JP2561844B2 - Photopolymerizable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel photopolymerizable composition, and particularly to decarboxylation of a carboxylic acid in a polymer by light to generate a radical species, The present invention relates to a photopolymerizable composition capable of forming a negative image with respect to an original image by insolubilizing it in a developing solution by polymerizing and crosslinking the contained radically polymerizable group.

[Prior art and its problems]

Compounds that decompose to form free radicals when exposed to light (free radical generators) are well known in the field of graphic arts. They are widely used as photoinitiators in photopolymerizable compositions, photoactivators in free radical photographic compositions and as photoinitiators of reactions catalyzed by photogenerated acids. Such free radical generators are used to make a variety of photosensitive materials useful in printing, reproduction, reproduction and other imaging systems.

As a compound that decomposes by light to generate a radical species, Journal of Photochemistry, Volume 33 (No. 2), pp. 237-255 (1986) [Journal of Pho
tochemistry, Vol.33 (No.2), pp237-255 (1986)] and Journal of the Chemical Society,
Section C, pp. 1682-1689 (1972) [Journal of t
he Chemical Society, Section C, pp1682-1689 (197
2)] and carboxylic acids or analogs thereof.

Also, U.S. Pat.No. 4,287,751, U.S. Pat.
U.S. Pat. No. 4,366,228 describes the use of those carboxylic acids as photoinitiator systems.

However, the sensitivity of these photopolymerizable compositions was insufficient.

[Object of the Invention]

Therefore, it is an object of the present invention to provide a photopolymerizable composition having a higher sensitivity than conventional ones.

[Structure of Invention]

As a result of various studies to achieve the above-mentioned object, the present inventors have found that the above-mentioned object is achieved by accidentally introducing the above-mentioned carboxylic acid into the polymer, and have reached the present invention. Is.

That is, the present invention comprises a compound having at least one ethylenically unsaturated double bond capable of addition polymerization, and a polymer containing a carboxyl group that undergoes decarboxylation upon exposure in the presence or absence of a sensitizer. It relates to a photopolymerizable composition.

 Hereinafter, the present invention will be described in detail.

The polymer having a carboxyl group-containing group that causes decarboxylation upon exposure in the presence or absence of a sensitizer used as the image forming layer of the present invention (hereinafter referred to as the polymer of the present invention) is the carboxyl group. The containing group is represented by the formula: Y ₁ XCH _{2 k} COOH (I), and this group is linked to the main chain of the polymer (P) with or without the linking group Z.

In the above formula (I), X is sulfur, oxygen, C = W
Or N--U, especially sulfur, C = W,
N-U is preferable in terms of sensitivity. Here, W means oxygen and sulfur. U means an aryl group which may have a substituent, an alkyl group or a hydrogen atom. Y is alkylene which may have a substituent, arylene, aralkylene, 2
Means a valent heterocycle. k is 0 or 1, and l is 1.

When X is sulfur, oxygen or N-U, -X
CH _{2 k} COOH is preferably bonded to an aryl nucleus or an aromatic heterocyclic nucleus for sensitivity. In this case, the aryl nucleus or the heterocyclic nucleus may be included in the side chain or the main chain of the polymer.

Preferred carboxyl group-containing groups include residues containing the skeleton of the following compounds.

Phenoxyacetic acid, 2-methylphenoxyacetic acid, 3-methoxyphenoxyacetic acid, 2-nitrophenoxyacetic acid, 3
-Chlorophenoxyacetic acid, 4-methylphenoxyacetic acid,
n-butoxyacetic acid, thiophenoxyacetic acid, 3-methoxythiophenoxyacetic acid, 2-chlorothiophenoxyacetic acid,
2-methylthiophenoxyacetic acid, 4-nitrothiophenoxyacetic acid, n-butylthioacetic acid, benzoylformic acid, 4-
Chlorobenzoylformic acid, thiobenzoylformic acid, pyruvic acid, N-phenylglycine, N- (3-chlorophenyl) glycine, N- (2,4-dichlorophenyl) glycine, N- (4-acetylphenyl) glycine, N -(2
-Nitrophenyl) glycine, N- (2,4-dinitrophenyl) glycine, N- (4-cyanophenyl) glycine, N- (2-bromophenyl) glycine, N- (2-
Methylphenyl) glycine, N- (2-methoxyphenyl) glycine, N- (2,4-dimethoxyphenyl) glycine, N- (n-butyl) glycine, N-methyl-N-
(2-methylphenyl) glycine, N-methyl-N-
(4-Chlorophenyl) glycine, N-methyl-N-
(2-Nitrophenyl) glycine, N-methyl-N-
(2-methoxyphenyl) glycine, N- (4-carbamoylphenyl) glycine, N- (4-sulfamoylphenyl) glycine and the like.

