JPS63180946A - Photopolymerizable composition having high sensitivity - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable compsn. having increased photosensitive velocity to either one of visible rays or ultraviolet rays by incorporating a specified coumarin compd. and a diaryl iodonium salt into a photopolymn. initiator. CONSTITUTION:A coumarin compd. expressed by the formula and a diaryl iodonium salt are incorporated into a photopolymn. initiator. in the formula, X is H or cyano group; each R<1>-R<3> is H, 1-6C alkoxy, amino group, etc. independently; R<4> is H, 1-4C alkyl, 6-12C aryl, or trihalomethyl group. 7- dimethylamino-3-(2-thenoyl) coumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), etc. are preferred among the coumarin compds. from the viewpoint of the degree of increase of the photopolymn. velocity. By this constitution, a photopolymerizable compsn. having high sensitivity for visible rays or ultraviolet rays is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to photopolymerizable compositions that exhibit high sensitivity to either visible light or ultraviolet light.

[Prior Art] When reproducing images by photographic techniques, compositions containing photosensitizing compounds such as diazonium salts, azides, and quinone diats, or photopolymerizable compositions containing photopolymerization initiators that act under ultraviolet light are used. things are being used.

These compositions usually exhibit photosensitivity to ultraviolet light, but many do not exhibit photosensitivity to visible light. Therefore, photopolymerizable compositions that are sensitive to visible light are currently being developed (JP-A-5L-114139, JP-A-59-142205, etc.).

However, the photopolymerizable compositions that are sensitive to either ultraviolet rays or visible rays do not necessarily have a sufficient photosensitive speed, and the time required for irradiation with actinic rays such as visible lasers or ultraviolet rays is long, resulting in poor workability. Furthermore, heat generation occurs in order to increase the output of the light source, which causes adverse effects (eg, thermal deformation, etc.) on the composition itself.

OBJECTS OF THE INVENTION It is an object of the present invention to provide photopolymerizable compositions with increased photosensitivity to either visible or ultraviolet radiation.

[Structure of the Invention] According to the research of the present inventors, photopolymerization can be initiated in a system of a photopolymerizable composition containing a photopolymerization initiator and an addition-polymerizable compound that forms an ethylenically unsaturated di-R bond. It has been found that the purpose of the ITfr period can be achieved by using a certain coumarin compound and diaryliodonium salt in combination as agents. Also, a methylene group at the α position of the nitrogen atom? It has been found that the sensitivity becomes higher when a compound with T is added.

According to the present invention, there is provided a photopolymerizable composition comprising an addition-polymerizable compound that forms an ethylenically unsaturated dual combination and a photopolymerization initiator, the photopolymerization initiator comprising (a) the following: General formula [Ico[wherein X is hydrogen, cyan group, or -C(CH=CI-
I)-R' (where n represents an integer from O to 2, n-
When I O is -(, -R5, R5 is a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and 1 to I
O substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, or 5 to 15 carbon atoms and heteroatoms constituting the ring represents a substituted or unsubstituted heterocycle. ), and R', R'' and R3 each independently represent hydrogen, an alkoxy group having 1 to 6 carbon atoms, an amino group, an alkylamino group or dialkylamino group having 1 to 4 carbon atoms in an alkyl group, or a hydroquine group. R1 and R2 or R1
and R3 are 5~! Fused ring systems or fused heterocyclic ring systems containing 0 carbon atoms may also be formed. R4 is hydrogen, carbon number 1-
4 alkyl group, an aryl group having 6 to 12 carbon atoms, or trihalomethyl. ] A photopolymerizable composition characterized by containing a coumarin compound represented by the following and (b) a diaryliodonium salt is provided.

