JPH0588842B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention relates to a photopolymerizable composition. More specifically, it relates to a photopolymerizable composition comprising a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and, if necessary, a binder. The present invention relates to a photopolymerizable composition useful for photosensitive layers used in the production, photoresists used in the production of printed circuit boards, and the like. "Prior Art" A photosensitive composition prepared by mixing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having an appropriate film-forming ability and a thermal polymerization inhibitor. 2. Description of the Related Art A method of copying an image using a photographic method using an object is now widely known. That is, U.S. Patent No. 2927022;
As described in No. 2902356 or No. 3870524, this type of photosensitive composition undergoes photopolymerization upon irradiation with light, hardening and becoming insolubilized. Light is irradiated through the negative of the image, and only the unexposed areas are removed using a suitable solvent (hereinafter simply referred to as development).
By this, a cured image of the desired photopolymerizable composition can be formed. It goes without saying that this type of photosensitive composition is extremely useful for making printing plates, photoresists, and the like. In addition, conventionally, polymerizable compounds having ethylenically unsaturated bonds alone do not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to increase photosensitivity. Benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc. have been used. However, when these photopolymerization initiators are used, the curing sensitivity of the photopolymerizable composition is low, so that image exposure during image formation requires a long time. For this reason, in the case of detailed images, if there is slight vibration in the operation during image exposure, a good quality image cannot be reproduced, and the amount of energy radiated by the exposure light source must be increased, resulting in It was necessary to consider the dissipation of a large amount of heat generated. In addition, there was a problem that the film of the composition was easily deformed and deteriorated due to heat. In addition, in recent years, increased sensitivity to ultraviolet rays has been studied, and UV projection exposure methods and the like in printing plates are already in practical use, and highly sensitive photosensitive materials that are compatible with these methods are being developed. However, it cannot be said that it has sufficient sensitivity yet. "Problems to be Solved by the Invention" Therefore, an object of the present invention is to provide a highly sensitive photopolymerizable composition. Another object of the present invention is to generally provide a photopolymerizable composition containing a photopolymerization initiator that increases the rate of photopolymerization of a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond. It is. "Means for Solving the Problems" As a result of extensive research to achieve the above object, the present inventors have discovered that a certain photoinitiator is capable of photopolymerizing a polymerizable compound having an ethylenically unsaturated bond. The present invention was developed based on the discovery that the speed can be significantly increased. That is, the present invention provides a photopolymerizable composition containing an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiator,
The photopolymerizable composition is characterized in that it contains a photopolymerization initiator represented by at least one compound represented by the following general formula (I).