These carboxyl group-containing groups, via the linking group Z,
Alternatively, it is bonded to the polymer main chain without intervention. The linking group is an ether bond, an amide bond, an ester bond, a urethane bond, a ureido bond or a linking group containing them. A part of the carboxylic acid-containing group may be contained in the polymer main chain.

Examples of the linking group containing an ether bond, an amide bond, an ester bond, a urethane bond, and a ureido bond include those represented by the following general formulas (III), (IV), (V), and (VI).

_{-LR-L n R- (III)} -LR-L n (IV) -RL-R n L- (V) -RL-R n (VI) wherein, R represents optionally say each alkylene,
It represents arylene, aralkylene, or a divalent heterocycle, and L represents an ether bond, an amide bond, an ester bond, a urethane bond, or a ureido bond, which may be different from each other. n is 0, 1 or 2.

Examples of the polymer having a carboxyl group-containing group include acrylic resins, vinyl polymerization resins including vinyl alcohol resins, polyurethane resins, polyurea resins, polyvinyl acetal resins, polyamide resins,
Epoxy resins and the like are included, but not limited to these.

For example, the acrylic resin includes a homopolymer of a monomer represented by the general formula (VII) or a copolymer with another monomer copolymerizable with the homopolymer (eg, acrylic acid ester, methacrylic acid ester, etc.).

Further, for example, the polyurethane resin can be obtained by reacting a diol represented by the general formula (VIII) with an isocyanate.

(HOCH ₂ CH _{2 2} The _{NY l XCH 2 k COOH ... (} VIII), for example, polyester resin has the general formula with a diol such as (VIII), that both ends obtained by reacting a compound became acid chloride You can

The above polymer is 3.0 wt% to 97 wt% of the total composition, especially 1
It is preferable to add 0.0 wt% to 96 wt%. This is because the sensitivity is reduced if it is at least 96 wt% or more than 10 wt%.

The acid value of the polymer of the present invention is preferably from 6.0 meq / g to 0.01 meq / g, particularly preferably from 2.0 meq / g to 0.1 meq / g. 0.01meq /
This is because, as the value becomes lower than g, the developability by the alkali developer decreases, and as the value becomes higher than 6.0 meq / g, the film strength and the adhesive strength to the support become lower. Further, the carboxylic acid in these resins may additionally contain one that is not decarboxylated by light.
In addition, two or more kinds of carboxylic acid-containing groups that are decarboxylated by light may be introduced into the same polymer.

The molecular weight of the polymer of the present invention is suitably 100 to 100,000, preferably 8,000 to 200,000 in terms of weight average molecular weight measured by gel permeation chromatography. As it becomes smaller than 8000, the image strength starts to decrease,
This is because if it exceeds 200,000, the developability will decrease.

Further, two or more kinds of the above polymers may be used, or the above polymers may be mixed with a polymer having a carboxylic acid that is not decarboxylated by light and used.

In this case, the proportion in which other polymers can be mixed is 95% by weight or less based on the entire photosensitive composition. This is because when the amount of the other resin is more than 95% by weight, the features of using the polymer according to the present invention decrease. Examples of the polymer to be mixed include polyamide resin, epoxy resin, polyurethane resin, acrylic resin, polyester resin, polyvinyl acetal resin and the like.

The polymerizable compound having an ethylenically unsaturated bond in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, which is a monomer, a prepolymer, that is, Dimer, 3
Polymers and other oligomers having a chemical form such as a mixture thereof and a copolymer thereof. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.

Salts of unsaturated carboxylic acids include the alkali metal salts of the acids mentioned above, for example the sodium and potassium salts.