Coumarin compound used in the present invention (hereinafter referred to as component (a))
There is something to be said. ) is represented by the above general formula [I]. Examples of such are 3-benzoylcoumarin, 3-benzoyl-57-simethoxycoumarin, 3-benzoyl-6-ethoxycoumarin, 3-benzoyl-7-ethoxycoumarin, 3-benzoyl-8-
Methoxycoumarin, 3-benzoyl-8-ethoxycoumarin, 3-benzoyl-6-bromocoumarin, 3-benzoylbenzo[f]coumarin, 3-benzoyl-7-dimedylaminocoumarin, 3-benzoyl-7-ethylaminocoumarin Coumarin, 3-benzoyl-7-(1-pyrrolinonyl)coumarin, 3-benzoyl-7-hydroxycoumarin, 3-benzoyl-6-nitrocycoumarin, 3-acedel-7-dinithylaminocoumarin, 3-acetyl-
7-methoxycoumarin, 3-acetyl-5,7-simethoxycoumarin, 3-acedelbenzo[r]coumarin, 3
-Carboxycoumarin, 3-carboxy-7-ethoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-7-methoxycoumarin, 7-dimethylamino-3-(4-iodobenzoyl)
Coumarin, 7-ethylamino-3-(4-iodobenzoyl)coumarin, 7-diethylamino-3-(4-diedylaminobenzoyl)coumarin, 7-methylamino-3-(2-thenoyl)coumarin, 7-ethylamino-3-(2- Furoyl) coumarin, 7-ethylamino-3-(2-thenoyl) coumarin, 7-pyrrolinyl-3-(2-thenoyl) coumarin, 7-pyrrolidinyl-3-(2-benzofuroyl) coumarin, 7-diethylamino-3-(4-dimethyl) aminocinnamoyl) coumarin, 7-dinithylamino-3-(4-noethylaminocinnamoyl)coumarin, 7-dinithylamino-3-(
4-diphenylaminocinnamoyl)coumarin, 7-dinithylamino-3-(4-dimethylaminocinnamylideneacetyl)coumarin, 7-dinithylamino-3-(4
-diphenylaminocinnamylideneacetyl)coumarin, 7-dinithylamino-3-(2-benzofuroyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3-
Cyano-6-ethoxycoumarin, 3-cyano-7-ethoxycoumarin, 3-(4-nitrobenzoyl)benzo[
f] Coumarin, 3-(4-ethoxycinnamoyl)-7
-Ethoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 7-medoxy 3-(p-nitrobenzoyl)coumarin, 5,7-simethoxy 3-(4 −
dimethylaminocinnamoyl)coumarin, 5,7-dimethoxy-3-(4-diphenylaminocinnamoyl)coumarin, 5,7-nomethoxy-3-(4-dimethylaminocinnamylideneacetyl)coumarin, 5,7-cymethoxy-3- (4-diphenylaminocinnamylideneacetyl)coumarin, 7-dinithylamino 3-[3-(
9-Noyurolidyl) acryloylcocoumarin, 5.7-
Nomethoxy 3-[3-(9-julolidyl)acryloylcocoumarin, 7-amino-4-methylcoumarin, 7
-amino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-
Dimethylaminone clopenta[c]coumarin, 7-dimethylamino-4-methylcoumarin, 8-(phenylazo)-7-hydroxy-4-methylcoumarin, 8-(o-
tolylazo)-7-hydroquine-4-methylcoumarin,
8-(m-tolylazo)-7-hydroxy-4-methylcoumarin, 8-(p-tolylazo)-7-hydroxy-
4-Methylcoumarin, 8-(o-, m-, or p-hydroxyphenylazo)-7-hydroquine-4-methylcoumarin, 8-, (.

