JPH0375750A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a negative type photopolymerizable composition capable of sufficiently forming an image even in a short exposure time by using a composition comprising a microgel having a functional group represented by the formula and an acid group with a pKa value of <= 14 and a photopolymerization initiator. CONSTITUTION:The microgel has the functional group represented by formula I in which R is H or methyl, and the acid group having a pKa value of <=14, and the microgel is spherical polymer having a diameter of 0.01 - 1 mum and a cross-linking structure, and the photopolymerizable composition capable of sufficiently forming a negative image in a short exposure time is obtained, for example, by adding, when needed, a compound of a D group having an ethylenically unsaturated bond to a compound of an A group having a polymerizable ethylenically unsaturated group and an active hydroxyl, glycidyl, halogen, or amino group inactive to a polymerization reaction but active to reaction for producing ester or amide and the like, and emulsion or dispersion polymerizing them to produce the microgel, and further reacting the functional group of the formula I, and that of the A group with the compound of an E group to be added.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive composition suitably used for manufacturing lithographic printing plates, IC circuits, photomasks, etc. The present invention relates to a novel photopolymerizable composition.

[Prior art and problems to be solved] There have been many attempts to use photopolymerizable compositions as photosensitive image forming layers of photosensitive lithographic printing plates, etc., as disclosed in Japanese Patent Publication No. 46-32714, Basic composition consisting of a polymer as a binder, a heptanomer, and a photopolymerization initiator, Japanese Patent Publication No. 49-34
As disclosed in Japanese Patent Publication No. 041, compositions in which unsaturated double bonds are introduced into a polymer as a binder to improve curing efficiency, Japanese Patent Publication No. 4B-38403, Japanese Patent Publication No. 53-
As disclosed in No. 27605 and British Patent No. 1388492, compositions using novel photopolymerization initiators are known, and some of them are in practical use.
Sufficient sensitivity was not obtained for any of the photosensitive Mll animals, and there was a problem in that sufficient images could not be obtained with short exposure times.

Therefore, an object of the present invention is to provide a highly sensitive negative photopolymerizable composition that can form sufficient images even with short exposure times.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be easily achieved by using a novel photosensitive composition, and have thus arrived at the present invention.

That is, the present invention relates to a photopolymerizable m-acid characterized by containing a microgel having a functional group represented by the following general formula (I) and an acid group having a pKa value of 14 or less, and a photopolymerization initiator. .

(However, in the formula, R represents -H or -CUt.) The present invention will be described in detail below.

The MIG50 gel used in the present invention, which has a functional group represented by the above-mentioned symbol (I) and an acid group with a pKa value of 14 or less, is a spherical gel with a crosslinked structure and a diameter of 0.01 to 1 μm. It refers to a high-molecular compound and is produced by emulsion polymerization, etc. Regarding the production and use of microgels, for example, British Patent No. 9
No. 67,051 and U.S. Pat. No. 3,895,082.

In the present invention, the acid group having a pKa value of 14 or less that is preferably used is, for example, -SO3H.

-CONHCO--SO,NH-,phenolic-OH
.

-COCHzCOo- and the like.

The microgel having a functional group represented by the general formula (I) and an acid group having a pKa value of 14 or less, which is preferably used in the present invention, is made of compounds of the following groups A to C and, if necessary, further of the group D. It is obtained by using a compound, preferably by emulsion polymerization or dispersion polymerization, to form a microgel, and then reacting it with a compound of Group E.

” Polymerizable ethylenically unsaturated bonds and other reactions that are inert to polymerization reactions (e.g., esterification, amidation)
Compounds (preferably 5 to 95 mol%) having an active functional group (e.g., hydroxyl group, glycidyl group, halogen atom, amine) group (preferably 5 to 95 mol%) Such compounds preferably used in the present invention include: For example, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, 2-(5-hydroxypentanoyloxy)ethyl methacrylate, glycidyl methacrylate, 2-chloroethyl methacrylate, 2
Methacrylic acid derivatives such as -bromoethyl methacrylate), N-(p-hydroxyphenyl) methacrylamide, N-(m-aminophenyl>methacrylamide), acrylic acid derivatives having the same substituents as above, and p-chloro Examples include styrene derivatives such as methylstyrene.

