CA1206031A - Use of substituted glyoxalate derivates as photoinitiators - Google Patents

Abstract

PROCESS AND COMPOSITIONS FOR PHOTOPOLYMERIZATION

ABSTRACT OF THE DISCLOSURE
The present invention relates to the use of aryl-glyoxalate, ring substituted arylglyoxalate and heterocy-clic glyoxalate compounds as photoinitiators in the photo-polymerization of monomeric and polymeric compositions under the influence of actinic radiation.
BACKGROUND OF THE INVENTION
Photopolymerization of unsaturated compositions where-in a photoinitiating compound is included in the polymerizable mass is well known in the art. The process has many advantages over thermal polymerization and is particularly useful where long holding life combined with rapid hardening at low tempera-ture is desirable. Photoinitiating compounds must absorb light and utilize the energy so acquired to initiate polymerization.
A large number of compounds have been found useful as photoinitiators for the polymerization of unsaturated com-pounds. Among those heretofore in most common usage in in-dustry are the benzoin ethers of primary and secondary alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol. Also, compounds such as phenyl glyoxal and 1-phenyl butane-1,2-dione are disclosed as photosensitizers in U.S. Patent No. 2,413,973. Additionally, various acetophenone compounds such as 2,2-diethoxyacetophone are claimed to have photoinitiating capability in Patent NO. 3,715,293.
While particular industrial applications often dictate certain requisite characteristics the primary determinants of

Description

~2~3~L

PROCESS AND COMPOSITIONS FOR PHOTOPOLYMERIZATION

ABSTRACT OF THE DISCLOSURE
The present invention relates to the use of aryl-glyoxa~late, ring substituted arylglyoxalate and heterocy-clic glyoxalate compounds as photoinitiators in the photo~
polymeriza~ion of tnonomeric and polymeric compositlons under the influence of actinic radiation.
BACKGRO~ND OF THE INVENTION
Photopolymerization o~ unsaturated compositions where-in a photolni.tiating compound i9 included in the polymerizable mass is well known in thé art~ The process has many advantages over thermal polymexization and is particularly useEul where long holding life co~bined with rap:icl hardening at low tempera-ture is desirable. Photoinitiating compounds must absorb light and utilize the energy so acquired to initia~e poly~erization~
A large number of compounds have been found useful as photoinitiators for the polymerization of unsatura~ed com-pounds. Among those heretofore in most common usage in in-dustry are the benzoin ethers of primary and secondary alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and i~obutyl alcohol. Al.so, compounds such as phenyl glyoxal and 1 phenyl butane-1,2-dione are disclosed as photosensitizers in U~S. Patent No. 2~413,973. Additionally, vaxious acetophenone compounds ~uch as 2,2-diethoxyacetophenone are cl~imed to haYe photoinitiating capability in U.SO Patent No. 3~7159293.
While particular industrial appli~ations oten dictate certain requisite characteristics, the primary determinants o:E

~36~?3~ c-l~569 universal application in the selec:tion of a suitable photoini-tiating compound are it~s level of reactivity and its ef~ect upon storage stabîlity when combined with the photopolymerizable medium wherein it is to function. This latter characteristic is significant in view of the desirability of one-component systems which wlll not gel prior to use.
While compounds in common use as photoinitiators do ef~ect rates of polymerization which are industrially acceptable and render photopolymerization superior to ~hermal polymeriza-lo tion in various applications, methods of achieving increased polymerization rates with increased stability are constantly being sought. Improved photoinitiators are part-icularly desir-able since photopolymerization techniques are gaining increas-ingly widespread acceptance due to the inherently lower equip-ment costs, reduction of vola~ile lemissions and reduced energy consumption which attend their use.
Collaterally, the ethers ~ benzoin, which are widely used as photoinitiation compounds, are not wholly satis~ac tory with regard to the one-component system storage stability