As a specific example of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, an acrylic ester,
Ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate Acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate , Sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,
There are polyester acrylate oligomers and the like. As the methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate,
Pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis- [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) Phenyl] dimethyl methane and the like. As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate , Sorbitol tetri taconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. As maleic acid ester, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate,
Sorbitol tetramalate and the like. Further, there may be mentioned a mixture of the above-mentioned esters.

Specific examples of the amide of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide,
Methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule, which is described in JP-B-48-41708, is prepared by adding the following general formula (V)
And a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl-containing vinyl monomer is added.

CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (V) (wherein R and R ′ represent H or CH ₃ ). The polymerizable compound having an ethylenically unsaturated bond is the whole composition. 1.0 to 90% by weight, especially 10 to 60% by weight
It is preferred to add. This is because if it is less than 10% by weight, the sensitivity and coating strength are lowered, and if it is more than 60% by weight, the plate becomes tacky.

In the present invention, the sensitivity can be increased by adding a photosensitizer. As the photosensitizer used in the present invention, xanthone, fluorenone, benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4
-Diethylthioxanthone, acetophenone, naphthylacetone, 4,4'-bisdimethylaminobenzophenone, trinitrofluorenone, dibenzosuberone, 2,5
-Bis- (4'diethylaminobenzal) cyclopentanone, α, α-dichloro-4-phenoxyacetophenone, aromatic ketone compounds such as 1-hydroxycyclohexyl phenyl ketone; 4,4'-bisdimethylaminothiobenzophenone Aromatic thioketone compounds; quinone compounds such as benzoquinone, dichlorobenzoquinone, tetrachlorobenzoquinone, dichloronaphthoquinone, anthraquinone, phenanthrenequinone, dichloroanthraquinone, dinitroanthraquinone, alizarin, benzanthraquinone; nitrobenzene, 1-nitronaphthalene, 4- Nitrobiphenyl, 4-nitrotoluene,
Aromatic nitro compounds such as 1,3-dinitrobenzene and 2,4,6-trinitroaniline; naphthalene, anthracene,
Aromatic hydrocarbons such as phenanthrene, benzanthracene, and benzpyrene; triarylpyrazoline compounds such as triphenylpyrazoline; monoimidazole compounds such as tetraphenylimidazole and triphenylimidazole; fluorescein, eosin Y, rose bengal, erythrosine B , Xanthene compounds such as phloxine; acridine compounds such as acriflavine, riboflavin, acridine, 9-phenylacridine, N-phenylacridine, phenazine, 2,3-diphenylquinoxaline, acenaphtho [1,2-b] quinoxaline; 7 -N, N-diethylaminoketocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-methoxycoumarin, 3,3'-carbonylbis (7
U.S. Patent No. 4,289,84
No. 4, coumarin compounds; triphenylmethane compounds such as thymol blue, bromthymol blue, and bromocresol green; 2-methyl-3-benzenesulfonyloxy-4 (3H) -quinazolinone,
-(Β-styryl) -3-benzenesulfonyloxy-
Quinazolinone compounds such as 4 (3H) quinazolinone. Two or more of the above sensitizers can be used in combination.

The photosensitizer is preferably added in an amount of 0.01 to 50% by weight, particularly 0.1 to 30% by weight, based on the total composition. When the amount is less than 0.1% by weight, the effect of the addition is small, and when the amount is more than 30% by weight, the coating strength is reduced and the sensitivity is also reduced.

Further, it is desirable to add a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound having an ethylenically unsaturated bond during the production or storage of the composition of the present invention. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-
Examples include cresol, pyrogallol, t-butylcatechol, benzoquinone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, nitrobenzene and dinitrobenzene.

To improve the performance of the photosensitive composition of the present invention, if necessary, by adding a dye, a pigment, a stabilizer, a filler, a surfactant, a plasticizer, an antifouling agent, and a sensitizer. Can also. Suitable dyes include oil-soluble dyes such as CI2610.
5 (Oil Red RR), CI21260 (Oil Scar Red # 308), CI74350 (Oil Blue), CI52015 (Methylene Blue), CI42555 (Crystal Violet) CI42595 (Victoria Pure Blue).