A compound having an ethylenically unsaturated bond capable of one-star polymerization and an acid group having a pKa value of 14 or less (preferably 1 to 80 mol%)
) Such compounds suitably used in the present invention include, for example, methacrylic acid, acrylic acid, 3-(2-methacryloyloxyethoxycarbonyl)propionic acid, N-(2-sulfo-1,1-dimethylethyl) Methacryl M derivatives such as methacrylamide, N-(phenylsulfonyl)methacrylamide, N-(p-sulfamoylphenyl)methacrylamide, N-(p-hydroxyphenyl)methacrylamide, 2-acetoacetoxyethyl methacrylate, and the above and Acrylic acid derivatives having similar substituents, maleimides, styrene derivatives such as p-vinylbenzenesulfonic acid, and EP 115410
Examples include compounds described in A2 and the like.

Compounds having two or more polymerizable ethylenically unsaturated bonds (crosslinking agent, preferably 1 to 50 mol%) Such compounds preferably used in the present invention include, for example, ethylene glycol di methacrylate,
Examples include methacrylic acid derivatives such as butanediol dimethacrylate, trimethylolpropane trimethacrylate, methylene bismethacrylamide, acrylic acid derivatives having the same substituents as above, and styrene derivatives such as divinylbenzene.

Compounds having a polymerizable ethylenically unsaturated bond (preferably 5 to 80 mol%) such as Dansei etc. Such compounds suitably used in the present invention include, for example, methacrylic acid esters having 20 or less carbon atoms. , acrylic esters, methacrylic acid esters, acrylamides, styrenes, acrylonitrile, methacrylate trile, and the like.

In addition, when carrying out dispersion polymerization, it is preferable to use a macromer or the like in which the terminal end of a polyester oligomer is a methacrylic ester.

A compound having a functional group represented by the 1-star general formula (1,) and a functional group capable of reacting with a functional group contained in a compound of Group A.

Examples of such compounds preferably used in the present invention include methacrylic acid, methacrylic acid chloride, methacrylic anhydride, mixed acid anhydride of methacrylic acid and toluenesulfonic acid, mixed acid anhydride of methacrylic acid and carbonic acid,
Examples include methacrylic acid derivatives such as 2-methacryloyloxyethyl isocyanate, and acrylic acid derivatives similar to those mentioned above.

The microgels of the present invention are preferably obtained by emulsion polymerization or dispersion polymerization, and these polymerization methods are described in US Pat. No. 3.895.082 and British Patent No. 967.0.
No. 51 and Immunological Communications (I
MMUNOLOGICAL COMMUNICATIO
NS), 12(5), 509-517 (1983
), and there are many other documents.

In addition, when a microgel is formed by emulsion polymerization using compounds of groups A to C and optionally a compound of group D, E
It is usually necessary to transform the microgel into a dry powder before carrying out the reaction with the compound. The known techniques of collection, filtration, washing and drying can be used for this purpose. Furthermore, by using a suitable organic solvent (for example, toluene, etc.), an aqueous dispersion of the microgel can be converted into an organic solvent dispersion by azeotropic distillation without turning the aqueous dispersion into a powder.

Furthermore, when the reaction with Group E is carried out, it is desirable to carry out the reaction in the presence of a base such as pyridine or amines.

The amount of the microgel of the present invention used is 5 to 95% by weight based on the total weight of the photopolymerizable composition, preferably 1O to a
% by weight.

Note that the use of microgel as one of the components in the photosensitive & It does not substantially contain the functional group represented by (I), and is distinguished from the present invention in this point.

Examples of photopolymerization initiators suitably used in the present invention include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367.660, U.S. Pat. No. 2,367,661 and α-carbonyl compounds disclosed in U.S. Pat. No. 2,367.670, asylloin ethers disclosed in U.S. Pat. No. 2,448.828, U.S. Pat. No. 2,722.512 Aromatic acyloin compounds substituted with a hydrocarbon at the α-position disclosed in U.S. Pat. No. 3,046,127 and U.S. Pat. The triarylimidazole dimer/p-aminophenyl ketone combination disclosed in U.S. Pat. No. 3,549,367;
Benzothiazole compounds disclosed in U.S. Pat. No. 870.524, acridine/phenazine compounds disclosed in U.S. Pat. No. 3,751.259, and U.S. Pat. No. 4,212.970. This includes oxadiazole compounds, etc.