-chlorophenylazo)-7-hydroxy-4-methylcoumarin, 8-(p-chlorophenylazo)-7-hydroxy-4-methylcoumarin, 8-(p-bromophenylazo), 8-(p-iodophenylazo) )-7-hydroxy-4-methylcoumarin, 8-(m-carboxylphenylazo)-7-hydroquine-4-methylcoumarin, 8-(p-carphoquinorphenylazo)-7-hydroxy-4-methylcoumarin , 8-(p-sulfonylphenylazo)nia-hydrokiller 4-methylcoumarin, 8
-(p-nitrophenylazo)-7-hydroxy-4-
Methylcoumarino, 8-(O-methoxyphenylazo)-
7-hytrogin-4-methylcoumarin, 8-(p-methquinphenylazo)-7-hydroxy-4-methylcoumarin, 8-(p-Umethylaminophenylazo)-7-
Hydroxy-4-methylcoumarino, 3.3'-carbonylbiscoumarin, 3.3'-carbonylbis(7-medoxycoumarin), 3.3'-carbonylbis(5,7-
cymethoxycoumarin), 3.3°-carbonylbis(6
-butoxycoumarin), 3.3゛-carbonylbis(7
-acetoxycoumarin), 3.3゛-carbonylbis(
5,7-diitubroboxycoumarin), 3,3°-carbonylbis(5°7-di-n-propoxycoumarin),
3.3°-carbonylbis(5,7-d-n-butoxycoumarin), 3.3′-carbonylbis(7-dimethylaminocoumarin), 3.3′-carbonylbis(7-dinithylaminocoumarin) , 3,3°-carbonylbis(
benzo[']coumarin), 7-danitylamino-5°-dimethoxy-3,3'-carbonylbiscoumarin,
5.7.6'-trimethoxy-3,3°-carbonylbiscoumarin and the like. The method for producing these coumarin compounds is described in Chemical Reviews, 36.
1 (1945); Agr, Univ, J, Re
5earch, 4.345 (1955) C,A.

52, 73076 and Chem, Eng, Dat
a, 12.624 (1'167), etc. Among these coumarin compounds, 7-nomethylamino-3
-(2-Thenoyl)coumarin, 7-dinithylamino-3
-(2-furoyl)coumarin, 7-dinithylamino-3
-(2-Thenoyl)coumarin, 7-virolidinyl-3-
(2-Thenoyl)coumarin, 7-virolidinyl-3-(
2-benzofuroyl)coumarin, 7-dinithylamino-3-(=1-dimethylaminocinnamoyl)coumarin,
7-Dinithylamino-3-(4-diethylaminocinnamoyl)coumarin, 7-noethylamino-3-(4-diphenylaminocinnamoyl)coumarin, 7-dinithylamino-3-(4-diethylaminocinnamylideneacetyl)coumarin, 7-noethylamino-3- (4-diethylaminocinnamylideneacetyl)coumarin, 7-dinithylamino-3-(4-diphenylaminocinnamylideneacetyl)coumarin, 7-dinithylamino-3-(
2-benzofuroyl)coumarin, 7-dinithylamino-3-[3-(9-julolidyl)acry[lylcocoumarin, 3,3'-carbonylbis(7-butoxycoumarin), 3,3°-carbonylbis(5,7- dimethquine coumarin), 3,3°-carbonylbis(6-butoxycoumarin), 3,3'-carbonylbis(7-dimethylaminocoumarin), 3,3'-carbonylbis(7-dinitylaminocoumarin) is preferred.

The diaryliodonium salt (hereinafter sometimes referred to as component (b)) is a compound represented by the following general formula [II].

[In the formula, R6-R8 are the same or different, hydrogen atoms,
Halogen atoms (e.g. chlorine, bromine), lower alkyl groups (
(e.g. methyl, ethyl, propyl, 1-butyl), lower alkoxy group (e.g. methoxy, ethoxy, propokine) or nitro group, and Y- represents a halogen ion (e.g. CQ', Br-, do), hydroxide ion, ISO ,−
1B F 4- , P Fo-1AsF11- or 5bFa-. The compound represented by general formula [II] is described in, for example, "Journal of Polymer Science Polymer Symbodia J (J, Polym,
It can be synthesized according to the method described in Sci.
Chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate of iodonium such as bis(p-chlorophenyl)iodonium, ditolyliodonium, bis(p-t-butylphenyl)iodonium, bis(m-nitrophenyl)iodonium , hexafluoroantimonate.

Examples of the compound having a methylene group at the alpha position of the nitrogen atom (hereinafter sometimes referred to as component (c)) include triethylamine, N-methyljetanolamine, triethanolamine, N-ethyl-N-benzyl Aniline, N, N-diethyl-p~phenylenediamine, N-
Examples include phenylglycine, with N-phenylglycine being particularly preferred.