The photosensitive composition of the present invention is usually used after being dissolved in a solvent, applied to a suitable support, and dried. The coating amount is about 0.01 to 500 g / m ^{2 on} a dry weight basis, preferably 0.1 to 200 g / m ² .
²

Examples of the solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethylacetate, ethylene glycol, tetrahydrofuran, dioxane, dimethylsulfoxide, N, N-. Dimethylformamide, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 2
-Methoxy-1-propanol, 1-methoxy-2-acetoxypropane, 2-methoxy-1-acetoxypropane, ethyl acetate, methyl acetate, toluene, xylene,
Etc. and mixtures of these are used.

As the support to which the photosensitive composition of the present invention is applied,
For example, paper, paper laminated with plastics (eg polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., eg cellulose diacetate, cellulose acetate produced, Films of plastics such as cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper or plastic film laminated or vapor-deposited with the above metals. Etc. are included. Among these supports, when used as a printing plate, an aluminum plate is particularly preferable because it is extremely stable in dimension and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of metal, especially aluminum, electrolytic grain treatment, composite grain treatment, graining treatment, soaking treatment with an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization Surface treatment such as treatment is preferably performed. Preferred anodizing treatments include a method of anodizing at high current density in sulfuric acid described in British Patent No. 1,412,768 and anodizing using phosphoric acid described in US Pat. No. 3,511,661 as an electrolytic bath. How to do it, Japanese Patent Publication No. 46-43124
And JP-A-52-103208 and 55-28400, a method of anodizing in a mixed acid of phosphoric acid and sulfuric acid is included. Also, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, JP-B-47-5125
As described in Japanese Patent Laid-Open Publication No. 2003-242242, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also suitably used. The anodizing treatment is, for example, an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid,
Alternatively, it is carried out by passing a current through an aluminum plate as an anode in an electrolytic solution of an acid, an organic acid such as sulfamic acid or the like, or an aqueous solution or a non-aqueous solution of a salt thereof, or a combination of two or more kinds.

Further, it is also preferable that the material is subjected to hydrophilization treatment after graining treatment and anodic oxidation. Such hydrophilic treatment is performed by immersion in an aqueous solution of sodium silicate, an aqueous solution of polyvinyl sulfonic acid, hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, and the like.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective.

Further, an overcoat layer made of polyvinyl alcohol or the like may be provided on the photosensitive layer of the photopolymerizable composition of the present invention coated on the support as described above.

The photosensitive composition of the present invention coated on a support is exposed through a transparent original having a line image, a halftone dot image, and the like, and then developed with an aqueous developer to give a negative relief image to the original. .

Light sources used for exposure include, but are not limited to, carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, argon lasers, excimer lasers, and the like.

Examples of the above-mentioned aqueous developers include JP-B-56-39464, JP-B-56-42860, JP-A-51-80228, and JP-A-55-52054.
As described in each of the publications, organic solvents having low solubility in water (eg, benzyl alcohol, 2-phenoxyethanol, etc.), alkaline agents (eg, sodium silicate, potassium silicate, monoethanolamine, triethanolamine, etc.) ), Anionic surfactants (eg, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, naphthalene alkyl sulfonate, sulfate ester salt of ethylene oxide adduct of naphthol,
Aqueous alkaline solutions consisting of branched alkyl sulphates) and water are preferred.

Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified,% in the examples means% by weight.

〔Example〕

 Hereinafter, the present invention will be described in more detail by way of examples.

A mixture of 17.6 parts by weight of m-aminomethacrylanilide, 6.9 parts by weight of potassium carbonate and 25 parts by weight of N, N-dimethylformamide was stirred, and 16.7 parts by weight of ethyl bromoacetate was added dropwise while cooling to 0 ° C. or lower. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, 80 parts by weight of water was added to the mixture, and the mixture was extracted with ethyl acetate. Next, the ethyl acetate layer was washed with dilute hydrochloric acid, washed with saturated saline, and dried over magnesium sulfate. Next, it was concentrated using an evaporator, and the obtained solid was recrystallized from methanol to obtain 15.0 parts by weight of the compound (B) represented by the structural formula (B).

Compound (B) (15.0 parts by weight) was dissolved in ethanol (20 parts by weight) and cooled with ice, and then sodium hydroxide (2.3 parts by weight / water 6) was added thereto.
0 parts by weight of the solution was added dropwise. After stirring at 20 ° C for 30 minutes,
Wash with ethyl acetate and add 1N aqueous hydrochloric acid to adjust the pH.
It was set to 2, and ethyl acetate washing was performed. Next, a 1N sodium hydroxide aqueous solution was added, the aqueous layer was returned to pH 3, and the mixture was extracted with ethyl acetate. After drying over magnesium sulfate, the mixture was concentrated using an evaporator to obtain 9.0 parts by weight of a compound (C) represented by the structural formula (C).