[Chemical Formula] (In the formula, R ₁ to _{R 4} each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group,
Represents a substituted alkoxy group, amino group, or substituted amino group. Further, R ₁ to _{R 4} may form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heteroaromatic group, an acyl group, a cyano group, an alkoxycarbonyl group, a carboxyl group, or a substituted alkenyl group. . Further, R ₅ and R ₆ may both form a ring composed of nonmetallic atoms. X represents an oxygen atom, a sulfur atom, or a nitrogen atom having a substituent. G ₁ and G ₂ may be the same or different from each other,
Hydrogen atom, cyano group, alkoxycarbonyl group, substituted alkoxycarbonyl group, aryloxycarbonyl group, substituted aryloxycarbonyl group, acyl group, substituted acyl group, arylcarbonyl group, substituted arylcarbonyl group, alkylthio group, arylthio group, alkyl Represents a sulfonyl group, arylsulfonyl group, or fluorosulfonyl group. However, G ₁ and G ₂ cannot become hydrogen atoms at the same time. Further, G ₁ and G ₂ may form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded. ) Hereinafter, the present invention will be explained in detail. The polymerizable compound having an ethylenically unsaturated bond used in the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, preferably at its terminal. For example, it has chemical forms such as monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of monomers and their copolymers include:
Examples include unsaturated carboxylic acids and their salts, esters with aliphatic polyhydric alcohol compounds, amides with aliphatic polyhydric amine compounds, and the like. Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, and maleic acid. Salts of unsaturated carboxylic acids include sodium and potassium salts of the aforementioned acids. Further, as specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, examples of acrylic esters include ethylene glycol diacrylate, triethylene glycol triacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. Acrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyl-oxypropyl) ether, trimethylolethane triacrylate,
1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, sorbitol triacrylate,
Examples include sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomers. Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol dimethacrylate. erythritol trimethacrylate,
Dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]
Examples include dimethylmethane, bis-[p-(acryloxyethoxy)phenyl]dimethylmethane, and the like. As the itaconic acid ester, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate,
Examples include tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetrataconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Other esters include ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate. In addition, ethylene glycol (meth)acrylate, trimethylolethane triacrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate,
Examples include trimethylolpropane tri(acryloyloxypropyl) ether and tri(acryloyloxyethyl) isocyanurate. Furthermore, mixtures of the aforementioned esters may also be mentioned. Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexamethylenebis-methacryl. amide, diethylenetriamine trisacrylamide, xylene bisacrylamide, xylene bismethacrylamide, etc. Other examples include polyisocyanate compounds having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-41708,
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by the following general formula () is added. CH ₂ =C(R)COOCH ₂ CH(R')OH () (However, R and R' represent H or CH _3. ) Also, Special Publication No. 48-41708, Special Publication No. 6034-1973,
Urethane acrylates as described in JP-A-51-37193, JP-A-48-64183,
Mention polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting epoxy resin with (meth)acrylic acid, which are described in Japanese Patent Publication No. 49-43191 and Japanese Patent Publication No. 52-30490. I can do it. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association Journal Vol. 20, No. 7, pages 300 to 308 can also be used. In addition,
The amount used is 5 to 50% by weight based on the total ingredients.
(Hereinafter abbreviated as %) Preferably it is 10 to 40%. Next, the photopolymerization initiator, which is a significant feature in the photopolymerizable composition of the present invention, will be explained. General formula (I) used in the present invention

In the photopolymerization initiator represented by [Chemical formula], R ₁ to _{R 6}
As the alkyl group, those having 1 to 20 carbon atoms such as methyl, ethyl and t-butyl can be used. Further, as the aryl group, one having 1 to 10 carbon atoms such as phenyl can be used. Furthermore, as the alkoxy group of R ₁ to R ₄ ,
Those having 1 to 6 carbon atoms such as methoxy, ethoxy and butoxy can be used. In addition, R ₁
As the substituted amino group for ~ _R4 , an alkylamino group or arylamino group having 1 to 20 carbon atoms, such as methylamino, dimethylamino, diethylamino, diphenylamino, piperidino, and monophorino, can be used. These alkyl groups, aryl groups, alkoxy groups, alkylamino groups, and arylamino groups may have a substituent. Examples of substituents include halogen atoms such as fluorine, chlorine, and bromine, alkoxycarbonyl groups such as ethoxycarbonyl, alkoxy groups such as methoxy and ethoxy, aryl groups such as phenyl, and cyano groups. When R ₁ to _{R 4} form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded, examples of structures containing the ring include those shown in (A), (B), and (C) below.

[ka]

[ka]

[Chemical formula] In addition, when R ₅ and R ₆ are acyl groups, acetyl,
Examples include those having an alkyl group having 1 to 10 carbon atoms or an aryl group such as benzoyl, and in the case of an alkoxycarbonyl group, those having an alkyl group having 1 to 6 carbon atoms such as ethoxycarbonyl. Furthermore, in the case of a substituted alkenyl group, those having 2 to 10 carbon atoms such as a styryl group can be used, and in the case of a heteroaromatic group, those shown in (D) to (F) below can be used.

【formula】

【formula】

[Formula] Furthermore, both R ₅ and R ₆ may form a ring together with the carbon atom to which they are bonded. An example is the structure shown in (G) below.