2~ factor. Any unsaturated system to which a benzoln e~her is added has considerably diminished dark storage stability and will gel prematurely. Various attempts have been made to remedy this deficiency of the benzoin compounds by including stabiliz-ing additives in the polymerization system. Thus, U.S. Patent

3,819,495 discloses the addition af organic chlorine containing compounds and copper compounds as a stablli2ation system while U~S~ Patent 3,819,496 teaches the use of organic chlorine com-pound~ wlth iron and/or manganese compounds for that purpose.
Many other stabilizers have been suggested and, while some ~ 3 ~ C-4569 improvements have been achieved in the stability of unsaturated systems containing benzoin-type photoinitiators, the necessity of incorporating stabilization compositions raises the cost of such systems appreciably while the results are still not wholly satis~actory.
Another highly desirable characteristic of a photoini-tiating composition is its capacity to ~unction acceptably in polymerizable systems which contain various pigments. This at-tribute is siignificant commercially because inorganic pigments ~-are one of the prime components of ~urface coating systems and contrLbute direc~ly to the useulness oE such systems by virtue of their protective ~unctlon, their decorative or artistic ~unctlon and other miscellaneous functions. The whi~e opaque plgments, characterized ~y titaniurn dioxide, are the most im-portant single group of pigments in use because o~ the predomi-nance of white as a color and because of the need to use white pigments in producing many tints and light hues o~ color.
With regard to rate of polymerization~ the resultant surface t~xture of the polymerized, pigmented coating and the e~fact of the photoinitiating compound on the color itself, none of the most widely used photoinitiating compounds is wholly ac-ceptable in titanium dioxide pigmented unsaturated systems.
It is an object of the present invention to introduce the use of a novel cla~s of polymerization photoinitiation com-pounds o enhanced reactivity.
Another object of the invention is to provide photoini tiating compounds which can be combined witn un~aturated com-pounds to form one-component polymerizable systems no~ sub-ject to premature gelation.

~; _ ~ 2~ 3 ~
A further obJect of the inventi.on is the provision of pigmentecl photopolymeri.zable composition$ ~h~rein a photo~
initlator of the ln~en~ion react~ a~ceptably while nnt adver~ely aEfecting the surface charac~eristics or the color of the resulting polymer~zed product.
SUMMARY ~F T~lE INVENTION
This invention relates to the polymerization, under th~ influence of light, of compositions subject to addition p~lymerizat-lon. More specifically3 the proces~ o ~he invan-tion relates to the use o a novel clas~ of phot~polymerizatlon photoinitial:ors of the general ~ormula:
O O
ll ll R' - C - C - OR
wherein R i9 a 9 ~raight or branched chaln hydrocarbon of ~rom 1-10 carbon atom~, aryl~ aralkyl or mono-, di- or trialkylsilyl and R' is a he~erocyclic radicalg aryl o~ 6 ~o 14 carbon atoms, phenyl or mono-, di- or polysubstituted phenyl with substituants selected from the group con~i~ting o~ alkylJ
alkoxy, aryloxy, alkylthio, arylthio and halogenO
In the foregoing deEinitions the term "str~ight or branched chai.n hydrocarbon of from 1 to 10 carbon ato~s" refers to acyrlic hydrocarbon groups which may con~ain un~aturated carbon-to-carbon bondsO The term "aryl", where unmodi~ied, lndica~.es an aromatic hydrocarbon of 6 carbon atoms while 'laralkyl" refers to a ~ carbon aromatic hydrocarbon containing a ~traight chain saturated hydrocarbon sub~tituant of ~rom 1 to 3 carbon atoms and being ethereally bonded to the carbonyl group ~h~reby. The alkylgxoup~ bonded to ~ilicon are lower C-~569 ~ 3 ~