In a nitrogen atmosphere, 2.34 parts by weight of compound (C) and 10.28 parts by weight of ethyl methacrylate were dissolved in 38.0 parts by weight of methyl cellosolve, stirred, heated to 70 ° C., and then 0.164 parts by weight of azobisisobutyronitrile (AIBN). Parts, and stirred for 5 hours and further stirred at 85 ° C for 3 hours to give a weight average molecular weight of 58,000.
Polymer (A) of

Dissolve 1.6 parts by weight of sodium hydroxide in ethanol,
A solution prepared by dissolving 5 parts by weight of p-aminothiophenol in 20 parts by weight of ethanol was added to the solution. Next, the obtained mixture was cooled to 0 ° C. or lower, and a solution prepared by dissolving 3.8 parts by weight of chloroacetic acid and 3.4 parts by weight of sodium bicarbonate in 10 parts by weight of water was added dropwise to the mixture while maintaining the temperature at 0 ° C. or lower. .
After the addition, the mixture was stirred at 0 ° C. for 3 hours, then the pH was adjusted to 3, and the precipitated solid was filtered to obtain 5.4 parts by weight of p-aminothiophenoxyacetic acid.

5 parts by weight of p-aminothiophenoxyacetic acid, pyridine 2.
7 parts by weight were dissolved in 40 parts by weight of DMF, and 3.2 parts by weight of methacrylic acid chloride was added dropwise at 0 ° C. or lower. After the dropwise addition, the mixture was stirred at 0 ° C for 1 hour, and further stirred at 25 ° C for 2 hours. Next, the obtained reaction solution was added to 500 parts by weight of a hydrochloric acid aqueous solution having a pH of 1, and extracted with ethyl acetate. Next, the ethyl acetate layer was dried over magnesium sulfate and concentrated, and the obtained crystals were recrystallized from ethyl acetate to obtain 1.26 parts by weight of a compound (E) having the following formula (E).

1.26 parts by weight of compound (E) and 5.14 parts by weight of ethyl methacrylate are dissolved in 25 parts by weight of methyl cellosolve under a nitrogen atmosphere, stirred and heated at 70 ° C. for 5 hours, then at 80 ° C. for 3 hours, and then weight average molecular weight. 40,000 polymers (D) were obtained.

With 20.8 parts by weight of polystyrene having a weight average molecular weight of 10,000,
13.5 parts by weight of ethyl oxalyl chloride and carbon disulfide
It was dissolved in 500 parts by weight, and 18.22 parts by weight of aluminum chloride was gradually added with stirring. Next, the obtained mixture was refluxed for 1.
After stirring for 5 hours, 70% of the charged carbon disulfide was distilled off, and the residue was put into a mixture of 40 parts by weight of concentrated hydrochloric acid and 100 parts by weight of ice. After decanting, further adding water and decanting and dissolving the remaining solid in acetone,
The precipitate was reprecipitated in methanol and the solid was filtered to obtain 11.5 g of a polymer (G).

Next, after dissolving 10 parts by weight of the polymer (G) in 600 parts by weight of THF, 50 parts by weight of a 1N aqueous sodium hydroxide solution and 150 parts by weight of water
And then refluxed for 2 hours. After the reaction, acetic acid 28.8
The resulting polymer was reprecipitated in methanol and dried to obtain 4.0 parts by weight of a polymer (F).

(Synthesis Example 4) 2.34 parts by weight of the compound B synthesized in Synthesis Example 1 and 5.04 parts by weight of allyl methacrylate were dissolved in 50.06 parts by weight of methyl cellosolve, and the mixture was heated to 70 ° C. under stirring in a nitrogen atmosphere.
2,2'-Azobis (2,4-dimethylvaleronitrile) 0.18
After 6 parts by weight was added and the mixture was reacted for 4 hours, it was reprecipitated in hexane. As a result, 14.0 g of polymer (H) was obtained.

The weight average molecular weight was 20,000.