embedded image When X is nitrogen having a substituent, the same substituents as the alkyl groups and aryl groups listed for R ₁ to _{R 6} can be used. G ₁ and G ₂ may be the same or different, and each is a hydrogen atom,
1 or more carbon atoms such as cyano group, ethoxycarbonyl group, etc.
Alkoxycarbonyl group having 10 alkyl groups, phenoxycarbonyl group, etc. Aryloxycarbonyl group having aryl group having 6 to 10 carbon atoms, acetyl group, propionyl group, etc. having 1 to 6 carbon atoms
acyl groups, arylcarbonyl groups with 7 to 11 carbon atoms such as benzoyl groups, alkylthio groups with 1 to 6 carbon atoms such as methylthio groups and ethylthio groups, arylthio groups with 6 to 10 carbon atoms such as phenylthio groups, phenyl It represents an arylsulfonyl group having 6 to 10 carbon atoms such as a sulfonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group, and an ethylsulfonyl group, or a fluorosulfonyl group. These alkoxycarbonyl groups, aryloxycarbonyl groups, acyl groups, arylcarbonyl groups, alkylthio groups, arylthio groups, arylsulfonyl groups, and alkylsulfonyl groups may have a substituent, and examples of the substituent include halogens such as chlorine. Examples include an alkoxycarbonyl group having an alkyl group having 1 to 6 carbon atoms, a carboxyl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group. Also, aryloxycarbonyl group, arylcarbonyl group,
In the case of an arylthio group or an arylsulfonyl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group can also be used in addition to the above-mentioned substituents. In addition, when G ₁ and G ₂ form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded, the ring is usually used as an acidic nucleus in merocyanine dyes, and the following may be mentioned. (a) 1,3-dicarbonyl nucleus, such as 1,3-indanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione It is. (b) Pyrazolinone nuclei, e.g. 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1-(2-
benzothiazoyl)-3-methyl-2-pyrazolin-5-one. (c) Isoxazolinone nucleus, such as 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc. (d) Oxindole nucleus, e.g. 1-alkyl-
2,3-dihydro-2-oxindole. (e) 2,4,6-triketohexahydropyrimidine core, such as barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of such derivatives include 1-alkyl derivatives such as 1-methyl and 1-ethyl, 1,3-dialkyl derivatives such as 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, and 1,3-dibutyl derivatives. (p-chlorophenyl), 1,
Examples include 1,3-diaryls such as 3-di(p-ethoxycarbonylphenyl) and 1-alkyl-3-aryls such as 1-ethyl-3-phenyl. (f) 2-thio-2,4-thiazolidinedione nucleus,
For example, rhodanine and its derivatives. Such derivatives include 3-ethylrhodanine, 3-
Examples include 3-alkylrhodanines such as allylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and the like. (g) 2-thio-2,4-oxazolidinedione (2-thio-2,4-(3H,5H)-oxazoledione) nucleus, e.g. 2-ethyl-2-thio-
It is 2,4-oxazolidinedione. (h) thianaphthenone nuclei, such as 3(2H)-thianaphthenone and 3(2H)-thianaphthenone-1,
1-dioxide. (i) 2-thio-2,5-thiazolidinedione nucleus,
For example, 3-ethyl-2-thio-2,5-thiazolidinedione. (j) 2,4-thiazolidinedione nucleus, e.g. 2,
4-thiazolidinedione, 3-ethyl-2,4
-thiazolidinedione, 3-phenyl-2,4
-thiazolidinedione. (h) Thiazolidione nucleus, such as 4-thiazolidinone, 3-ethyl-4-thiazolidinone. (l) 4-thiazozolinone nucleus, e.g. 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-
It's on. (m) 2-imino-2-oxozolin-4-one (hydantoin) nucleus. (n) 2,4-imidazolidinedione (hydantoin) nucleus, such as 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione. (o) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus, such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione It is. (p) 2-imidazolin-5-one nucleus, e.g. 2
-n-propyl-mercapto-2-imidazolin-5-one. (q) Furan-5-one. The photopolymerization initiator represented by the general formula (I) used in the present invention can be synthesized from the general formula () or a compound represented by () and a compound represented by ().