alkyl of from l-to 3 carbon atoms. The term "aryl of from 6 to 14 carbon atoms" refers to mono- or polycyclic aromatic ~ubstituents such as phenyl, biphenyl, naphthyl, anthracyl, tolyl, xylyl, methoxyphenyl, nitrophenyl, etc. Regarding th~
phenyl substituents, all alkyl groups, whether directly bonded to the aromatic group or bonded thereto by oxygen or sulur are straight or branched chain hydrocarbons of 1 to 5 carbon atoms~ The term "aryl-" in "aryloxy" and "arylthio'l refers to phenyl. The term "heterocyclic radical" indlcates a flve to L0 six membered cyclic nueleu~ which may contain up to two atoms s)f oxygenJ nitrogen or sul~ur, or combinations thereof, in addition to carbon. The halogen atoms can be any o the four halogens, ~luorlne, chlorine J bromlne or iodine.
The compositions curable by actinlc radiation according to ~he invention can contain a photcpolymerizable pol~ner in a reactive ethylenically unsaturated monomeric medium, a reactive polymer aloneJ a reactive monomer alone~ or any of the~e combined with an iner~ solvent. Additionally, the polymerizable composition can ~ontain any of the pigmPnts commonly used in photopolymerization techniques.
The process can be carried out by mi~ing a quantlty of a photoinitiating compound of the in~ention wi.th a photopoly-merizable composition and exposing the resu1 tant mixture to actinic radiation. Alternatively, a one component ~ystem comprising the photopolymerizable composition, the photo-ini~ia~or o the inven~ion and, i~ de~ired~ plgmen~a~ion~ ~an be stored in the dark for a prolonged period of time prior to use without fear of galation.

C - L~569 ~ ~O~DO 3 1 DESCRIPTION OF THE INVENTION
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The utility of the present invention resides in the capabili~y of ~he disclosed class of novel photoini~iating com-pounds to provide markedly enhanced reactivity over known com-pounds and to make available, dar~-stable~ one-component photopolymerization systems without the need for stabilizing additives. Additional utility is found ln the ~atis~actory performance o~ the compounds of the invention in pigmented sys-tems in genexal and, in particular~ in titanium dioxide pigmented sys~ems.
The photoinitia~ing compounds of the Lnvention have proven to be very suitable in the ~ICtilliC light curing of un-saturated monomeric compounds either alone or as copolymerizable constituent~ of unsaturated polym~r/monomer systems. Such sys-tems are composed o~ mixtures o~ conventional unsaturated polymers and unsaturated monomers.
Monomers which are useful in practicing the invention are acrylic, ~-alkacrylic and cG-chloroacrylic acid compounds such as esters, amides and nitriles~ Examples of such compounds are acrylonitrile, methacrylonitrile3 methyl acrylate, ethyl acrylate, methyl methacrylate, isobutyl methacrylate, 2-ethylo hexyl acrylate, methacrylamide and methyl ~-chloroacryla~e.
Also use~ul,although not preferred due to their slower rates of reactivity9 are vinyl and vinylidene esters, ethers and ketones. Additionally~ compounds having more tha~ one terminal unsaturation carl be used Examples o these mclude diallyl phthaLate/ diallyl maleate, diallyl fumarateJ triallyl cyanurate5 triallyl phosphate, ethylene glycol dimethacrylateJ

C-~56~
~21:)6~3~

glycerol trimethacrylate, pentaerythritol triacrylate, penta-arythritol tetraacrylate, trimethylolpropane triacrylate, methacrylic anhydride and allyl ethers of monohydroxy or polyhydroxy compounds such as ethylene glycol diallyl etherJ pentaerthritol tetraallyl ether, and the like. Non-terminally unsaturated compounds such as diethyl fumarate can similarly be used.
~ . .
The acrylic acid derivitives are particularly well suited to the practice of the invention and are consequently preferred components as monomers in monomer-containing polymer-izable systems and as reactive centers in polymerizable poly-mers. While monomeric styrene can be used in the practice of the invention, it is not a preferred constituent of systems polymerizable thereby due to i~s 910w rate o~ reaction.
A preferred manner of practicing the invention is by the use o~ photopolymeri~able molding and coating compositions which consist o mixtures of unsaturated polymeric compounds and monomeric compounds copolymerizable therewith. The polymeric compounds can be conventional polyesters prepared from unsatu-rated polycarboxylic acids such as maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, mesaconic acid and the like, and polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentaerythritol, trimethylolpropane alld the like. The carboxylic acid content can also contain satura~ed components. The inclusion of a monobasic atty acid content, e~ther as such or in the form of a triglyceride or oil, in ~he photopolymerizable polyester composition to comprise an alkyd .. ..

