JPS6049892B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable composition, particularly a photopolymerizable composition that can be developed with water and is suitable for use in planographic printing plates, resin relief plates, resists for producing printed circuit boards, etc. The present invention relates to a sexual composition.

Conventionally, there are two types of photosensitive lithographic printing plates: one is a type of ink that adheres only to the image area of the plate surface after the printing plate is exposed and developed to improve the adhesion and printing durability of the ink image on the plate. This is an external printing plate that is coated with a lacquer that makes the printing process easier.Other types include a material that improves ink adhesion and printing durability in the photosensitive layer of the lithographic printing plate, and can be loaded directly into the printing machine after exposure and development. It is an internal printing plate that can be printed on.

It is desirable for all types of lithographic printing plates to be able to be developed with neutral, ordinary water during the plate-making process from the viewpoint of reducing plate-making costs, reducing pollution, and controlling the work process. Some type printing plates, such as water-soluble diazo resins, can be developed with water, but internal type printing plates can usually be developed with water and have satisfactory printability. For example, printing plates using photopolymerizable compositions that are usually water-developable and consist mainly of water-soluble resins and monomers having unsaturated bonds may cause image areas to swell during development. Alternatively, even without swelling, the lipophilicity of the image area was weak and ink adhesion was poor, so as a countermeasure to this problem, a method was taken to increase the proportion of lipophilic components added to increase the lipophilicity of the image area. However, in this case, there were various problems when using the lithographic printing plate, such as the component oozing out, crystallizing and precipitating as solid particles, or reducing the viscosity of the photosensitive layer and causing stickiness on the plate surface. The inventors
Research has been carried out by preparing photopolymerizable photosensitive compositions using various hydrophilic and water-soluble resins. The present invention was achieved by discovering that a photosensitive material using the photopolymerizable photosensitive composition can be developed with water and provides a good image after development. That is, the present invention relates to a water-soluble methacrylic acid resin, an ethylenically unsaturated compound having a boiling point of 100° C. or higher at atmospheric pressure and having at least two polymerizable unsaturated groups in one molecule, and a photopolymerization initiator. In the photopolymerizable composition containing the methacrylic acid resin, the methacrylic acid resin has a 2 volume % aqueous solution of about 5,000 Cps (centiboads) to about 300,000 Cps.
and the ethylenically unsaturated compound is 0.5 parts by weight of the methacrylic acid resin.
A water-developable photopolymerizable photosensitive composition characterized in that it contains both in a proportion of up to 5 parts by weight, and the photopolymerizable photosensitive composition described above is combined with an alkanol having 6 or less carbon atoms or an alkanol having 6 or less carbon atoms. This is a solution of a photopolymerizable photosensitive composition dissolved in a mixture of alkanol and water. The methacrylic acid resin (polymethacrylic acid) that can be used in the present invention has a viscosity of about 5,000 Cps (centiboads) as a 2% aqueous solution at 25°C.
to about 300,000 Cps, preferably from about 30,000 Cps to about 150,000 Cps.

In a photopolymerizable photosensitive composition containing a methacrylic acid resin having a viscosity within the above-mentioned range, for example, trimethylol as an ethylenically unsaturated compound is added to 1 part by weight of the resin in order to increase the lipophilicity of the image area. Propane triacrylate 1. The photosensitive layer of a photosensitive material obtained by applying the composition added to the heel portion onto a support and drying it is a hard layer with almost no stickiness, and the photosensitive layer in unexposed areas can be easily removed by developing with water after image exposure. The photosensitive layer, which had been photopolymerized and hardened and became water-insoluble, remained on the support to form an image. It is surprising that a photosensitive layer with such a composition is hardly sticky, and this is because the degree of polymerization of the methacrylic acid resin is high and its glass transition temperature (Tg) is higher than that of other hydrophilic or water-soluble resins. This is thought to be due to the fact that it is extremely high compared to plastic resins (polymers). Tg (0K) of hydrophilic or water-soluble polymers Polymethacrylic acid 501 Polyvinyl alcohol 358 Polyvinylpyrrolidone 359 Polyethylene oxide 230 Polyacrylamide 379 (RPOIymerHand, edited by J. Brandrup et al.
bOOk. 2nd edition (Wlley-1interscje
The methacrylic acid resin used in the present invention contains a photosensitive material after photopolymerization to the extent that the water-developable property of the photopolymerizable photosensitive composition is not substantially impaired. In order to increase the lipophilicity of the composition, other tyrenically unsaturated compounds (e.g. methyl methacrylate, methyl acrylate, styrene, butadiene,
Ethylene, etc.) can be copolymerized and contained.