Preferred examples include trihalomethyl-3-triazine compounds and trihalomethyloxadiazole compounds represented by the following general formula (n) or (I[[).

Zl In the formula, N2 represents a substituted or unsubstituted aryl or alkenyl group, and Zl represents z', -cy, or a substituted or unsubstituted alkyl group. Y represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (n) include Wakabayashi et al., Bull, Chem, Soc, Japan.
, Vol. 42, p. 2924 (1969), British Patent No. 1.388.492, West German Patent No. 2.
No. 718.259, and West German patent N3.337.02
Examples include the compounds described in Specification No. 4. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis(trichloromethyl)-5-)riazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-8-triazine, 2
-(p-)lyl)-4,6-his()IJchloromethyl)-S-)riazine, 2-(p-methoxyphenyl)-
4,6-bis(trichloromethyl)-3-)riazine,
2-(2',4'-dichlorophenyl)-4,6-bis(trichloromethyl')-3-)riazine, 2°4.6
-tris(trichloromethyl)-3-) riazine, 2-
Methyl-4,6-bis(trichloromethyl)-5-) riazine, 2-n-nonyl-4゜6-bis(trichloromethyl)-3-) riazine, 2-(α,α,β-trichloroethyl) -4,,6-bis(trichloromethyl)-5
-) riazine, 2-styryl-4,6-bis(trichloromethyl)-8-triazine, 2-(p-methylstyryl)-4,6-bis(trichloromethyl)-3-triazine, 2-(p- methoxystyryl)-4,6-bis(
Trichloromethyl)-3-triazine, 2-(4-methoxy-naphth-1-yl)-4゜6-bis(trichloromethyl)-3-)riazine, 2-(4-ethoxy-naphth-1-yl) -4゜6-bis(trichloromethyl)-
S-Triazine, 2-', (4-(2-ethoxyethyl)-naphth-1-yl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4,7-diphthoxyethyl)-naphtho -l-yl)-4,6-bis(trichloromethyl)-5-)riazine, 2-(acenaphth-5-yl)-4,6-bis(trichloromethyl)-3-triazine, 2-(4- styrylphenyl)-4,6-bis(
(trichloromethyl)-3-triazine and the like.

Further, as the compound represented by the general formula (III), for example, JP-A-54-74728, JP-A-55-7
Examples thereof include compounds described in JP-A No. 7742 and JP-A-59-148784.

Specific examples include the compounds shown below.

That is, 2-styryl-5-trichloromethyl-1,3,
4-Oxadiazole, 2-(4-chlorostyryl)-
5-) Dichloromethyl-1,3゜4-oxadiazole, 2-(4-methylstyryl)-5-)dichloromethyl-1,3,4-oxadiazole, 2-(4-methoxystyryl)- 5-Trichloromethyl-1,3,4-oxadiazole, 2-(4-butoxystyryl)-5-
) dichloromethyl-1,3,4-oxadiazole, 2
-(4-styrylstyryl)-5-)dichloromethyl-
1,3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-
(4-methoxyphenyl)-5-trichloromethyl-1
, 3,4-oxadiazole, 2-(3,4-dimethoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(4-styrylphenyl)-5-
Trichloromethyl-1,3,4-oxadiazole, 2
-(l-naphthyl)-5-)lichloromethyl-1.3.
Includes 4-oxadiazole and the like.

If necessary, a sensitizer can be added to the photopolymerizable composition of the present invention. Specifically, aromatic thiazole compounds disclosed in Japanese Patent Publication No. 59-28328,
Merocyanine dyes shown in JP-A No. 151024, aromatic thiopyrylium salts and aromatic pyrylium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthine, ketochlorins, etc. Can be mentioned. Furthermore, these include N-phenylglycine, 2-mercaptobenzothiazole, N,N'-
Systems in combination with hydrogen donors such as ethyl dimethylaminobenzoate are also effectively used in the present invention.