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resin is also acceptable. These resins can, in turn, be modified by silicones, epoxides, isocyanates, etc., by known techniques.
Additionally, the photopolymerizable composition can con~ain a sensitizex capable of enhancing the photo-initiating reactivity of the photoinitiating compound of the invention by triplet sensitiæation. Examples of sensitizers useful in the practlce of the invention are such compounds as blphenyl, xanthone, thio~anthone~ acetophenone and the like. Tnese are typically added in amounts ranging from about o.l to about 6 weight percent~ The techniques whereby such sensitizers are selected for use in con~unction with particular photoinitiators are well known in the art. See, for example, MUROV, Handbook o~ Photochemistry, Marcel Dekker, Inc., New York (1~7~).
Thus it is seen that the constitution of photopoly-merizable compositions which can be used in the practlce of the in~ention is widely variable~ Ho-~ever,` the compounds enumerated above are purely illustrative. Materials subject to polymerization by actinic radiation as well as permissable variations and substitutions of equivalent components within particular types of compositions are well known to those skilled in the ar~.
The photoinitiating compounds oi the invention are esters of heterocyclic substituted gyloxalic acid, es~ers of arylglyoxalic acid and ring substituted derivatives thereof.
These compounds are known and may be readily prepared by the C-ll569 ~ 3~ ~ ~

methods set for~h in U.S. Patent 3,532Jr~7. Alternatively, the procedures of U.S. Patent 3~065,25~ can be followed. A
preferred repre~entative of the novel phot~initiators of the invention is the methyl ester of phenylglyoxalic acid.
In addition to the methods indicated above, this compound can be prepared easily by the reaction of methyl oxalyl chloride with benzene in the presence of aluminum trichloride or by the oxidation of mandelic acid to phenylglyoxalic acid and subsequent esterification with methyl alcohol.
lo The photoinitiators of the invention can be utilized in amountsranging from o.Ol to about ~o~lO by weight based on the photopolymerizable composition. However, preferable amounts of the compounds are between 0.5 and 20 weight pexcent with optimal results being achieved with amounts in the range of l.o to about 16 weight perc~ent.
An acceptable source of actinic light radiation is any apparatus which emits light radiation in the approximate region of about 2000 Angstroms to about 8000 Angstroms and pre~erably between about 2400 Angstroms and 5400 Angstroms.
One such apparatus is PPG Model QC 1202 AN UV Processor manufactured by PPG Industries~ Inc.
The radiation source for this apparatus consists of ts~o high intensity~ medium pressure quartz mercury lamps 12 inches in length and each operating at a linear power density f about 200 watts per inch or 2400 watts per lamp The lamps are housed in an eliptical reflector above a variable ~2~t6C3 3~

speed conveyor belt and each lamp provides a 2-inch band of high flux actinic radiation on the conveyor. This 2-inch exposure area is bordered on both sides by an additional 2-inch area of medium flux energy for a total radiation area of 6 inches for each lamp. In the curing data presented below, cure rate of the polymerizable compositions is pre-sented in feet-per-min~te-per-lamp (ft./min.~lamp). Thus~
.. . ` o a conveyor belt speed of one foot/min. will, with a 12-inch exp~sùre area or the two lamps, provide 60 seconds of ex-posure or a cure rate of o.5 ft./min.~'lamp. Similarly, a belt speed of 10 ft./min. will provide 6 seconds of ex-posure or a rate of 5.0 ft./min.~lamp while a speed of 20.0 ft./min. will give 3 seconds exposure or a rate o~ 1 ft./mi./lamp, etc.
Extent of curing was determined by a standard pencil hardness test with all samples being coated on steel plate to a thickness of 2 mils and polymerized to achieve a standard pencil hardness between IIH and 6X where thi~ was attainable.
The examples which follow will further illustrate the inven~ion.

