JP3112771B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition.

[0002]

2. Description of the Related Art A photosensitive composition obtained by mixing a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having a suitable film-forming ability and a thermal polymerization inhibitor. A method of duplicating an image by a photographic method using a conventional method is known, for example, US Pat. No. 2,927,022, US Pat. No. 2,902,356 or US Pat. No. 524 and the like. As described in these U.S. patents, this type of photosensitive composition undergoes photopolymerization upon irradiation with light, and is cured and insolubilized. The cured image of the desired photopolymerizable composition can be formed by irradiating light through the negative image and removing only the unexposed portions with an appropriate solvent (hereinafter simply referred to as development). It is clear that this type of photosensitive composition is extremely useful as a material used for producing a printing plate or the like.

[0003] Further, conventionally, only a polymerizable compound having an addition-polymerizable unsaturated bond alone does not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to enhance photosensitivity. As the polymerization initiator, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone and the like have been used. However, when these photopolymerization initiators are used, it takes a long time for image exposure in image formation because the photopolymerizable composition has low sensitivity to curing. Therefore, in the case of a fine image, if there is a slight vibration in the operation, a good quality image cannot be reproduced, and the energy emission amount of the exposure light source must be increased. Exothermic radiation had to be considered. In addition, there has been a problem that the composition is easily deformed and deteriorated by heat. In recent years, a method of forming an image using a laser with high sensitivity to ultraviolet light has been studied, and a UV projection exposure method in printing plate preparation, laser direct plate making, laser facsimile, holography, etc. are already in a practical stage, Highly sensitive photosensitive materials corresponding to these have been desired and are being developed. However, it cannot be said that a photosensitive material having sufficient sensitivity has been found yet.

[0004]

It is an object of the present invention to provide a highly sensitive photopolymerizable composition. That is,
An object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator which generally increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an addition-polymerizable unsaturated bond. is there. Another object of the present invention is to provide a light-emitting device comprising:
It is an object of the present invention to provide a photopolymerizable composition containing a photopolymerization initiator having high sensitivity to the above visible light, especially to light near 488 nm corresponding to the output of an Ar ⁺ laser.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific photopolymerization initiator is capable of photopolymerizing a polymerizable compound having an addition-polymerizable unsaturated bond. The inventors have found that the present invention has a remarkably increased speed and exhibits high sensitivity to visible light of 400 nm or more, and has reached the present invention. That is, the present invention is a photopolymerizable composition containing the following components (i) to (iii). (I) an addition-polymerizable compound having at least one ethylenically unsaturated double bond; (ii) a photopolymerization initiator; (iii) represented by the following general formula (I), (II) or (III) At least one of the compounds (I) R ¹ S-CHR ² R ³ R ¹ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or a substituted alkenyl group, and R ² , R ³ Is the same as R ¹ , or a hydrogen atom or a group having a positive Hammett σ _p value, -OR ¹ or -SR ¹ , or R ¹ is bonded to R ² or R ³ to form a ring Is also good. (II) Y-CS-SR ⁴ R ⁴ has the same meaning as R ¹ or Y-CS-S-, and Y is -OR ⁵ or
Indicates -NR ⁶ R ^7, R ^5, R ^6, R ⁷ is an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or a substituted alkenyl group, R ⁶ and R ⁷ are bonded to the ring May be formed. (III) Z-CHR ⁸ R ⁹ Z represents R ¹⁰ -SO ₂ -or R ¹⁰ -O-SO _2- , and R ¹⁰ represents R ⁵ ,
It is synonymous with R ⁶ and R ⁷ , and R ⁸ and R ⁹ : R ¹ , R ¹⁰ and Z
Or a hydrogen atom or a group having a positive Hammett σ _p value described for R ² or R ³ , or —OR ¹ or —SR ¹ .

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail. Component (i) used in the present invention
The polymerizable compound having an addition-polymerizable unsaturated bond of
It is selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. For example, those having a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds. Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate ,
Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (acryloxy ethoxy)
Phenyl] dimethylmethane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetramethacrylate.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis -Methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, see Japanese Patent Publication No. 48-417.
JP-A-08-208, in which a hydroxyl-containing vinyl monomer represented by the following general formula (A) is added to a polyisocyanate compound having two or more isocyanate groups in one molecule. Vinyl urethane compounds containing the above polymerizable vinyl groups are exemplified. CH ₂ CC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ ). Further, as described in JP-A-51-37193. Urethane acrylates, JP-A-48-64183,
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-B-49-43191 and JP-B-52-30490 are exemplified. be able to. In addition, Japan Adhesion Association Journal vol. 20, No. 7, pages 300-308 (198
(4 years) as photocurable monomers and oligomers can also be used. The amount of these used is 5 to 50% by weight (hereinafter abbreviated as%), preferably 10 to 40% with respect to all components.