The addition-polymerizable compound having an ethylenically unsaturated double bond (hereinafter referred to as a double-bond-containing compound) undergoes addition polymerization and hardening due to the action of a photopolymerization initiator, so that it becomes substantially insolubilized. Any monomer or polymer having an ethylenically unsaturated double bond may be used. Specific examples include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds, and addition reaction products of unsaturated carboxylic acids and epoxides. , unsaturated carboxylic acids and polyhydric carboxylic acids and aliphatic polyhydroxy compounds,
Examples include esters obtained by esterification reaction with polyhydric hydroxy compounds such as aromatic polyhydroxy compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid. Aliphatic polyhydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, propylene glycol, dihydric alcohols such as l,2-butanediol, trimethylolethane, trimethylolpropane, glycerol, etc. Examples include trihydric alcohols, tetrahydric or higher polyhydric alcohols such as pentaerythritol and tripentaerythritol, and polyhydric hydroxycarboxylic acids. Examples of aromatic polyhydroxy compounds include hydroquinone, resorcinol, catechol, and pyrogallol. Epoxides include trimedylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, diglycidyl ester of phthalic acid, and a reaction product of epichlorohydrin and 2,2-bis(4-hydroxyphenyl)-propane. There is. Examples of polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, trimellitic acid, pyromellitic acid, benzophenonedicarboxylic acid, maleic acid, fumaric acid, malonic acid, geltaric acid, adipic acid, sebacic acid, Examples include tetrahydrophthalic acid.

Typical examples of esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds or esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds include acrylics of the above aliphatic polyhydroxy compounds or aromatic polyhydroxy compounds. Acids or esters of methacrylic acid may be mentioned. Typical examples of esters obtained by the esterification reaction of unsaturated carboxylic acids and polyhydric carboxylic acids with polyhydric hydroxy compounds include those shown below. (However, Zo is an acryloyl group or a methacryloyl group.): z′-oc, ■, -ooc-13-coo-c, H, o
-z'Z' -(oct H4+T-00C(C1l
t h Co0(Ct II-Oh Z'Z' -(O
cJ4Th 0OC-CII=CH-Coo(CJI-
OTh Z'z'-0CzlL-00COCOO-Ct
Examples of double bond-containing compounds that can be used in the invention include acrylamide, acrylamides such as ethylenebisacrylamide and hexamethylenebisacrylamide, and methacrylamide such as ethylenebismethacrylamide and hexamethylenebismethacrylamide. Examples include double bond-containing compounds such as allyl esters such as diallyl phthalate, allyl malonate, diallyl fumarate, and triallyl isocyanurate.

Examples of double bond-containing compounds as polymers having a double bond in the main chain include unsaturated dihydric carboxylic acids (e.g. maleic acid, fumaric acid) and dihydropear compounds (e.g. the dihydric alcohols mentioned above). ), polyamides obtained by polycondensation reaction of the above-mentioned unsaturated dicarboxylic acids and diamines (eg, ethylenediamine, hexamethylenediamine), and the like. Examples of compounds having a double bond in the side chain include dicarboxylic acids having a double bond in the side chain (e.g. itaconic acid, α-methyl itaconic acid, γ-medyl itaconic acid, propylidenesuccinic acid, α- ethylidene glutaric acid,
Examples include polyesters obtained by a polycondensation reaction between (ethylidenemalonic acid, propylidenemalonic acid) and the above dihydroxy compounds, and polyamides obtained by a polycondensation reaction with the above diamines. Additionally, polymers obtained by a polymer reaction between a polymer having a functional group such as a hydroxyl group or a halogenated methyl group in a side chain and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, or crotonic acid can also be used. . In addition, as a polymer having a functional group in the side chain,
Polyvinyl alcohol, partially saponified polyvinyl acetate, copolymers of acrylonitrile and styrene, vinyl chloride, vinylidene chloride, etc., completely saponified copolymers of acrylonitrile and vinyl acetate, 2-hydroxyethyl methacrylate and acrylonitrile, methyl Copolymers with methacrylate, butyl methacrylate, styrene, vinylidene chloride, vinyl acetate, etc., poly(4-hydroxystyrene), poly(N-medylolacrylamide)
Examples include.