This example illustrates the effect of concentration of a preferred embodiment of the invention, namely9 methyl phenylglyoxalate on the induced rate of photopolymerization of a standard test solution of acrylate/alkyd resin compo~ition.
This standard test solution consists of 42~ by weight of C-~56g 6~

trimethylolpropane triacrylate (TMPTA~, 17~ hy weight o~
ethylhexyl acrylate (E~A) and ~ by weight of an unsaturated long oil linseed oil alkyd resin.

MET~YL PHENYLGLYOXALATE (Wt ~l0) ~Ft./min./lamp) .~ . ' o 1Ø........................ .1~
2.0 . . . . . . . . . . . . . . 8

4.o . . . . . O . . . . . . . ~ 15 8.o . . . . . . . . . . . . . . 35 12.0 . . . . . . . . . . . . . . I~o 16Ø........................ 1l5 20.0 . . . . . . . . . . . O . . 45 This example illustrates the dark-storage stabili~y of various one-component photopolymerizable systems wherein dif-ferent photoinitiating compounds have been incorporated. The systems consist of benzoin isobutyl ether or methyl phenylgly-oxalate combined with various photopolyrnerizable monomers or with 2Q monomer/polymer combinations. The two polymers used in this example are EP0CRYL ~ Resîn DRH-303, a di~crylate ester of 3~ ~

Bisphenol A Epoxy Resin, available from Shell Chemical Compa`ny and W IME ~ Resin 540, composed ~f 49 par~s urethane oligomer B, 19 part~ hydroxyethyl acrylate and 32 parts pentaerythritol tetraacryla~e, available from Polychrome Corporation. The quantlty of inltia~or used was 1.2 weight percent in ~he case of the monomer/polymer systems as well as for the pentaerythritol triacrylate ~PEA3 m~nomer systems and 3.7 weight p~rcent in the TMPTA monomer systems. Storage stability was me~sured in days at 65~C.

_ . Stora~e Stabilit - (D ~ u 1 ---_ Y Y .~_, benzoin Polymerizable isobutyl Methyl Component etherPhenylglyoxalate __ . ........ . . _ __ ~
TMPTA <1*** 7o PEA <1 100-IP**
TMPTAJUVIM~R*
Resln 540 <1 50~IP
TMPTA/EPOCR~L*
Resin DRH-303 ~1 50 IP

. . .. ~
* 50 weight percen~ of each component ** IP indicates test still in progress with no indication of gelationO
~* ~ indlcates "less than"

20 6~!3 1 This example illustrates the photoefficiency of the methyl ester and ethyl ester embodiments of the invention as compared with various other photolnitiators. The composition polymerized was ~he standard test solution of Example 1 and photopolymerization was achieved as described1 uti:Lizing the PPG Industries curing unit. A quantity of 4 weight percent of photoinitiator was used in eclch case.

~ _ . . = ................................. . . .
Cure Rate (Air) Photoinitiator Ft./Min,/Lamp . . _ . . .
Me~hyl phenylglyoxalate................................ , 15 Ethyl phenylglyoxalate................................ 0. ~0 p-tertbutyl~~C,~c,oc -trichloroacetophenone............... 5 Valerophenone............. n ~ r ~ 2.5 ~c~c-niethoxyacetophenone~....... ~........ ~............ 7.5 C~-Methoxyacetophenone......................... ......... 2.5 l-benzoyl acetone......... 0........,........ ~.............. o l-phenyl-1,2-propane dione-2-oxime.............................. ~ 2.5 benzoin Methyl Ether...............,..................... 7.5 benzoin Ethyl Ether................,..................... 7.5 benæoin isopropyl Ether...........Ø.................... 7.5 benzoin Sec-butyl Ether............~..................... 7.5 benzoin isobutyl Et~er ................................. 7.5 benzoin benzyl Ether~....Ø............................. 7~5 The following example compares the photoefficiency of various ring substituted embodiments of the invention with that of ~everal dione photoinitiators. The procedure, materials and quantities were as stated in Example 3.