Generally, the binder used in the photosensitive layer is one with a low degree of polymerization in order to improve developability. It is surprising that it can be easily developed with water.

Another advantage of using the water-soluble methacrylic acid resin is that the resin is also soluble in alcohol.

That is, conventionally known techniques, for example, using polyvinyl alcohol as a binding resin, dispersing monomers in an aqueous solution because polyvinyl alcohol is insoluble in organic solvents, or using it in a photopolymerizable photosensitive composition system. Sensitizers have always been very limited. However, since the photopolymerizable photosensitive composition using the water-soluble methacrylic acid resin of the present invention is soluble in an alcohol alone or an alcohol-water mixture, various monomers and stimulants can be used, and the composition is transparent. It has the effect of being able to be applied as a photosensitive liquid. The ethylenically unsaturated compound that can be contained in the photopolymerizable photosensitive composition of the present invention has a boiling point of 100'C or higher under atmospheric pressure, and has at least two polymerizable unsaturated groups in one molecule. It is a compound with

Ethylenically unsaturated compounds include monomers, prepolymers (dimers, trimers, tetramers, etc.), oligomers (polymers with a polymerization degree of around 10), mixtures thereof, and copolymers thereof (with a polymerization degree of around 10). up to about 15). Ethylenically unsaturated compounds include acrylic esters and methacrylic esters. More specifically, the esters include polyacrylates and polymethacrylates of polyhydric alcohols (here, 1 point refers to diacrylate or higher).
Examples of the polyhydric alcohols include polyethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.), polypropylene oxide (propylene oxide, dipropylene oxide, tripropylene oxide, tetrapropylene oxide, etc.), polybutylene oxide, polycyclohexene oxide, Polyethylene oxide propylene oxide, polystyrene oxide, polyoxetane, polytetrahydrofuran,
Cyclohexanediol, xylylenediol, bis(
β-hydroxyethoxy)benzene, glycerin, diglycerin, tetramethylene glycol, neopentyl glycol. 1,10-
Decanediol, butanetriol, 2-butene-1,
4-diol, 2-n-butyl-2-ethyl-propanediol, 2-butyne-1,4-diol, 3-chloro-1,2-propanediol, 1,4 cyclohexane dimethanol, 3-cyclohexene 1,1-dimethanol, decalin Diol, 2,3-dibromo-2-butene-1,4-diol, 2,2-diethyl-1,3-propanediol, 1,5-dihydroxy-1,2,3,4-
Tetrahydronaphthalene, 2,5-dimethyl-2,5-
Hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diphenyl-1,3-propanediol, dodecanediol, mesoerythritol, 2-
Ethyl-1,3-hexanediol, 2-ethyl-2-
(Hydroxymethyl)-1,3-propanediol, 2
-ethyl-2-methyl-1,3-propanediol, heptanediol, hexanediol, 3-hexene-2
, 5-diol, hydroxybenzyl alcohol, hydroxyethylresorcinol, 2-methyl-1,4-butanediol, 2-methyl-2,4-pentanediol, nonanediol, octanediol, 1,5-pentanediol, 1-phenyl-1 ,2-ethanediol,
1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 2,3,5,6
-tetramethyl-p-xylene-α,α″-diol,
1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,2,6-trihydroxyhexane, 1, 1″-bi-2-naphthol, dihydroxynaphthalene, 1,1″-methylene di-2-naphthol, 1,
2,4-benzenetriol, biphenol, 2,2″
-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, 4-chlorresorcinol, 3,4-dihydroxyhydrocinnamic acid,
Hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, methyl 2,4,6-trihydroxybenzoate, phloroglycinol, pyrogallol, resorcinol, glucose, α-(1-aminoethyl)-p
-Hydroxybenzyl alcohol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2
-Propanediol, N-(3-aminopropyl)-diethanolamine, N,N''-bis(2-hydroxyethyl)piperazine, 2,2-bis(hydroxymethyl)-2,2'',2''-nitrilotriethanol, 2 ,2
-Bis(hydroxymethyl)propionic acid, 1,3-bis(hydroxymethyl)urea, 1,2-bis(4-pyridyl)-1,2-ethanediol, N-n-butyldiethanolamine, diethanolamine, N-ethyl Diethanolamine, 3-mercapto 1,2-propanediol, 3-piperidino 1,2-propanediol, 2-(2-pyridyl)-1,3-propanediol,
Triethanololamine, α-(1-aminoethyl)
-p-hydroxybenzyl alcohol, 3-amino-4
-Hydroxyphenyl, sulfone, etc. Among these acrylic esters and methacrylic esters, preferred are ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate,
Pentaerythritol triacrylate, pentaerythritol dimethacrylate, dipentaerythritol pentaacrylate, glycerin triacrylate, diglycerin dimethacrylate, 1,3-propanediol diacrylate, 1,2, 4-butanetriol trimethacrylate ester, 1,4-cyclohexanediol diacrylate ester, 1,5-pentanediol diacrylate ester, neopentyl glycol diacrylate ester, sorbitol diacrylate ester, sorbitol triacrylate ester, These include sorbitol tetraacrylate ester, sorbitol tetramethacrylate ester, sorbitol hexaacrylate ester, and triacrylate ester of trimethylolpropane added with ethylene oxide. Next, there are acrylamides and methacrylamides.