[ka]

[ka]

[Formula] (In the above formula, L ₁ and L ₂ represent an alkyl group, and Z ^- represents an anion.) Specific examples of the photopolymerization initiator represented by the general formula (1) used in the present invention are shown below.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

embedded image A binder may be used in the polymerizable composition of the present invention, if necessary. The binder should be compatible with the polymerizable ethylenically unsaturated bond compound and the photopolymerization initiator so that demixing does not occur in all of the manufacturing steps of the photosensitive material, from preparation of the coating solution of the composition to coating and drying. be as good as possible;
The photosensitive layer or resist layer is required to have characteristics such as being able to be developed after image exposure, whether by solution development or peeling image, and being able to form a tough film as the photosensitive layer or resist layer. be done. It is usually selected from linear organic polymers as appropriate. Specific examples of binders include chlorinated polyethylene, chlorinated polypropylene, polyacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-butyl group, iso-butyl group, n-hexyl group, -ethylhexyl group, etc.), acrylic acid alkyl ester (same as alkyl group) and acrylonitrile,
Copolymers with at least one monomer such as vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, copolymers of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, Vinyl acetate, polyvinyl alcohol, polyacrylonitrile, copolymers of acrylonitrile and styrene, copolymers of acrylonitrile with butadiene and styrene, polymethacrylic acid alkyl esters (alkyl groups include methyl group, ethyl group, n-propyl group) group, n-butyl group, iso-
Butyl group, n-hexyl group, cyclohexyl group,
(2-ethylhexyl group, etc.), copolymers of methacrylic acid alkyl esters (alkyl groups are the same as above) and at least one monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polystyrene, poly-α-methylstyrene , polyamide (6-nylon, 6,6-
nylon, etc.), methylcellulose, ethylcellulose, acetylcellulose, polyvinyl formal, polyvinyl butyral, and the like. Furthermore, when a water or alkaline water soluble organic polymer is used, a water or alkaline water phenomenon becomes possible. Examples of such polymers include addition polymers having carboxylic acid in the side chain, such as methacrylic acid copolymers (for example, copolymers of methyl methacrylate and methacrylic acid, and copolymers of ethyl methacrylate and methacrylic acid). polymers, copolymers of butyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of allyl methacrylate and methacrylic acid,
Copolymer of ethyl acrylate and methacrylic acid,
Copolymers of methacrylic acid and styrene and ethyl methacrylate), acrylic acid copolymers (copolymers of ethyl acrylate and acrylic acid, copolymers of butyl acrylate and acrylic acid, copolymers of ethyl acrylate and acrylic acid, etc.) copolymers with styrene and acrylic acid), as well as itaconic acid copolymers, crotonic acid copolymers, and partially esterified maleic acid copolymers. Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. These high molecular weight polymers can be used alone as a binder. Furthermore, two or more types of high molecular weight polymers that are compatible with each other to the extent that no demixing occurs during the manufacturing process from preparation of the coating liquid to application and drying are mixed in an appropriate ratio and used as a binder. You can also do it. The molecular weight of the high molecular weight polymer used as a binder can vary widely depending on the type of polymer. The range is preferably from about 5,000 to about 2 million, more preferably from 10,000 to 1 million. Furthermore, during the production or storage of the composition of the present invention, it is desirable to add a thermal polymerization inhibitor to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol,
Examples include pyrogallol, t-butylcatechol, benzoquinone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, nitrobenzene, and dinitrobenzene. In some cases, dyes or pigments may also be used for coloring purposes, such as methylene blue, crystal violet, rhodamine B, fuchsin, auramine, azo dyes, anthraquinone dyes, titanium oxide, carbon black, iron oxide, phthalocyanine pigments, azo Pigments and the like may also be added. After anodizing (sulfuric or phosphoric acid), negative-working diazo resins, e.g. p-
A PF ₆ salt of a condensate of diazodiphenylamine and formaldehyde may be added. Furthermore, a plasticizer can be added to the photopolymerizable composition of the present invention, if necessary. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. Examples include glycol esters, phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate, and aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dibutyl sebacate, and dibutyl maleate. The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various components in a solvent and coating it on a suitable support by a known method. Next, preferred ratios of the various constituent components in this case are expressed in parts by weight based on 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond.