C- 1~569 ~16~3~

Cure Rate (Air) Photoini~iator Ft./Min./Lamp , _ . . , Ethyl-p-methylthio phenylglyoxalate .......................... 12 Ethyl-p-phenylthio phenylglyoxalate .......................... 11 Ethyl-p-methoxy phenylglyoxalate ............................ ~10 l-phenyl propane-1,2~dione ......~ ........................... 8 Benzil ................ a~ 7~5 4,4~-bis(methoxy)-benzil ................................ 0 2 ~5 4,4~-bis(methyl)-benzil ........Ø........................... 6 9,10-phenanthraquinone ........................ ............ 0. 5 Ace~aphthenequinone ... ~.................................... 0......... 3.3 1,2-naphthoquinone .............. 0............ ~... O........... o N,N-diethyl benzoyl formamide .................... ...... ...... 5 This example compares ~he photoinitiating efficiency of methyl phenylglyoxalate and benzoin isobutyl ether in various polymerizable systems. The polye9t~er component referred to in this example is a standard, commercial ~nsaturated polyester and both photoinitiators were used at 4 weight percent.

. ~
Cure Rate ( Air ) _ Ft./Min./Lamp ___ Polymerizable Methyl phenyl- Benzoin Formula~ion glyoxalate isobutyl Ether _ _ _ _ I~IPTA/ WIMER 540 Resin* 25 10 TMPTA/EPOCRYL ~ Resin D~H-~O~* 50 ~0 PETA*** 60 20 ~0 TMPTA/Polyester ** 20 7 _ _ _ __ _ _ _ * 50 weight percent of each component ** 80 weight percent TMPTA; 20 weight percent polyester.
*** Pentaerythritol tetraacrylate ~-4569 ~o~a~3~

This example sets forth the photoefficiency of addi-tional embodiments of the invention when tested at 4 weight percent loading ln the standard test solution of Example 1 with curing as indicated with the PPG Industries unit.

~ . .
Photoinitiator Cure Rate ~Air) ~_ Ethyl 2-FuranglyoxalateO..........~.................... 15 ~thyl-p-phenoxyphenylglyoxalate... O.....~.............. 10 Benzyl phenylglyoxalate ..,............................. g lo Allyl phenylglyoxalate............ ~ .... ,............... 8 trlmethylsilyl phenylglyoxalate ..................... ... 7 tert-butyl phenylglyoxalate.................~........... 5 phenyl phenylglyoxalate ~r~ 2 Ethyl-p-ethylphenylglyoxalate.................... .... ~. g S Ethyl-2,4-dimethoxyphenylglyoxalate.............. .... ~. 4 Ethyl~2,4,6-trimethylphenylglyoxalate............ .... O. 3 EShyl Naphthylglyoxalate~ -----.-. 6 Ethyl-p-phenylphenylglyoxalate................... ....... 6 EXA~LR 7 This example illustrates the comparative performance of me~hyl phenylgl~oxalate and various other photoinitiators in tit~nium dioxide pigmented systems with regard to cure xa~e, surface texture of the polymerized coating and color.
Standard test procedure was followed. The additîons to the ~tandard test solution of Example 1 were 15 weight percent of titanium dioxide pigment (TIQPURE R 900: DuPont~ and 4 welght percent of each photoinitiator candidate.

~ 15 -- .