The photopolymerization initiator used in the present invention as component (ii) includes benzyl, benzoin, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, trihalomethyltriazine compound, keto Oxime esters, and also certain photoreducing dyes described in U.S. Pat. No. 2,850,445, such as rose bengal, eosin, erythrosine, or the like, or a combination of a dye and an initiator; (JP-B-44-20189), a system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-20189).
-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292), a system of a dye and an organic peroxide (Japanese Patent Publication No. 62-1982). 1641
JP-A-59-1504, JP-A-59-14020
No. 3, JP-A-59-189340, U.S. Pat.
No. 6,055, JP-A-62-174203), a system of a dye and an active halogen compound (JP-A-54-15102).
JP-A-58-15503, JP-A-63-1781
No. 05, JP-A-63-258903, JP-A-2-63
No. 054), a system of a dye and a borate compound (JP-A-6
2-143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141,
JP-A-64-13142, JP-A-64-13143
JP-A-64-13144, JP-A-64-1704
No. 8, JP-A-64-72150, JP-A-1-2290
03, JP-A-1-298348, JP-A-1-138
No. 204, JP-A-2-179463, JP-A-2-24
No. 4050).

Next, the compound used as the component (iii) of the present invention will be described. The alkyl group of R ^{1 in} the compound of the formula (I) includes straight-chain, branched and cyclic alkyl groups, and preferably has 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
Further, as the substituted alkyl group, a halogen atom (for example, -Cl, -Br or the like), a cyano group, a nitro group, an aryl group (preferably a phenyl group),
A hydroxy group, -NR ¹¹ R ¹² (wherein R ¹¹ and R ¹² independently represent a hydrogen atom,
Represents an alkyl group or an aryl group. ), -COOR
¹³ (wherein, R ¹³ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.), -OCOR ¹⁴ or -OR
¹⁴ (wherein, R ¹⁴ represents an alkyl group having 1 to ¹⁴ carbon atoms or an aryl group) as a substituent. The aryl group of R ¹ includes a 1 to 3 ring aryl group such as a phenyl group and a naphthyl group, and the substituted aryl group includes a substituent of the above-mentioned substituted alkyl group in the above-described aryl group, or Those having an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group for R ¹ include straight-chain, branched, and cyclic groups having 2 to 18 carbon atoms. Examples of the substituent for the substituted alkenyl group include those described above as the substituent for the substituted alkyl group. included. R above
Examples of the ¹ alkynyl group include linear or branched ones having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group.

Specific examples of the compound of the formula (I) of the component (iii) used in the present invention include the following compounds. (I) -1 nC ₄ H ₉ -S-nC ₄ H ₉ (I) -2 nC ₈ H ₁₇ -S-nC ₈ H ₁₇ (I) -3 (H ₅ C ₆ -S) ₃ -CH (I _{) -4 (H 5 C 6 -S} ) 2 -CH 2 (I) -5 H 5 C 6 -S-CH 3 (I) -6 HOOC-C 6 H 4 -pS-CH 3 (I) -7 OHC-C ₆ H ₄ -pS-CH ₃ (I) -8 NC-C ₆ H ₄ -pS-CH ₃ (I) -9 H ₅ C ₆ -S-CH (CH ₃ ) -CO-CH ₃ ( _{I) -10 H 5 C 6 -S} -CH (CH 3) -CN (I) -11 H 5 C 6 -S-CH 2 Cl

[0013]