Examples include methylenebisacrylamide, methylenebismethacrylamide, ethylenediamine, diaminopropane, diaminobutane, pentamethylenediamine, hexamethylenebis(2-aminopropyl)amine, diethylenetriaminediamine, heptamethylenediamine, octamethylenediamine, and Polyamines interrupted by heteroatoms, polyamines containing rings (e.g. phenylenediamine, xylylenediamine, β-(4-
(aminophenyl)ethylamine, diaminobenzoic acid, diaminotoluene, diaminoanthraquinone, diaminofluorene, etc.) polyacrylamides and polymethacrylamides. Next are allyl compounds.

Examples include diallyl esters of dicarboxylic acids such as phthalic acid, terephthalic acid, sebacic acid, adipic acid, glutaric acid, malonic acid, oxalic acid, such as anthraquinone disulfonic acid, benzenedisulfonic acid, 2,5-
Examples include diallyl esters and diallylamides of disulfonic acids such as dihydroxylebenzenedisulfonic acid, dihydroxynaphthalenedisulfonic acid, and naphthalenedisulfonic acid. Next are vinyl ether compounds.

Examples include polyvinyl ethers of the polyhydric alcohols, such as ethylene glycol divinyl ether, 1,3,5-triβ-vinyloxyethoxybenzene, 1,3-diβ-vinyloxyethoxybenzene,
Examples include glycerol trivinyl ether. Next are vinyl esters.

Examples include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, divinylbutane-1,4-disulfonate, and the like. Next are styrene compounds.

Examples include divinylbenzene, p-allylstyrene, p-isopropenestyrene, and the like. Next are esters of itaconic acid and the aforementioned polyhydric alcohols.