The amount of the photopolymerization initiator and/or sensitizer in the present invention is
0.01% by weight, based on the total weight of the photopolymerizable composition
A range of from 20% by weight is sufficient, more preferably from 0 to 20% by weight.
．． Good results are obtained with 5% to 10% by weight.

The photopolymerizable composition of the present invention may further contain unsaturated monomers or oligomers, alkali-soluble resins, diazo resins, thermal polymerization inhibitors, etc., if necessary.

As the unsaturated monomer or oligomer used in the photopolymerizable composition of the present invention, compounds having at least one addition-polymerizable unsaturated group are useful, and particularly desirable ones include ethylene glycol di(meth)acrylate. , polyethylene glycol di(meth)acrylate, trimethylolethanetri(meth)acrylate, trimethylolpropanetri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol and dipentaerythritol tritetra
Or hexa(meth)acrylate, epoxy di(meth)acrylate, oligoacrylate as disclosed in Japanese Patent Publication No. 52-7361, Japanese Patent Publication No. 48-4
Examples include acrylic urethane resin or acrylic urethane oligomer as disclosed in Japanese Patent No. 1708.

These unsaturated monomers and oligomers are preferably used in an amount of 70% by weight or less based on the total weight of the photopolymerizable composition.

Examples of the alkali-soluble resin used in the photopolymerizable composition of the present invention include polymer compounds described in JP-A-59-46643, phenol formaldehyde resin, cresol formaldehyde resin, polyhydroxystyrene, and carboxyl group. Examples include known alkali-soluble resins such as (meth)acrylate resins containing carboxyl groups and polyurethane resins containing carboxyl groups. These alkali-soluble resins are preferably used in an amount of 70% by weight or less based on the total weight of the photopolymerizable composition.

The diazo resins used in the photopolymerizable material of the present invention include 4-diazodiphenylene, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4
-N,N-diethylaminobenzene, 1-diazo-4-
N-ethyl-N-hydroxyethylaminobenzene, 1
-Diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-jethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-4° -N,N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p-)lylmercabutobenzene, 1-diazo-2-ethoxy-4
-N,N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-
Morpholinobenzene, 1-diazo-2,5-jethoxy-4-morpholinobenzene, 1-diazo-2,5-
Dimethoxy-4-morpholinobenzene, 1-diacy2,5-jethoxy-4-morpholinobenzene, 1-
Diazo-2,5-jethoxy-4-p-)lylmercabutobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N.

N-diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-
4-N,N-dimethylamino-5-methoxybenzene,
1-diazo-3-methoxy-4-pyrrolidinobenzene,
Diazo monomers such as 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazophenylamine, 3-(n-propoxy)-4-diazophenylamine, 3-impropoxy-4-diazodiphenylamine, and formaldehyde. , acetaldehyde, propionaldehyde, butyraldehyde, inftyraldehyde, and benzaldehyde in a molar ratio of 1:1 to 1:0.5, preferably 1:0.8 to 1:0.
6, and a reaction product of a condensate obtained by condensing this by a conventional method and an anion. Examples of anions include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitroortho-toluenesulfonic acid, 5-sulfosalicylic acid, 2.5-dimethylbenzenesulfonic acid, 2.4.6- Dodecylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 13-bromobenzenesulfonic acid, 2-
Fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2
Examples include -methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid and para-toluenesulfonic acid. Among these, particularly preferred are hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, and alkyl aromatic sulfonic acids such as 2,5-dimethylbenzenesulfonic acid.

In addition, the aforementioned diazo monomer and an aldehyde or its acetal having a carboxylic acid and/or phenol (
Furthermore, if necessary, a reaction product of the condensate obtained with the above-mentioned condensing agent) and the above-mentioned anion, or JP-A-1-102
Diazo resins described in No. 456 and JP-A-102457 are also preferably used in the present invention.

The amount of these diazo resins added to the total composition is preferably 15% by weight or less.

Note that these diazo resins can also be used as an intermediate layer between the photosensitive layer and the support in a lithographic printing plate.