Examples 1 to 10 An aluminum plate having a thickness of 0.24 mm and a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then washed well with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating waveform current of 7 V and V _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% sulfuric acid aqueous solution to an electric quantity at the anode of 160 Coulomb / dm ³ . Then, soak in 30% sulfuric acid aqueous solution
After desmutting at 55 ° C. for 2 minutes, anodization treatment was performed in a 7% aqueous solution of sulfuric acid to a thickness of 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C for 1 minute, washed with water and dried.

The aluminum plate thus obtained was coated with the following photosensitive solution using a wheeler and dried at 80 ° C. for 2 minutes. The dry weight was 2.0 g / m ² . Compounding amount of photosensitive solution 25% solution of polymer (A) in methyl cellosolve 2 g Sensitizer (Table-1) Table-1 Victoria Pure Blue BOH 0.018 g Pentaerythritol tetraacrylate 0.15 g 2-Methoxyethanol 8.5 g The thus-obtained photosensitive lithographic printing plate precursor was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m through a step wedge for 2 minutes, immersed in the following developer at room temperature for 1 minute, and then washed with water. Then, the unexposed portion was removed to obtain planographic printing plates (Examples 1 to 10) having a bright blue image. Amount of developer mixed Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate 5g Sodium isopropylnaphthalene sulfonate 12g Water 1000g The results were as follows.

Examples 11 to 20 A 0.24 mm thick aluminum plate was applied to a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then washed well with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating wave current of 7 V and V _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% sulfuric acid aqueous solution at an anode-time electricity quantity of 160 Coulomb / dm ³ . Subsequent immersion in 30% sulfuric acid solution 55
After desmutting at 2 ° C. for 2 minutes, anodization treatment was performed in a 7% aqueous solution of sulfuric acid to a thickness of 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. The aluminum plate obtained as described above was coated with the following photosensitive solution using a wheeler and dried at 80 ° C. for 2 minutes. The dry weight was 2.0 g / m ² . Amount of photosensitive solution blended 25% solution of polymer (D) in methyl cellosolve 2 g Sensitizer (Table-3) Table-3 Oil blue 0.018 g Trimethylolpropane triacrylate 0.15 g 2-Methoxyethanol 8.5 g The thus-obtained photosensitive lithographic printing plate precursor was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m through a step wedge for 2 minutes, immersed in the following developer at room temperature for 1 minute, and then washed with water. Then, the unexposed portion was removed to obtain planographic printing plates (Examples 11 to 20) having a bright blue image. Amount of developer mixed Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate 5g Sodium isopropylnaphthalene sulfonate 12g Water 1000g The results were as follows.

Examples 21 to 30 An aluminum plate having a thickness of 0.24 mm and a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then washed well with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating wave current of 7 V and V _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% sulfuric acid aqueous solution at an anode-time electricity quantity of 160 Coulomb / dm ³ . Continue to soak in 30% sulfuric acid aqueous solution,
After desmutting at 55 ° C. for 2 minutes, anodization treatment was performed in a 7% aqueous solution of sulfuric acid to a thickness of 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. The aluminum plate obtained as described above was coated with the following photosensitive solution using a wheeler and dried at 80 ° C. for 2 minutes. The dry weight was 2.0 g / m ² . Blending amount of photosensitive solution Polymer (F) 0.5 g Sensitizer (Table-5) Table-5 Victoria Pure Blue B-OH 0.018 g Dipentaerythritol hexaacrylate 0.17 g Tetrahydrofuran 10 g The photosensitive lithographic printing plate precursor thus obtained was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m through a step wedge for 2 minutes, and then soaked in the following developing solution at room temperature for 1 minute, followed by absorbent cotton. The surface was lightly rubbed to remove the unexposed areas, and a bright blue image lithographic printing plate (Example 21
~ 30) was obtained. Compounding amount of developer 5 g of sodium sulfite 5 g of tetrahydrofuran 30 g of sodium carbonate 5 g of sodium isopropylnaphthalene sulfonate 12 g of water 1000 g The results were as follows.