Among the double bond-containing compounds mentioned above, it is particularly preferable to use monomers of acrylic esters or methacrylic esters.

In the composition of the present invention, 0.00% of component (a) is added to 1 part by weight of the double bond-containing compound. 1 to 0.2 parts by weight of O, preferably 0.02 to 0.1 parts by weight, and 0.00 parts of component (b)
5 to 0.2 parts by weight, preferably 0.2 parts by weight. 0.005 to 0.2 parts by weight, preferably 0.005 to 0.2 parts by weight of O1 to 0.08 parts by weight and optionally component (c). It is used in a proportion of 1 to 0.08 parts by weight. If the proportion of any of these two or three components used is less than the respective lower limits, the photosensitivity will decrease and it will take a long time to insolubilize the composition. Moreover, if the amount exceeds the upper limit, the strength and solvent solubility resistance of the film formed from the composition will decrease, making it unsuitable for practical use.

The composition of the present invention comprises the above-mentioned double bond-containing compound and the component (a).
) A photopolymerization initiator consisting of a combination of (b) and component (C) as necessary is an essential component, but polymer binders, thermal polymerization inhibitors, plasticizers, colorants, etc. may be added as necessary. May be used together. The polymeric binder has various purposes for improving compatibility, film-forming properties, developability, adhesion, etc., and an appropriate type may be selected depending on the purpose. For example, to improve developability with an aqueous solvent, use acrylic acid (or methacrylic acid) and acrylic acid (or methacrylic acid).
Copolymers with alkyl esters (e.g. methyl esters, ethyl esters, butyl esters), itaconic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose modified products having carboxyl groups in side chains, polyethylene oxide, polyvinyl Pyrrolidone is useful,
To improve film strength and adhesion, shrimp chlorohydrin and 2
．． Polyethers, polyamides, etc. with 2-bis(4-hydroxyphenyl)propane are useful. Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, and 2.6-not-t-
Butyl-p-cresol, β-naphthol, and the like are useful. Examples of plasticizers include didodecyl phthalate,
Useful examples include phthalic acid diesters such as didodecyl phthalate and dibutyl phthalate, and aliphatic dibasic acid esters such as dibutyl adipate, dibutyl adipate and dibutyl sebacate. Useful coloring agents include, for example, phthalonoamine pigments, azo pigments, carbon black, titanium oxide pigments, triphenylmethane dyes, azo dyes, anthraquinone dyes, and the like.

The composition of the invention may be prepared in a conventional manner.

For example, the above-mentioned essential components and optional components may be used as they are or as needed in a solvent (for example, a ketone solvent such as methyl ethyl ketone, acetone, or cyclohexanone, an ester solvent such as ethyl acetate or butyl acetate, an aromatic solvent such as toluene or xylene, Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve,
It can be prepared by blending alcoholic solvents such as methanol, ethanol and propatool, and ethereal solvents such as tetrahydrofuran and dioxane) and mixing them in a cool, dark place using, for example, a high-speed stirrer.

A photosensitive layer made of the composition of the present invention can be formed by applying the composition onto a support according to a conventional method, for example, using a bar coater or a spinner, and drying it. Note that known techniques may be applied to the formed photosensitive layer to protect its surface and prevent adverse effects such as a decrease in sensitivity due to oxygen. For example, a removable transparent cover sheet may be provided on the photosensitive layer, or a coating layer made of a waxy material with low oxygen permeability, a water-soluble or alkali-soluble polymer, etc. may be provided. For the photosensitive layer, a light source that emits light with a wavelength in the absorption wavelength region of the coumarin compound (a) used can be used.

Examples of light sources include lasers such as argon laser, helium cadmium laser, krypton laser, etc.
General-purpose light sources that generate ultraviolet or visible light include ultra-high-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, metal halide lamps, xenon lamps, and tungsten lamps. The development after the light irradiation may be carried out using an appropriate developer that can avoid dissolving the unexposed photosensitive layer depending on the composition of the photosensitive layer.