〔Effect of the invention〕

The photopolymerizable composition of the present invention has high sensitivity to actinic light. Therefore, as a light source, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, etc. can be used. "Examples" Hereinafter, synthesis examples of the photopolymerization initiator used in the present invention and examples of the present invention will be described, but the present invention is not limited thereto. Synthesis example Method for producing compound (13) 2-methoxy-2-ethoxy-4-methyl-7
-Diethylamino-2H-benzopyran 6.5g and ethylcyanoacetate 4g were mixed and heated at 150℃.
Heat for 30 minutes. After cooling, the reaction mixture was passed through a silica gel column using hexane-ethyl acetate 1:1 (volume ratio) as an eluent to remove black impurities, and then recrystallized from 50 ml of ethanol. The crystals were collected by filtration and dried to obtain 1.2 g of brown crystals with a melting point of 146-148°C. Electronic spectrum (in tetrahydrofuran) λmax 473 nm ε=3.25×10 ⁴ Infrared absorption spectrum (KBr) cm ^-1 2200, 1683, 1583, 1512, 1420, 1350, 1140. Examples 1 to 5 The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly washed with water.
After etching by immersing in 10% sodium hydroxide at 70°C for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and then washing with water. This was electrolytically blocked in a 1% nitric acid aqueous solution using an alternating sinusoidal waveform current under the condition of V _A =12.7V with an anodic electricity amount of 160 clones/dm ² . When the surface roughness was measured, it was 0.6μ (Ra display). 30 in a row
% H ₂ SO ₄ aqueous solution and desmatted for 2 minutes at 55 °C, the current density in 20% H ₂ SO ₄ aqueous solution
It was anodized for 2 minutes at 2 A/dm ² to a thickness of 2.7 g/m ² . A photosensitive solution having the composition shown below was coated onto the aluminum plate thus treated so that the dry coating weight was 1.5 g/m ² and dried to form a photosensitive layer. Allyl methacrylate/methacrylic acid copolymer (copolymerization molar ratio 80/20) 3.2g Pentaerythritol Tetraacrylate 1.7g Photopolymerization initiator 5 mol% relative to monomer Methyl ethyl ketone 20g Propylene glycol monomethyl ether acetate 20g Fluorinated nonionic interface Activator 0.03g [Fluorad FC-430 (trade name) manufactured by 3M] A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification 86.5-89 mol%, degree of polymerization 1000) was applied on this photosensitive layer by dry coating weight. It was coated at a concentration of 2 g/m ² and dried at 100° C. for 2 minutes. Exposure was performed for 1 minute from a distance of 1 m using a vacuum baking device using a PS Light S type (metal halide lamp, 2 KW) manufactured by Fuji Photo Film Co., Ltd. The metal halide lamp has a bright line spectrum between 300 and 450 nm. For sensitivity measurement, a continuous step wedge with an LTF concentration step of 0.15 was used. Development was carried out by immersing the film in the following developer solution at 25°C for 1 minute. Benzyl alcohol 10g Monoethanolamine 1g Triethanolamine 10g Isopropylnaphthalene 2g Sodium sulfonate pure water 1000ml Table 1 shows the sensitivity results when the photopolymerization initiator was changed.

【table】

Claims (1)

[Scope of Claims] 1. A photopolymerizable composition comprising an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiator, the photopolymerization initiator being at least one of the following: A photopolymerizable composition containing a compound represented by general formula (I). [Chemical formula] (However, in the formula, R ₁ to _{R 4} each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, Represents a substituted amino group. Also, R ₁ to _{R 4} may form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, It represents a substituted alkyl group, aryl group, substituted aryl group, heteroaromatic group, acyl group, cyano group, alkoxycarbonyl group, carboxyl group, substituted alkenyl group. R ₅ and R ₆ both represent a ring consisting of a nonmetallic atom. may be formed. X represents O, S, NH, or a nitrogen atom having a substituent. G ₁ and G ₂ may be the same or different from each other,
Hydrogen atom, cyano group, alkoxycarbonyl group, substituted alkoxycarbonyl group, aryloxycarbonyl group, substituted aryloxycarbonyl group, acyl group, substituted acyl group, arylcarbonyl group, substituted arylcarbonyl group, alkylthio group, arylthio group, alkyl Represents a sulfonyl group, arylsulfonyl group, or fluorosulfonyl group. However, G ₁ and G ₂ cannot become hydrogen atoms at the same time. Further, G ₁ and G ₂ may form a ring consisting of a nonmetallic atom together with the carbon atom to which they are bonded. )