Examples include diitaconate 1,4-butanediol ester, diitaconate ethylene glycol ester,
Pentaerythritol diitaconate ester, dipentaerythritol triitaconate ester, dipentaerythritol pentitaconate ester, hexaythritol j
dipentaerythritol ester, etc. Next, there are modified acrylic esters, modified methacrylic esters, modified itaconic esters, acrylated prepolymers, methacrylated prepolymers, and itaconylated prepolymers. Examples include modified diacrylic acid 1,4-butanediol ester, modified triacrylic acid trimethylolpropane ester, modified triacrylic acid pentaerythritol, methacrylated epoxy prepolymer, and acrylated linear polyester. Furthermore, two or more different addition-polymerizable unsaturated bonds such as N-β-hydroxyethyl-β-(methacrylamide)ethyl acrylate, N,N-bis(β-methacryloxyethyl)acrylamide, allyl methacrylate, etc. Compounds having the above are also suitably used in the present invention.

Two or more such ethylenically unsaturated compounds can also be used in combination.

These compounds are used in an amount ranging from 0.5 parts by weight to 5 parts by weight, preferably from 0.8 parts by weight to 3 parts by weight, and particularly preferably from 1 part by weight to 2 parts by weight, based on 1 part by weight of the methacrylic acid resin. used. As the photopolymerization initiator to be contained in the photopolymerizable photosensitive composition of the present invention, conventionally known ones can be suitably used.

For example, J. Rubonyl compounds, nitrogen-containing heterocyclic compounds, organic sulfur compounds, peroxides, as described in Chapter 5 of 1 Light Sensitive Systems by KOsar.
Examples include redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. Typical specific examples include carbonyl compounds such as benzoin, benzoin methyl ether, benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butyl-anthraquinone, 9,1
0-phenanthrenequinone, diacetyl, benzyl, and further compounds represented by the following general formula are useful. In the formula, R1 represents an alkyl group commonly known in cyanine dyes, such as an unsubstituted lower alkyl group such as a methyl group, an ethyl group, or a propyl group; a hydroxyalkyl group such as a 2-hydroxyethyl group; Alkoxyalkyl groups such as methoxyethyl group, for example carboxymethyl group, carboxyalkyl group such as 2-carboxyethyl group, sulfoalkyl group such as 2-sulfoethyl group, 3-sulfopropyl group, e.g. benzyl group, phenethyl group, p Aralkyl groups such as -sulfophenethyl group and p-carboxyphenethyl group, vinylmethyl group, etc. are preferred.

R2 is an alkyl group (for example, a lower alkyl group such as a methyl group, an ethyl group, or a propyl group is preferable) or an aryl group (
For example, phenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, p-chlorophenyl group, naphthyl group, etc. are preferable. ) or a thienyl group. Z is a group of nonmetallic atoms necessary to form the nitrogen-containing heterocyclic nucleus normally used in cyanine dyes, such as benzothiazoles (
For example, benzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 4-methylbenzothiazole, 6-methylbenzothiazole, 5-phenylbenzothiazole, 6-methoxybenzothiazole, 4-
ethoxybenzothiazole, 5-methoxybenzothiazole, 5-hydroxybenzothiazole, 5,6-dimethylbenzothiazole, 5,6 dimethoxybenzothiazole, etc.), naphthothiazoles, (e.g. α-naphthothiazole, β-naphthothiazole, etc.) ), benzoselenazoles (e.g. benzoselenazole, 5-chlorobenzoselenazole, 6-methylbenzoselenazole, 6
-methoxybenzoselenazole, etc.), naphthoselenazoles (e.g. α-naphthoselenazole, β-naphthoselenazole, etc.), benzoxazoles (e.g. benzoxazole, 5-methylbenzoxazole, 5-methoxybenzoselenazole, etc.),
-phenylbenzoxazole, 6-methoxybenzoxazole, etc.), naphthoxazole (e.g. α-
naphthoxazole, β-naphthoxazole, etc.). Specific examples of the compound represented by the above general formula include 2-benzoylmethylene-3-methyl-β-
naphthothiazoline, 2-benzoylmethylene-3-ethyl-β-naphthothiazoline, 3-ethyl-2-(2-
Examples include (tenoyl)methylene-β-naphthothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline, and 5-chloro-3-ethyl-2-p-methoxybenzoylmethylenebenzothiazoline.