[Effects of the Invention] The composition of the present invention exhibits high sensitivity to visible light or ultraviolet light. For example, by using an argon laser as a visible light beam, a scanning exposure device can be used to directly transmit the image signal to the image line body provided with the composition of the present invention, without using a conventional negative film, etc. lithographic printing plate,
It can be written on resists for producing printed wiring boards, master plates for producing hologram matrices, etc., and its practical effects are extremely large.

[Examples] Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited to these Examples.

Methyl methacrylate/methacrylic acid copolymer (manufactured by Mitsubishi Rayon Co., Ltd. [Br (-774, weight average molecular weight approximately 700
00) was dissolved in 21,000 parts of methyl ethyl keto (parts by weight, the same applies hereinafter), and then 100 parts of pentaerythritol triacrylate was dissolved therein to obtain a first liquid.

Next, photopolymerization initiators (components (a) to
(C)) was dissolved in 300 parts of methyl cellosolve and a second
The total amount of each liquid was added to the first liquid and thoroughly stirred to obtain a solution (photosensitive liquid) of the photopolymerizable composition.

Preparation of photosensitive layer (test plate) The above photosensitive solution was coated on an aluminum support using a bar coater so that the coating m was 29/m'' when dry.
It was dried for 3 minutes in a drying mold at 60°C.

A photosensitive layer with a thickness of 2.0 μm was obtained. On this photosensitive layer,
Using a bar coater, apply a 5% polyvinyl alcohol (saponification degree 88%, polymerization degree 500) aqueous solution to a thickness of 2.0 μm.
This was applied to form an overcoat layer.

Measurement of sensitivity The above test plate was placed on Kodak Step Tablet No. 2 (21 steps), and light with a wavelength of around 490 nm was extracted from a xenon lamp (150 W) manufactured by Ushio Inc. through a Toshiba KL-49 filter. A light intensity of 4,011W/C was irradiated from above for 0 seconds.Developed with a developing solution (10 parts by weight of anhydrous sodium carbonate, 50 parts of butyl cellosolve and 3 parts of anionic activator dissolved in 1000 parts of water). The exposure energy required for curing was calculated based on the number of photocured stages, and the value was defined as "sensitivity".The results are shown in Table 1.

Image forming output by argon laser 0. Laser light (488nm) focused from IW's argon laser light source through the optical system to a beam diameter of 20μ
Cylindrical scanning (1000
rpm, 600 lines/inch).

This was then developed with the developer described above to obtain an "argon laser image." The results are shown in Table 1.

Table 1 (a): 3,3°-carbonylbis(7-dinithylaminocoumarin) (b) Dinophenyliodonium tetrafluoroborate (c): N-phenylglycine* The smaller the number, the higher the sensitivity. Show that.

**Evaluation of images by argon laser was performed in four stages: A, B, C, and D. A is clear, B is slightly clear, C
indicates that the image is unclear and D indicates that the image cannot be obtained.

As is clear from the results in Table 1, when components (a) and (b) and, if necessary, (c) are used in combination as photopolymerization initiators, the combination of components (a) and (c) Compared to the case where a combination mechanism is adopted, the sensitivity is up to 12 times higher, indicating its high practicality, and it is also recognized that it exhibits high photosensitivity to visible laser light.

Example 8 Preparation of a test plate, measurement of sensitivity, and image formation with argon laser were carried out in the same manner as in Example 4, except that 6f4 of diphenyliodonium chloride was used instead of 6 parts of diphenyliodonium tetrafluoroborate in Example 4. I did it. As a result, the sensitivity is 0, 1
mJ/cry'', and the argon laser image was as clear as that obtained in Example 4.

Example 9 Except that 6 parts of di-p-)dyliodonium hexafluorophosphate salt was used instead of 6 parts of diphenyliodonium tetrafluoroborate in Example 4.
A test plate was prepared, the sensitivity was measured, and an image was formed using an argon laser in the same manner as in Example 4. As a result, the sensitivity was 0.1 mJ 7 cm'', and the image obtained by the argon laser was as clear as that obtained in Example 4.