C-l~5~9 ~ 2~ ~ 3 ~

_._ _ _ . .
Cure Rate(Air) Surace Photoinitiator Ft/Min/Lamp Texture Colo~
_ 2-chlorothioxanthone/
dimethylethanol amine* 25 Acceptable Yellow methyl phenylglyoxalate 5 Acceptable White benzophenone/Michler' 5 ketone** 5 Acceptable Yellow .
benzil 2.5 Wrinkled White 4,4l-bis(methoxy)-benzil 2.5 Wrinkled Yellow lo l-phenyl propane-1,2-dione 2.5 Wrinkled Yellow oc~C -diethoxyacetophe-none 2.5 Wrinkled White benzoin isobutyl ether 2 Wrinkled White 4,4~-dimethoxy benzoin isobutyl ether 5 Wrinkled Yell.ow * 50 weight percent o each component ** 87.5:12.5 weight percent benzophenone to Michler's ketone.

Claims (16)

What is claimed is:

1. In the photopolymerization of monomeric and polymeric compositions of photopolymerizable substances wherein a photo-initiator is admixed with a photopolymerizable composition and the mixture exposed to actinic radiation, the improvement wherein photopolymerization is effectively initiated by allyl phenylglyoxalate or a compound of the formula:

wherein R is straight or branched chain hydrocarbon of from one to ten carbon atoms, aryl, aralkyl, or mono-, di or trialkyl-silyl and R1 is a heterocyclic radical, axyl of from 6 to 14 carbon atoms or mono-, di- or polysubstituted phenyl with substituents selected from the group consisting of alkyl, alkoxy, aryloxy, alkylthio, arylthio and halogen with the proviso that when R is alkyl or benzyl R' is other than phenyl, said photoinitiator being present in said composition at a concentration of 0.01 to about 30 weight percent.

2. The method of Claim 1 wherein the photopolymerizable substance additionally contains a pigmentation additive.

3. The method of Claim 2 wherein the pigmentation addi-tive is titanium dioxide.

4. The method of Claim 1 wherein the photoinitiating compound is trimethylsilyl phenylglyoxalate.

5. The method of Claim 1 wherein the photoinitiating compound is allyl phenylglyoxalate.

6. The method of Claim 1 wherein the photoinitiating compound is ethyl-p-phenylphenylglyoxalate.

7. The method of Claim 1 wherein the photoinitiating compound is ethyl naphthylglyoxalate.

8 . The method of Claim 1 wherein the photoinitiating compound is ethyl-p-phenoxyphenylglyoxalate.

9 . The method of Claim 1 wherein the photoinitiating compound is ethyl-p-methylthio phenylglyoxalate.

10 . The method of Claim 1 wherein the photoinitiaing compound is ethyl-p-phenylthio phenylglyoxalate.

11. The method of Claim 1 wherein the photoinitiating compound is present at a concentration of about 0.5 percent by weight to about 16 percent by weight.

12. The method of Claim 1 wherein the photoinitiating compound is present at a concentration of about 1.0 percent by weight to about 16 percent by weight.

13. A composition photopolymerizable by actinic radia-tion comprising unsaturated polymerizable constituents contain-ing dispersed therein from 0.01 to 30 weight percent of a photoinitiating compound of the formula:

wherein R is straight or branched chain hydrocarbon of from one to ten carbon atoms, aryl, aralkyl, or mono-, di- or trialkylsilyl and R' is a heterocyclic radical, aryl of from 6 to 14 carbon atoms or mono-, di- or polysubstituted phenyl with substituents selected from the group consisting or alkyl, alkoxy, aryloxy, alkylthio, arylthio, and halogen, with the proviso that when R is alkyl or benzyl R' is other than phenyl.

14. The composition of Claim 13 which additionally contains a photosensitizer.

15. The composition of Claim 13 which additionally contains a pigmentation additive.

16. The composition of Claim 15 wherein said pigmentation additive is titanium dioxide.