Examples of the thermal polymerization inhibitor used in the photopolymerizable composition of the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-
-Butylcatechol, benzoquinone, 4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2
Examples include '-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc.If necessary, dyes or pigments or baking powders may be used for the purpose of coloring the layer of the photopolymerizable composition. A pH indicator or the like can also be added as a solvent.

Typical printing agents include a combination of a photosensitive compound that releases an acid upon exposure to light and an organic dye that can form a salt.

Furthermore, when using a diazo resin, as a stabilizer,
Phosphoric acid, phosphorous acid, tartaric acid, citric acid, malic acid, dipicolinic acid, polynuclear aromatic sulfonic acid and its salts, sulfosalicylic acid, etc. can be added as necessary.

In addition, the photopolymerizable product of the present invention may contain a plasticizer, etc. Examples of the plasticizer include dialkyl phthalate such as dibutyl phthalate and dibutyl phthalate, oligoethylene glycol alkyl ester, and phosphate ester plasticizer. etc. can be used.

Photopolymerizable &Il compound acids such as those mentioned above, such as toluene, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol monomethyl ether, 3-
A suitable solvent such as methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, N,N-dimethylformamide, N,N-dimethylacedeamide, dimethyl sulfoxide, ethylene dichloride, methyl lactate, ethyl lactate, etc. alone or in combination It is dissolved or dispersed in a mixed solvent combined with the above and applied on a support.

The coating amount is generally 0.1g/rd to 1% by weight after drying.
0 g/cd, preferably 0.5-5 g/rrl.

In addition, on the layer of the photopolymerizable composition provided on the support, in order to prevent the polymerization inhibiting effect due to the influence of oxygen in the air, an oxygen-blocking material such as polyvinyl alcohol or acidic cellulose may be used. A method of applying such a protective layer, which is preferably made of a superior polymer, is described, for example, in U.S. Pat. No. 3,458,311;
It is described in detail in Japanese Patent Publication No. 55-49729.

When the photopolymerizable material of the present invention is used as a photosensitive lithographic printing plate, an aluminum plate is preferred as the support, and aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used; for example, alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel are used. These compositions contain some iron and titanium as well as other negligible impurities.

The aluminum plate is surface treated as necessary.0 For example, surface treatments such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorinated zirconate, phosphate, etc., or anodizing are carried out. Also preferred is an aluminum plate grained and immersed in an aqueous sodium silicate solution, as described in U.S. Pat. No. 2,714,066;
181.461, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The above-mentioned anodizing treatment can be carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as Schereric acid or sulfuric acid, or a salt thereof. It is carried out by passing a current through a combined electrolyte using an aluminum plate as an anode.

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

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve adhesion with the photosensitive layer. It is applied to improve sex.

Prior to graining the aluminum plate, if necessary, the surface may be pretreated to remove rolling oil and expose a clean aluminum surface; for the former, Solvents such as trichlene, surfactants, etc. are used.

For the latter, a method using an alkaline etching agent such as sodium hydroxide or potassium hydroxide is widely used.

Mechanical, chemical, and electrochemical methods are all effective for graining. Mechanical methods include ball polishing, plastic polishing, and water-dispersed slurry of abrasives such as pumice. There is a brush polishing method in which the material is rubbed with a nylon brush, and chemical methods include
A method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Publication No. 31187 is suitable.
As the electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid, or a combination thereof is preferred.

Among these surface roughening methods, especially Japanese Patent Application Laid-Open No. 55-1379
A surface roughening method that combines mechanical roughening and electrochemical roughening as described in Japanese Patent No. 93 is preferred because it provides strong adhesion of the oil-sensitive image to the support.

Graining by the method described above is preferably carried out in such a range that the centerline surface roughness (Ra) of the surface of the aluminum plate is 0.3 to 1.0 μ.

The thus grained aluminum plate is washed with water and chemically etched as required.

The 2'-touching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, it is necessary that no film different from aluminum derived from the etching solution components is formed on the etched surface. Examples of preferred etching agents include basic substances such as sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate; acidic substances such as sulfuric acid and peroxide. Examples include sulfuric acid, phosphoric acid, hydrochloric acid, and their salts, but salts of metals with a lower ionization tendency than aluminum, such as zinc, chromium, cobalt, nickel, copper, etc., are not preferred because they form an unnecessary film on the etched surface.