Example 1O Preparation of a test plate, measurement of sensitivity, and argon Image formation was performed using a laser. As a result, the sensitivity was 0.3 mJ/am'', and the image obtained by the argon laser was as clear as that obtained in Example 4.

Example II All tests were conducted in the same manner as in Example 4, except that 100 parts of a compound obtained by adding 2 moles of acrylic acid to 1 mole of propylene glycol diglyndyl ether was used instead of 100 parts of pentaerythritol triacrylate in Example 4. A plate was prepared, sensitivity was measured, and an image was formed using an argon laser. As a result, the sensitivity is O, I mJ
7 cm'', and the argon laser image was as clear as that obtained in Example 4.

Example I2 and its Comparative Example Except for using 6 parts of 7-(diethylamino)-4-trifluoromethylcoumarin instead of 6 parts of 3,3°-carbonylbis(7-dinithylaminocoumarin) in Example 4. A test plate was prepared in the same manner as in Example 4. Next, Kodak Step Tablet No. 2 (
21 step) and the above test plate were stacked on top of each other and irradiated with light from a 3KW high pressure mercury lamp for 5 seconds from a distance of 60cm shoulder. When this test plate was developed with the developer, the number of photocured plates was 10.

For comparison, a test plate was prepared without diphenyliodonium tetrafluoroborate, and exposed and exposed in the same manner as above.
When development was performed, the number of photocured stages was 5.

Example 13 All except using 6 parts of 7-diethylamino-3-(4-dimethylaminonnamoyl)coumarin instead of 6 parts of 3,3°-carbonylbis(7-enethylaminocoumarin) in Example 4. When a test plate was prepared and the sensitivity was measured in the same manner as in Example 4, the sensitivity was 0.
, 3 mJ/c, x''.

Example 14 All the same procedures as Example 4 except that 6 parts of 7-diethylamino-3-(2-thenoyl)coumarin were used instead of 6 parts of 3,3'-carbonylbis(7-dinithylaminocoumarin) in Example 4. When a test plate was prepared and the sensitivity was measured in the same manner as above, the sensitivity was 0.2 mJ/cx
"Met.

Claims (1)

[Claims] 1. A photopolymerizable composition containing an addition polymerizable compound having an ethylenically unsaturated double bond and a photopolymerization initiator,
The photopolymerization initiator has the following general formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula, X is hydrogen, cyano group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, n indicates an integer from 0 to 2, and when n = 0, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
R^5 is a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms,
It represents a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms or a substituted or unsubstituted heterocycle having 5 to 15 carbon atoms and different atoms constituting the ring. ) and R^1
, R^2 and R^3 are each independently hydrogen, carbon number 1
~6 alkoxy groups, amino groups, alkylamino groups or dialkylamino groups in which the alkyl group has 1 to 4 carbon atoms,
It represents a hydroxyl group, a halogen, a nitro group, a 5- to 6-membered heterocyclic group, a substituted or unsubstituted arylazo group having 6 to 12 carbon atoms, and R^1 and R^2 or R^2 and R^3 are 5 to
Fused ring systems or fused heterocyclic ring systems containing 10 carbon atoms may be formed. R^4 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or trihalomethyl. ] A photopolymerizable composition characterized by containing a coumarin compound represented by these and (b) a diaryliodonium salt. 2. Diaryliodonium salt has a general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, R^6 to R^9 are the same or different and represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower Represents an alkoxy group or a nitro group, and Y^- is a halogen ion, a hydroxyl ion, HSO_4^-, BF_4^-, PF_6^
-, represents AsF_6^- or SbF_8^-. ]
2. The photopolymerizable composition according to claim 1, comprising: 3. The photopolymerizable composition according to item 1, wherein the photopolymerizable composition further contains a compound having a methylene group at the α-position of the nitrogen atom. 4. A compound having a methylene group at the α-position of the nitrogen atom is N-
4. The photopolymerizable composition according to item 3, which is selected from the group consisting of phenylglycine, triethylamine, and triethanolamine.