As the nitrogen-containing heterocyclic compound, acridine derivatives such as 9-phenyl-acridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benz(
a) Acridine, phenazine derivatives, such as 9,10-
Dimethyl-benz(a) phenazine, 9-methyl-benz(a)-phenazine, 10-methoxybenz(a) phenazine, quinoxaline derivatives such as 6,4″,4″
Monotrimethoxy-2,3-diphenylquinoxaline, 4
",4"-dimethoxy2,3-diphenyl-5-azaquinoxaline, quinazoline derivatives such as 2-methylquinazoline, 4-phenylquinazoline, imidazole derivatives such as 2,4,5,2",4",5"- Examples of organic sulfur compounds include di-n-butyl disulfide, di-n-octyl disulfide, dibenzyl disulfide, diphenyl disulfide, dibenzoyl disulfide, and diacetyl disulfide. 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, thiophenol, thiocresol, p-methoxybenzenethiol, carboxymethyl-N,N-dimethyldithiocarbamate, ethyl trichlormethane sulfenate Examples of peroxides include hydrogen peroxide, di-t-butyl peroxide,
Examples include benzoyl peroxide and methyl ethyl ketone peroxide. Redox compounds consist of a combination of a peroxide and a reducing agent, such as ferrous ions and hydrogen peroxide, ferrous ions and persulfate ions, ferric ions and hydrogen peroxide, and ferric ions and hydrogen peroxide. There are combinations such as persulfate ions.

Examples of azo and diazo compounds include α,α1-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azobiscyclohexanecarbonitrile, and diazonium salts of p-aminodiphenylamine.

Examples of the halogen compound include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, β-naphthalenesulfonyl chloride, and xylene sulfonyl chloride.

Photoreducible pigments include rose bengal, erythrosin, eosin, acriflavin, riboflavin, and thionin.

Any one compound or a combination of two or more of the above-mentioned compounds can be used as a photopolymerization initiator.

These photopolymerization initiators are used in an amount of 0.1 part by weight to 1 part by weight, preferably in a range of 0.5 part by weight to 1 part by weight, per 10 parts by weight of the ethylenically unsaturated compound. It is.

Although the photopolymerizable photosensitive resin composition of the present invention is composed of the above-mentioned components, it is preferable to further add a thermal polymerization inhibitor.

Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, and 2,6-dihydroquinone. Examples include t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, and organic acid copper (such as copper acetate). These thermal polymerization inhibitors are 0.0 parts by weight per 10 parts by weight of the ethylenically unsaturated compound.
The content is preferably within the range of 0.01 parts by weight. The photopolymerizable photosensitive resin composition of the present invention can further contain various additives such as colorants, plasticizers, and resins.

Examples of colorants include pigments such as titanium oxide, carbon black, iron oxide, phthalocyanine pigments, and azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes. However, it is preferable that the colorant used does not absorb light at the absorption wavelength of the photopolymerization initiator. In the case of a pigment, the amount of such coloring agent is 0 per 100 parts by weight of the total amount of methacrylic acid resin and ethylenically unsaturated.
．． 1 part by weight to 3 parts by weight, in the case of dyes from 0.01 part by weight to 1 part by weight, preferably 0.1 part to 3 parts by weight.
It can be contained in a range of parts by weight. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihebutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditri)decyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, and diallyl phthalate. glycol esters such as dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, triethylene glycol dicaprylate, tricresyl phosphate, triphenyl phosphate, etc. phosphoric acid esters, aliphatic dibasic acid esters such as diisobutyl dipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dihexyl azelate, dioctyl azelate, dibutyl maleate, triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, 4,
Examples include 5-diepoxycyclohexane-1,2-dicarboxylic acid and di-2-ethylhexyl. When the photosensitive material using the photopolymerizable photosensitive composition of the present invention is imagewise exposed, in order to make it less susceptible to the photopolymerization inhibiting effect of oxygen in the air, the photosensitive composition has 18 or more carbon atoms. Higher fatty acids can be contained in the photosensitive composition in an amount of 0.1% to 5% by weight.