It is most preferable to use these etching agents in such a way that the dissolution rate of the aluminum or alloy used is 0.3 to 40 g/m' per minute of immersion time by setting the concentration and temperature. There is no problem even if it exceeds or falls below.

Etching is performed by immersing the aluminum plate in the above etching solution or applying the etching solution to the aluminum plate, and the etching amount is 0.5 to 10 g/m.
' is preferably processed.

As the above-mentioned etching agent, it is desirable to use an aqueous base solution because of its high etching rate. In this case, since smut is generated, desmut processing is usually performed. Acids used for desmutting include nitric acid,
Sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, hydrofluoroboric acid, etc. are used.

The etched aluminum plate is washed with water and anodized if necessary. Anodic oxidation can be performed by methods conventionally practiced in this field. Specifically, when a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more of these, aluminum An anodic oxide film can be formed on the surface of the support.

The treatment conditions for anodic oxidation vary depending on the electrolyte used and cannot be determined unconditionally; however, for boat fishing, the concentration of the electrolyte is 1 to 80% by weight, the liquid temperature is 5 to 70°C, Appropriate ranges are a current density of 0.5 to 60 A/dm'', a voltage of 1 to 100 V, and an electrolysis time of 30 seconds to 50 minutes.

Among these anodizing treatments, especially British Patent No. 1.4
12,768 and U.S. Pat. No. 3,511.6.
The method of anodizing using phosphoric acid as an electrolytic bath described in No. 61 is preferred.

The aluminum plate roughened as described above and further anodized may be subjected to a hydrophilic treatment if necessary. Preferred examples thereof include US Pat. No. 2,714.066 and US Pat. Alkali metal silicates, such as aqueous sodium silicate solutions as disclosed in Japanese Patent Publication No. 36-22063, and potassium fluorozirconate as disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. No. 4.153.4.
There is a method of treating with polyvinylsulfonic acid as disclosed in No. 61.

Furthermore, after these treatments, aqueous resins such as polyacrylic acid, polymers and copolymers having sulfonic acid groups in their side chains, other low molecular weight compounds soluble in alkaline aqueous solutions, triethanolamine salts, and alanine compounds are removed. It is also suitable to use an undercoat.

The photosensitive composition applied specifically in the present invention coated on a support is exposed to light through a transparent original having line images, halftone dot images, etc., and then developed into an original image by developing with an aqueous alkaline developer. gives a negative relief image.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, laser beams, and the like.

As the developer suitably used for the above photosensitive composition,
Benzyl alcohol, 2-phenoxyethanol, 2-
It is an alkaline aqueous solution containing a small amount of an organic solvent such as butoxethanol, for example, in U.S. Pat. No. 3,475,171.
No. 3,615,480. Furthermore, JP-A-50-2660
The developing solutions described in Japanese Patent Publications No. 1, No. 57-192951, No. 59-84241, Japanese Patent Publication No. 56-39464, and Japanese Patent Publication No. 56-42860 are also excellent.

〔Effect of the invention〕

The photopolymerizable composition of the present invention has excellent sensitivity during image exposure,
Sufficient images can be obtained even with short exposure times.

Therefore, working efficiency etc. are significantly improved, and the film has sufficient sensitivity to scanning exposure using laser beams and the like.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to synthesis examples and examples, but the content of the present invention is not limited thereto.

Synthesis Example 1 25.38 g (0,195 m
ole'), n-butyl methacrylate 4.27g
(0,03mole), xchi L/7 glycol dimethacrylate) 2.97g (0,015mole)
, ethyl hydrogen succinate (2-methacryloyloxy) 1
3.81 g (0.06 mole), 4.63 g of sodium dodecyl sulfate, and 750 g of water were added and heated to 50° C. under a nitrogen stream. This mixed solution contains 0 potassium persulfate.
．． 58 g and sodium thiosulfate pentahydrate 0,54
g and stirred for 5 hours. After the reaction was completed, the mixture was salted out, centrifuged, and dried under reduced pressure to obtain 43 g of white powder.