Embedded image Examples of the group having a positive Hammett σ _p value of R ² , R ³ , R ⁸ , and R ⁹ of the compound of the formula (II) include a halogen atom, a cyano group, a nitro group, a —CO ₂ C ₂ H ₅ group, COCH ₃ groups, -N ⁺ (CH ₃ ) ₃
Groups and the like. Examples of the alkyl group, substituted alkyl group, aryl group, substituted aryl group, alkenyl group, and substituted alkenyl group of R ⁵ , R ⁶ , and R ⁷ include the same as those for R ¹ . R ⁶ and R ⁷ may form an alkylene group or a 5- or more-membered ring containing at least one of S and O, preferably a 5- to 7-membered ring.
Examples of the compound (II) include the following. (II) -1 (CH ₃ ) ₂ CHCH ₂ -O-CS-S-nC ₄ H ₉ (II) -2 (CH ₃ ) ₂ CHCH ₂ -O-CS-S-CH ₂ -C ₆ H ₅ ( II) -3 (CH ₃ ) ₂ CH-O-CS-SS-CS-O-CH (CH ₃ ) ₂ (II) -4 (C ₂ H ₅ ) ₂ N-CS-S-nC ₄ H ₉ ( II) -5 (C ₂ H ₅ ) ₂ N-CS-S-CH ₂ -C ₆ H ₅ (II) -6 (C ₂ H ₅ ) ₂ N-CS-SS-CS-N (C ₂ H ₅ ) ₂ (II) -7 (C ₂ H ₅ ) ₂ N-CS-SS-CS-N (nC ₄ H ₉ ) ₂ (II) -8 (C ₂ H ₅ ) ₂ N-CS-S-CH ₂ CH (-S-CS-N (C
_{2 H 5) 2) CH 2} -S-CS-N (C 2 H 5) 2

The following are examples of the compound (III). (III) -1 nC ₄ H ₉ -SO ₂ -nC ₄ H ₉ (III) -2 p-CH ₃ -C ₆ H ₄ -SO ₂ -CH ₂ -CH ₃ (III) -3 p-CH _3- C ₆ H ₄ -SO ₂ -CH ₂ -SCH ₃ (III) -4 p-CH ₃ -C ₆ H ₄ -SO ₂ -CH ₂ -CO-CH ₃ (III) -5 p-CH ₃ -C ₆ H ₄ -SO ₂ -CH ₂ -SO ₂ -C ₆ H ₄ -p-CH ₃ (III) -6 p-CH ₃ -C ₆ H ₄ -SO ₂ -CH ₂ -CN (III) -7 p- CH ₃ -C ₆ H ₄ -SO ₂ -O-nC ₄ H ₉ (III) -8 CH ₃ -SO ₂ -OC ₂ H ₅ (III) -9 C ₆ H ₅ -O-SO ₂ -CH _2- CO-CH ₃ (III) -10 C ₆ H ₅ -O-SO ₂ -CH ₂ -SO ₂ -OC ₆ H ₅ (III) -11 C ₆ H ₅ -O-SO ₂ -CH ₂ -CN

[0015]

Embedded image The compounds of the above (I) to (III) are obtained from Comprehensive Organ
ic Chemistry Volume 3 Part 11 (D, Barton, WD, Olli
s, Pergamon Press), Polym, Rep. Jap, 37 , 3
508 (1988), JP-A-64-111, JP-A-6-111
4-26619, M, Niwa, Macromolecules, 18
9 , 2187 (1988) and the like. Also, (I) -1 to 12,
(III) -1, 3, 12, 13 can be purchased from Aldrich, Wako Pure Chemical Industries, etc., and (II) -3, 4 are marketed by Sanshin Chemical Co., Ltd. as rubber vulcanization accelerators. ing. The concentration of the photopolymerization initiator of the component (ii) and the compound of the component (iii) in the composition of the present invention is usually low. Is generated. Component (ii) and component (iii) in the present invention
Is preferably used in the range of 0.01% to 60% with respect to the photopolymerizable compound of the component (i). More preferably, 0.5% to 30% gives good results.

The photopolymerizable composition of the present invention preferably contains a linear organic polymer as a binder. As such a “linear organic polymer”, any material can be used as long as it is a linear organic polymer having compatibility with a photopolymerizable ethylenically unsaturated compound. May be. Preferably, a water- or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer functions as a film-forming agent of the composition, and is selected and used depending on the type of a developer to be used, that is, a developer such as water, weakly alkaline water, or an organic solvent. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, for example, JP-A-59-44615 and JP-B-54-3432.
7, JP-B-58-12577, JP-B-54-259
No. 57, JP-A-54-92723, JP-A-59-53
No. 836 and JP-A-59-71048, namely, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, Examples include an esterified maleic acid copolymer. In addition, an acidic cellulose derivative having a carboxylic acid group in a side chain is also included. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are also useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, an alcohol-soluble polyamide or a polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin is also useful.

These linear organic high molecular polymers can be incorporated into the entire composition in any amount. But 90%
In the case where the ratio exceeds the above range, no preferable result is obtained in view of the intensity of the formed image and the like. Preferably it is 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5. In addition, in the composition of the present invention, in addition to the above basic components, a small amount of a polymerizable compound having an addition-polymerizable unsaturated bond may be used to prevent unnecessary thermal polymerization during the production or storage of the photosensitive composition. It is desirable to add a thermal polymerization inhibitor. Hydroquinone, as a suitable thermal polymerization inhibitor,
p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4 -Methyl-6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, aluminum aluminum N-nitrosophenylhydroxyamine and the like.
The amount of the thermal polymerization inhibitor added is about 0.
Preferably from 01% to about 5%. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of dye and pigment added is preferably from about 0.5% to about 5% of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 2 to 50%. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, it is 0.5 to 5 g / m ² .