Examples of higher fatty acids are stearic acid, arachic acid,
Examples include heneicosanoic acid, behenic acid, triconanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, octacosanoic acid, montanic acid, melisic acid, lactacic acid, and the like. Among these, fatty acids having 20 or more carbon atoms (arachic acid and the fatty acids described thereafter) are preferred. The photopolymerizable composition of the present invention is dissolved in a solvent to form a coating solution, which is applied to glass, wood, paper, cloth, metals (such as aluminum, zinc, copper, iron, nickel, chromium, iron, etc.).
chromium-nickel alloy, etc.) plates, foils, screen cloth,
It is generally used by applying it to a support such as a plastic film (for example, polyethylene terephthalate, nylon, polyethylene, polypropylene, cellulose triacetate), and drying it to form a coating.

As the solvent for dissolving the photopolymerizable photosensitive composition of the present invention,
Number of carbon atoms is 6 or less, boiling point under atmospheric pressure is 1600C
The following alkanols can be used.

Examples of alkanols include methanol, ethanol,
Propanol, butanol, pentanol, hexanol, isopropyl alcohol, isobutyl alcohol,
Sec-butyl alcohol, tert-butyl alcohol, Sec-amyl alcohol, Tel-amyl alcohol, 3-pentanol, isohexyl alcohol, 2
-hexanol, 3-hexanol, etc. One type or a combination of two or more types of the above-mentioned alkanols can be used as the solvent. Among these alkanols, propanol, butanol, isopropyl alcohol, isobutyl alcohol, and Sec-butyl alcohol are preferred. The above-mentioned mixture of alkanol and water can also be used as a solvent for the photopolymerizable photosensitive composition of the present invention. Among them are propanol-water, butano-
A mixed solution of roux water, isopropyl alcohol-water, isobutyl alcohol-water, and Sec-butyl alcohol-water is preferred. If necessary, other organic solvents can be added to the above-mentioned alkanol or alkanol-water mixture as long as the effects of the present invention are not impaired. The water-developable photoheavy sensitive compositions of the present invention form clear homogeneous phase solutions when dissolved in the aforementioned alkanols or alkanol-water mixtures.

The photopolymerizable photosensitive composition solution obtained in this way, which is one embodiment of the present invention, is a homogeneous phase solution and has various features. That is, since it is a homogeneous phase solution, it is easy to prepare and can be stably stored for a long time after being prepared, and it is easy to apply the photosensitive composition solution to a support. It has features such as a uniform layer of the photosensitive composition applied to the support. When a photosensitive material having a layer of the photopolymerizable photosensitive composition of the present invention is used as a photoresist material, the resist image obtained by curing the exposed area after image exposure is , about 2% by weight to about 2% by weight of strong alkalis such as sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, etc.
It can be easily removed by applying an aqueous solution in the range of up to 50% by volume.

The above-mentioned alkaline aqueous solution can be appropriately selected within the range of about 15°C to about 90°C. Example 1 Degreased thickness of 0.24wn? 1? After making grains on a grade aluminum plate with a nylon brush, it was immersed in dilute sulfuric acid (approximately 30°C) at a current density of 3A/D.
A current of d was applied for 2 minutes to anodize the surface of the aluminum plate.

After this, take out the aluminum plate and wash it with water, then 2%
It was immersed in a phosphoric acid solution (65° C.) for 1 minute, washed with water and dried, and then coated with the following photosensitive composition so that the thickness after drying was 3 μm. 1 weighing part Polymethacrylic acid 20% aqueous solution (1) Honyaku KK brand name AC-30,12
500■PS/25°C) 4 parts by weight n-butyl alcohol 2.5 parts by weight Trimethylolpropanetria
Acrylate 1 part by weight Dihebutyl phthalate 0.1 part by weight N-methyl-2-benzoylmethane
Thyrene-β-naphthothiazole overnight after applying the above solution 5
After keeping the photosensitive plate at 0°C, the photosensitive plate was exposed to 3 intermediate patterns at a distance of 50 cm from Jet Light 2000 (2KW ultra-high pressure mercury lamp manufactured by Oak Seisakusho Co., Ltd.).
After immersing it in tap water at 5°C for 1 minute, it was rubbed lightly with a sponge, the non-printed area was removed, and it was directly attached to a printing machine, and 20,000 excellent prints were printed without any rough curling.