Examples 31 to 40 An aluminum plate having a thickness of 0.24 mm and a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then washed well with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating wave current of 7 V and V _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% sulfuric acid aqueous solution at an anode-time electricity quantity of 160 Coulomb / dm ³ . Subsequent immersion in 30% sulfuric acid solution 55
After desmutting at 2 ° C. for 2 minutes, anodization treatment was performed in a 7% aqueous solution of sulfuric acid to a thickness of 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. The aluminum plate obtained as described above was coated with the following photosensitive solution using a wheeler and dried at 80 ° C. for 2 minutes. The dry weight was 2.0 g / m ² . Blending amount of photosensitive solution 25% solution of polymer (H) in methyl cellosolve 2 g Sensitizer (Table-7) Table-7 Oil blue 0.018 g Trimethylolpropane triacrylate 0.15 g 2-Methoxyethanol 8.5 g The thus-obtained photosensitive lithographic printing plate precursor was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m through a step wedge for 2 minutes, immersed in the following developer at room temperature for 1 minute, and then washed with water. Then, the unexposed portion was removed to obtain a lithographic printing plate (Examples 31 to 40) having a bright blue image. Amount of developer mixed Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate 5g Sodium isopropylnaphthalene sulfonate 12g Water 1000g The results were as follows.

Comparative Examples 1 to 20 An aluminum plate with a thickness of 0.24 mm and a nylon brush and 400
The surface was grained with an aqueous suspension of mesh pumice and then washed well with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating wave current of 7 V and V _C = 9.1 V, electrolytic surface roughening treatment was performed in a 1% sulfuric acid aqueous solution at an anode-time electricity quantity of 160 Coulomb / dm ³ . Subsequent immersion in 30% sulfuric acid solution 55
After desmutting at 2 ° C. for 2 minutes, anodization treatment was performed in a 7% aqueous solution of sulfuric acid to a thickness of 2.0 g / m ² . Then, it was immersed in a 3% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. The aluminum plate obtained as described above was coated with the following photosensitive solution using a wheeler and dried at 80 ° C. for 2 minutes. The dry weight was 2.0 g / m ² .

Photosensitive solution formulation (Comparative Examples 1 to 10) 25% solution of polymer (I) in methylcellosolve 2 g Sensitizer (Table-9) Table-9 Oil blue 0.018 g Pentaerythritol tetraacrylate 0.15 g N-phenylglycine 60 mg 2-methoxyethanol 8.5 g The photosensitive lithographic printing plate precursor thus obtained was image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m through a Fuji PS Step Guide manufactured by Fuji Film Co., Ltd. for 2 minutes, and at room temperature with the following developing solution. After immersion for 1 minute, the results were as follows. Compounding amount of developer Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate 5g Sodium isopropylnaphthalene sulfonate 12g Water 1000g As described above, it can be seen that a highly sensitive photopolymerizable composition can be obtained by introducing into the polymer a carboxyl group that causes decarboxylation upon exposure.

Claims (3)

(57) [Claims] 1. The following components: (a) a compound having at least one ethylenically unsaturated double bond capable of addition polymerization, and (b) decarboxylation by exposure in the presence or absence of a sensitizer. A photopolymerizable composition comprising a polymer having a carboxyl group-containing group, wherein the carboxyl group-containing group of the component (b) is represented by the following general formula (I): Polymerizable composition. Y _l XCH _{2 k} COOH (I) (wherein X is sulfur, oxygen, C = W or N-U
Means W, oxygen means sulfur, U means an aryl group which may have a substituent, an alkyl group or a hydrogen atom, and Y means an alkylene which may have a substituent, arylene or aralkylene. Means a divalent heterocycle, k is 0 or 1, and l is 1.) 2. The photopolymerizable composition according to claim 1, wherein the polymer (b) has the following general formula (II). PZ _m Y _l XCH _{2 k} COOH] _n (II) (wherein X represents sulfur, oxygen, C = W or N-U, W represents oxygen or sulfur, and U has a substituent. Optionally represents an aryl group, an alkyl group or a hydrogen atom, Y
Represents an alkylene which may have a substituent, arylene, aralkylene, a divalent heterocyclic ring, P represents a polymer main chain, and Z connects the polymer main chain and the group of general formula (I). A group having an ether bond, an amide bond, an ester bond, a urethane bond, a ureido bond, or a group containing them, k is 0 or 1, l is 1, and m is 0.
Alternatively, it is 1, and n is 0.01 (me).
q / g) to 6.0 (meq / g) 3. The photopolymerizable composition according to claim 1, which contains a sensitizer.