10 g of white powder and 100 ml of pyridine! 200m1 with a stirrer and cooling pipe! The mixture was placed in a flask and stirred in an ice water bath. Add 1 part of methacrylic acid chloride to this mixture.
0 g was slowly added, and the mixture was stirred for 30 minutes in an ice water bath. Further, the mixture was heated to 50°C and stirred for 2 hours.

After the reaction was completed, the mixture was poured into ice water 11 with stirring and made acidic with hydrochloric acid. The precipitate was collected by filtration, thoroughly washed with an aqueous sodium chloride solution, and dried under reduced pressure to obtain 9 g of white powder (microgel (p) of the present invention).

The spherical shape of the powder particles was confirmed under a microscope.

Synthesis Examples 2 to 11 In the same manner as Synthesis Example 1, microgels (q) to (2) of the present invention shown in Table 1 below were synthesized.

EXAMPLE A substrate was prepared by the method disclosed in Japanese Patent Application Laid-Open No. 56-28893. That is, the surface of an aluminum plate having a thickness of 0.24 mm was gritted using a nylon brush and a 400 mesh water suspension of pumice stone, and then thoroughly washed with water. Then add 6% to 10% sodium hydroxide at 70°C.
After immersion for 0 seconds and etching, after washing with running water, 20%
Neutralization washing was performed with H, NOx, and washing was performed with water. This was calculated by using a sinusoidal alternating waveform current under the conditions that the anode special voltage was 12.7μ and the ratio of the cathode special electricity amount to the anode special electricity amount was 0.8.
% nitric acid aqueous solution with an anode special electricity amount of 160 corons/dm2. When the surface roughness at this time was measured, it was 0.6μ (expressed as Ra). Subsequently, it was immersed in 30% sulfuric acid and desmutted at 55°C for 2 minutes, and then anodized in 20% sulfuric acid at a current density of 2 A/dm2 for 2 minutes to a thickness of 2.7 g/m'. Thereafter, it was immersed in a 2.5% sodium silicate aqueous solution at 70° C. for 1 minute, then washed with water and dried. The following photosensitive liquids CVI-1 to (V)-11 were applied onto the thus prepared substrate.

Table 2 shows the microgels of the present invention used in photosensitive solutions CV)-1 to (V)-11.

Photosensitive liquid [v] After dissolving and dispersing these, use a spin coating machine to coat approximately 2
00r, p, m, and was spin-coated onto the substrate.

It was then dried at 100°C for 2 minutes. Dry coating weight is 3
g/mX. Next, polyvinyl alcohol (viscosity was 5.3 ± 0.5 by Hepler method using a 4% solution (20°C))
(cp), degree of saponification 86.5 to 89.0 mol%, degree of polymerization 1000 or less) was spin-coated onto the surface of the photosensitive layer at about 18 Qr, plm. The dry coating weight was 1.5 g/m''.

Next, as a comparative example, in place of the microgel of the present invention in the photosensitive solution, allyl methacrylate/methacrylic acid copolymer (molar ratio 85/15) described in Examples in JP-A-59-46643 was used. A photosensitive liquid (W) using the same method was applied in the same manner, and a layer of polyvinyl alcohol was further provided in the same manner.

Each photosensitive lithographic printing plate (V)-1 to (V]-11 obtained using photosensitive liquids CVE-1 to i'V)-11 and (W)
A gray scale tablet made by Fuji Photo Film ■ was placed on top of and [W], exposed with a Berkey printer (I2 Adalux 2KW) made by Berkey Technical Co., USA, and immersed in the following developer for 50 seconds at room temperature, The surface was lightly rubbed with absorbent cotton to remove the unexposed areas.

The sensitivity of the obtained lithographic printing plate to the exposure amount was visually read from the number of platens in the solid area. The results are shown in Table 2. Photosensitive planographic printing plate 1' using the microgel of the present invention
V)-1 to I''V)-11 all had a larger number of plates and higher sensitivity than the photosensitive lithographic printing plate [W] of the comparative example.

Table 2 Procedural amendment

Claims (1)

[Claims] A functional group represented by the following general formula (I) and a pKa value of 1
A photopolymerizable composition comprising a microgel having 4 or less acid groups and a photopolymerization initiator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, R in the formula represents -H or -CH_3.)