859,561. Benzyltriphenyl borates can be made by the reaction of either benzylmagnesium chloride or benzyllithium with the corresponding triphenylboron. The resulting borate is metastisized with an appropriate dye. Example To compare the photographic characteristics of dye complexes in accordance with the present invention and previous dye complexes, dye complexes in accordance with the present invention and comparative complexes were encapsulated with photopolymerizable compositions. The encapsulated compositions were coated on a sheet of AlPET in an amount of 6 g/cm 2 using a slot head coater and dried. The coated compositions were exposed through a 30 step wedge and subjected to densitometry. The results are shown in Table 1. Initiator Dmax Dmin Log 10% sens. Log 90% sens. DR Gamma Magenta System Green light exposure SI-253 (N-Butyltriphenylborate) 2.57 0.09 3.17 2.90 0.37 5.44 SI-308 (Benzyltriphenylborate) 2.59 0.09 3.06 2.78 0.26 7.11 Differences +0.11 +0.12 Cyan System Red light exposure SI-252 (N-Butyltriphenylborate) 2.47 0.05 3.74 3.11 0.53 3.06 SI-309 (Benzyltriphenylborate) 2.52 0.08 3.53 2.88 0.55 2.95 Differences +0.21 +0.23 The data shows an increase in speed of two steps for the cyan photoinitiator system using benzyltriphenylborate over the comparative system made with n-butylborate, while the magenta system showed a one step improvement in speed.

Claims: A photoinitiator complex of the formula (I): capable of absorbing actinic radiation and producing free radicals, D + being a cationic dye moiety; characterised in that R 1 is a benzyl or substituted benzyl group, and R 2 , R 3 and R 4 are aryl or substituted aryl groups. A photoinitiator complex according to Claim 1, further characterised in that the anionic borate moiety is benzyltriphenylborate. A photoinitiator complex according to Claims 1 or 2, further characterised in that D + is represented by the formula: where Y 1 and Y 2 are the same or different and represent an oxygen, a sulphur, a selenium atom, a vinyl group, >C(CH 3 ) 2 , or >N-R 7 where R 7 , is a short chain alkyl group; n is 0, 1, 2 or 3; Z is 1 to 4; R 5 and R 6 represent alkyl groups and X represents a hydrogen atom, an electron withdrawing group or an electron donating group. A photoinitiator complex according to Claim 3, further characterised in that said cationic dye is selected from cationic cyanine, carbocyanine and hemicyanine dyes. A photohardenable composition which comprises a free radical polymerizable or crosslinkable compound and a photoinitiator complex according to any preceding Claim. A photohardenable composition according to Claim 5, further characterised in that said complex is present in an amount of up to about 1% by weight, and preferably from about 0.2% to 0.5% by weight, based on the weight of the photohardenable composition. A photohardenable composition according to Claims 5 or 6, further characterised in being microencapsulated. A photohardenable composition according to any of Claims 5, 6 or 7, further characterised in additionally comprising an autooxidizer. A photosensitive material comprising a support having a layer of photohardenable composition according to any of Claims 5 to 8 on the surface thereof.

Inventors: SHANKLIN MICHAEL SAMUEL, SHANKLIN, MICHAEL SAMUEL
Applicants: CYCOLOR INC, CYCOLOR, INC.
Application year: 1990
Main classification: G03F7
IPC codes: G03F7, C08F4