A dimensionally stable plate is used as the support. Examples of such materials include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), and metal plates such as aluminum (including aluminum alloys), zinc, copper, and the like. Plastic films such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include vapor-deposited paper or plastic films. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. In addition,
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in No. 18327 is also preferable. In the case of a support having a metal, particularly aluminum surface, a graining treatment,
Surface treatment such as immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation is preferably performed.

Further, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is, for example, electrolysis using an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. It is carried out by flowing a current in the liquid using an aluminum plate as an anode. Also, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is effective. Further, a support provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503, and the above-described anodizing treatment and sodium silicate treatment were carried out. Combined surface treatments are also useful. Also,
It is also preferable to sequentially perform mechanical roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893.

Further, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) ) Or those coated with a yellow dye, an amine salt or the like are also suitable. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to improve the adhesion of the photosensitive layer. It is done for things. On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, acidic celluloses, etc., in order to prevent polymerization inhibition by oxygen in the air. A protective layer made of a polymer having excellent oxygen barrier properties as described above may be provided. For a method of applying such a protective layer, see, for example, US Pat. No. 3,458,311.
And Japanese Patent Publication No. 55-49729. The photopolymerizable composition of the present invention can be used for a usual photopolymerization reaction. Further, the present invention can be applied to various fields such as a photoresist for producing a printing plate, a printed board, and the like.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to image exposure, and then an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developers when the photopolymerizable composition of the present invention is used for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and silicate. Potassium, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of such an inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. The alkali solution is added so as to have a concentration of 0.1 to 10%, preferably 0.5 to 5%. The alkaline aqueous solution may contain a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol, or 2-butoxyethanol, if necessary. For example, U.S. Pat. Nos. 3,375,171 and 3,375,171.
No. 615,480. Further, Japanese Patent Application Laid-Open Nos. 50-26601 and 58-5
No. 4341, JP-B-56-39464, 56-42
The developer described in each of the publications of No. 860 is also excellent.

[0023]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light.
Therefore, as the light source, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp,
Metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, sunlight and the like can be used.

[0024]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 6 and Comparative Examples 1 and 2 An aluminum plate having a thickness of 0.30 mm was coated with a nylon brush and
The surface was sand-grained with a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. After immersing in 10% sodium hydroxide at 70 ° C for 60 seconds and etching,
After washing with running water, it was neutralized and washed with 20% nitric acid, and then washed with water. This was converted to 160 coulombs / dm ^{2 in} a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of _VA = 12.7 V.
The electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. When the surface roughness was measured, it was 0.6 μ ( _Ra display). Subsequently, it was immersed in a 30% aqueous sulfuric acid solution and desmutted at 55 ° C. for 2 minutes.
Anodizing treatment was performed for 2 minutes so that the thickness of the anodic oxide film became 2.7 g / m ² at / dm ² . On the aluminum plate thus treated, a photopolymerizable composition having the following composition was applied so as to have a dry coating weight of 1.4 g / m ² ,
After drying for a minute, a photosensitive layer was formed.

Trimethylolpropane tri (acryloyloxypropyl) ether 2.0 g Allyl methacrylate / methacrylic acid 2.0 g Copolymer (copolymer molar ratio 80/20) Photopolymerization initiator Xg Fluorine nonionic surfactant 0. 03 g methyl ethyl ketone 20 g propylene glycol monomethyl ether acetate 20 g Polyvinyl alcohol (degree of saponification 98-
A 3% by weight aqueous solution of 99 mol% and a polymerization degree of 550) was applied so that the dry application weight was 2 g / m ² ,
Dried for minutes. Sensitivity measurement was performed using Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd.
At step 0.05, the step tablet was increased by 0.15 in order and used up to 15 steps. In the photosensitivity test, in Examples 1 to 12, a xenon lamp was used as a light source, and a PS step was performed for 120 seconds at an illuminance of 0.0132 mW / cm ² on the surface of the photosensitive film using monochromatic light obtained through a Kenko optical filter BP-49. The photosensitivity was indicated by the number of clear steps of the guide. Examples 13 to 18 were carried out with a PS light S type (metal halide lamp, 2 KW) manufactured by Fuji Photo Film Co., Ltd. for a distance of 1 m to 20 seconds using a vacuum furnace. The development was performed by immersing in the following developer at 25 ° C. for 1 minute. 1K potassium silicate 30g potassium hydroxide _{15g C 12 H 25 -C 6 H} 4 -OC 6 H 4 -SO 3 Na 3g Water 1000g The results are shown in Table 1.