Example 2 The same procedure as in Example 1 was carried out except that the following photosensitive composition was used, and the same results as in Example 1 were obtained.

1 part polymethacrylic acid
20% aqueous solution (same as Example 1) 40 parts by weight n-butyl alcohol 2.5 parts by weight Pentaerythritol
1 part by weight of tetraacrylate 0.1 part by weight of dihebutyl phthalate N-methyl-21 benzoylmethylene-β-naphtho Thiazole Example 3 Example 1 except that the following was used as the photosensitive composition.
The same results as in Example 1 were obtained in the same manner as in Example 1.

1 part Polymethacrylic acid
20% aqueous solution (same as Example 1) 4 parts n-butyl alcohol 2.5 parts by weight Trimethylol
Pantrimethacrylate 1 part by weight Dihebutyl phthalate 0.0 parts Michler-ketone 0.04 parts by weight Benzanthrone Example 4 After polishing a copper printed circuit board and drying a photosensitive solution with the following composition, the film thickness becomes 5 μm. It was applied and dried.

1 part by weight 20% aqueous solution of polymethacrylic acid (same as Example 1) 4 parts by weight n-butyl alcohol 3.5 parts by weight Trimethylolpropane triacrylate 0.0 part by weight N-methyl-2-benzoylmethylene-β -Naphthothiazole 0.04 parts by weight Lofin dimer
(2,4,5,2'',4'',5''-hexaphenyl-1,1''-biimidazole) After that, it was pattern exposed in the same manner as in Example 1, immersed in tap water at 35°C for 1 minute, and then Rub lightly with a sponge and apply approximately 40W
Although the copper in the non-image area was etched by spraying a t% Fece3 aqueous solution (40°C), the organic layer in the exposed area was sufficiently durable as a resist.

Claims (1)

[Claims] 1 Water-soluble methacrylic acid resin, at a temperature of 1 at atmospheric pressure
In the photopolymerizable photosensitive composition containing a photopolymerization initiator and an ethylenically unsaturated compound having a boiling point of 00°C or higher and having at least two polymerizable unsaturated groups in one molecule, the methacrylic acid resin is The 20% aqueous solution has a temperature of 2
Approximately 5,000 cps (centipoise) to approximately 30 at 5°C
The ethylenically unsaturated compound has a viscosity in the range of up to 10,000 cps, and the ethylenically unsaturated compound is present in a proportion of 0.5 to 5 parts by weight per 1 part by weight of the methacrylic acid resin. A water-developable photopolymerizable composition comprising: 2 Water-soluble methacrylic acid resin, temperature 1 under atmospheric pressure
The methacrylic acid resin contains an ethylenically unsaturated compound having a boiling point of 00°C or more and having at least two or more polymerizable unsaturated groups in one molecule and a photopolymerization initiator, and the methacrylic acid resin contains 20% by weight of the methacrylic acid resin. The aqueous solution is approximately 5,000 cp at a temperature of 25°C.
having a viscosity ranging from s to about 300,000 cps;
and a water-developable photopolymerizable composition containing both the ethylenically unsaturated compound at a ratio of 0.5 to 5 parts by weight per 1 part by weight of the methacrylic acid resin. A photopolymerizable composition solution characterized by being dissolved in the following alkanol or a mixture of the alkanol and water. 3 The alkanol is methanol, ethanol, propanol, butanol, pentanol, hexanol, isopropyl alcohol, isobutyl alcohol, sec
-butyl alcohol, tert-butyl alcohol, s
The water polymerizable composition according to claim 2, which is at least one selected from the group consisting of ec-amyl alcohol, tert-amyl alcohol, 3-pentanol, isohexyl alcohol, 2-hexanol, and 3-hexanol. substance solution.