[0026]

[Table 1] Component (iii) Photoinitiator Light source C / S Clear stages ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (I) -2 PI-1 ( 0.13 g) Xenon + BP-49 8 1 (0.06 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ Example (I) -12 PI-1 (0.13 g) xenon + BP-4992 (0.03 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━ Example (I) -3 PI-1 (0.13 g) Xenon + BP-4993 (0.04 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (I) -13 PI-1 (0.13 g ) Xenon + BP-498 4 (0.04 g) PI-2 (0.1 g) ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (I) -6 PI-1 (0.13 g) Xenon + BP- 49 9 5 (0.04 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Implementation Example (I) -15 PI-1 (0.13 g) Xenon + BP-4976 (0.04 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━ Example (II) -3 PI-1 (0.13 g) Xenon + BP-4997 (0.06 g) PI-2 (0.1 g) ━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (II) -4 PI-1 (0.13 g) Xenon + BP-498 8 (0.05g) PI-2 (0.1g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example ( III) -1 PI-1 (0.13 g) Xenon + BP-49 79 0.04 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (III) -3 PI-1 (0.13 g) Xenon + BP-49 7 10 (0.05 g) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━ Example (III) -12 PI-1 (0.13 g) xenon + BP-49811 (0.03 g) PI-2 (0.1 g) ━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (III) -13 PI-1 (0.13 g) Xenon + BP-49 7 12 (0.03 g ) PI-2 (0.1 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (I) -12 PI-3 (0.1 g) Metal halide 12 13 (0.03 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Implementation Example (I) -3 PI-3 (0.1g) Metal halide 12 14 (0.04g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example (II) -3 PI- 3 (0.1g) Metal halide 13 15 (0.06g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example ( II) -4 PI-3 (0.1g) Metal halide 12 16 (0.05g) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━ Example (III) -1 PI-3 (0.1 g) Metal halide 11 17 (0.04 g) ━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━ Example (III) -12 PI-3 (0.1 g) Metal halide 12 18 (0.05 g) ━━━━━━━━━━━━━━━━━━━━比較 Comparative Example None PI-1 (0.13 g) Xenon + BP-49 61 PI-2 (0.1 g) ━━━━━━━━━━━比較 Comparative Example 2 None PI-3 (0.1 g) Metal halide 10 ━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━

[0027]

Embedded image From the results in Table 1, it can be seen that the addition of the compounds represented by formulas (I), (II) and (III) clearly increases the sensitivity.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G03F 7/038 G03F 7/038 (72) Inventor Keitaro Aoshima 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Photo Film Co., Ltd. (56 (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/027 G03F 7/00 503 G03F 7/004 G03F 7/028 G03F 7 / 038

Claims (1)

(57) [Claims] 1. A photopolymerizable composition comprising the following components (i), (ii) and (iii). (I) an addition-polymerizable compound having at least one ethylenically unsaturated double bond; (ii) a photopolymerization initiator; (iii) represented by the following general formula (I), (II) or (III) at least one of the compounds ^{(I) R 1 -S-CHR} 2 R 3 R 1 is an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or a substituted alkenyl group, R ² and R ³ is the same as R ¹ , or a hydrogen atom or a group having a positive Hammett σ _p value, -OR ¹ or -SR ¹ , or R ¹ is bonded to R ² or R ³ to form a ring You may. (II) Y-CS-SR 4 R 4 is R ¹ as defined or Y-CS-S- are shown, Y represents a -OR ⁵ or ^{-NR 6 R 7, R 5,} R 6, R 7 is an alkyl Represents a group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or a substituted alkenyl group, and R ⁶ and R ⁷ may combine to form a ring. (III) Z-CHR ⁸ R ⁹ Z represents R ¹⁰ -SO ₂ -or R ¹⁰ -O-SO _2- , and R ¹⁰ has the same meaning as R ⁵ , R ⁶ , R ⁷ , and R ⁸ , R ⁹ Is synonymous with R ¹ , R ¹⁰ , Z, or represents a hydrogen atom, a group having a positive Hammett σ _p value as described in R ² and R ³ , or —OR ¹ or —SR ¹ .