JP3275367B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition. More particularly, the present invention relates to a photosensitive composition which is coated on a support and developed with an alkali developer after image exposure.

[0002]

2. Description of the Related Art In recent years, various fields of application using photosensitive compositions have been studied. For example, there are a photosensitive layer for a printing plate such as a lithographic plate, a letterpress plate, a lithographic plate, an intaglio plate, and a photoresist for forming an electronic circuit such as an LSI and a printed board. In all of these, an image is formed by coating a photosensitive composition on some support or a workpiece, and then usually exposing the image, and removing exposed or unexposed portions with a developing solution.

As the developer used here, an aqueous alkaline developer and an organic solvent-based developer are known. In recent years, attention has been paid to an alkali developing type developer for occupational safety and health, but this is determined mainly by the properties of the binder polymer. Examples of a method for imparting alkali developability to a binder polymer include a method of copolymerizing a carboxylic acid-containing monomer and a method of reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride to form a carboxylic acid in the polymer. There are known methods for introducing

[0004]

However, the carboxylic acid-introduced binder polymer alone is insufficient in relaxation to stress and insufficient adhesion to the support. For this reason, the composition of the copolymer and the skeletal structure of the polymer itself have been devised in various ways, but sufficient results have not yet been obtained, and further measures are required.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that such problems can be solved by using a photosensitive material and a copolymer containing a specific structural unit as a binder polymer. The invention has been reached. That is, an object of the present invention is to provide a photosensitive composition which is developed with an alkali developing solution, and which has excellent mechanical properties and sensitivity, and further has excellent adhesion to a support. The object of the present invention is to provide a photosensitive composition comprising a photosensitive material and a polymer containing a structural unit represented by the following general formula (I).

[0006]

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(Wherein, R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 4 to 10). Hereinafter, the present invention will be described in detail. The photosensitive material in the present invention is not particularly limited, and conventionally known materials can be used. As a typical example, a diazo resin will be described below.

As the diazo resin, conventionally known ones can be used as appropriate. Examples thereof include diazo resins represented by condensates of an aromatic diazonium salt with, for example, an active carbonyl-containing compound, especially formaldehyde, in which an organic solvent-soluble compound is contained. Are preferred. Examples of the diazo resin include a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, hexafluorophosphate,
Diazo resin inorganic salts, which are organic solvent-soluble reaction products with tetrafluoroborate, or US Pat.
No. 309, a sulfonic acid such as p-toluenesulfonic acid or a salt thereof, a phosphinic acid such as benzenephosphinic acid or a salt thereof, a hydroxyl group-containing compound such as 2,4-dihydroxybenzophenone, and the like. , 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid or a salt thereof, and the like, and organic solvent-soluble diazo resin organic acid salts, which are reaction products, and the like.

Further, other diazo resins that can be suitably used in the present invention include an aromatic compound having at least one organic group among at least one carboxyl group and at least one hydroxyl group, and a diazonium compound. And (preferably) a (co) condensate containing an aromatic diazonium compound as a structural unit. The aromatic compound having a carboxyl group and / or a hydroxyl group contains in the molecule an aromatic ring substituted with at least one carboxyl group and / or an aromatic ring substituted with at least one hydroxyl group, In this case, the carboxyl group and the hydroxyl group may be substituted with the same aromatic ring.

The aromatic ring preferably includes an aryl group such as a phenyl group and a naphthyl group. Further, the carboxyl group or hydroxyl group may be directly bonded to the aromatic ring, or may be bonded via a joint. In the above case, 1
The number of carboxyl groups bonded to one aromatic ring is 1
Or 2 is preferable, and the number of hydroxyl groups bonded to one aromatic ring is preferably 1 to 3. Further, examples of the joint include an alkylene group having 1 to 4 carbon atoms.

Specific examples of the above-mentioned aromatic compound containing a carboxyl group and / or a hydroxyl group include benzoic acid, (o, m, p) -chlorobenzoic acid, phthalic acid,
Terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-
Methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4
Dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p
-Phenoxybenzoic acid, 4-anilinobenzoic acid, 4-
(M-methoxyanilino) benzoic acid, 4- (p-methoxybenzoyl) benzoic acid, 4- (p-methylanilino)
Benzoic acid, 4-phenylsulfonylbenzoic acid, phenol, (o, m, p) -cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p) -methoxyphenol, m-ethoxyphenol, catechol, fluoro Glycine, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin,
Biphenyl 4,4'-diol, 1,2,4-benzenetriol, bisphenol A, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, p-hydroxyacetophenone, 4,4-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenylsulfide cumylphenol, (o, m, p) -chlorophenol, (o, m, p) -bromophenol, salicylic acid, 4-methylsalicylic acid, 6- Methyl salicylic acid, 4-ethyl salicylic acid, 6-propyl salicylic acid,
6-lauryl salicylic acid, 6-stearyl salicylic acid,
4,6-dimethylsalicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-acid
Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid,
2,4-dihydroxy-6-methylbenzoic acid, 2,6-
Dihydroxybenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucin carboxylic acid, 2 4,4,5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m- (p-toluyl) gallic acid, protocatechu oil-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl)
Acetic acid, (2,4-dihydroxyphenyl) acetic acid, (3
4,5-trihydroxyphenyl) acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid,
-(P-hydroxyphenyl) methylbenzoic acid, 4-
(O-hydroxybenzoyl) benzoic acid, 4- (2,4
-Dihydroxybenzoyl) benzoic acid, 4- (p-hydroxyphenoxy) benzoic acid, 4- (p-hydroxyanilino) benzoic acid, bis (3-carboxy-4-hydroxyphenyl) amine, 4- (p-hydroxyphenyl) Sulfonyl) benzoic acid, 4- (p-hydroxyphenylthio) benzoic acid and the like can be mentioned, among which salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid and metachlorobenzoic acid are particularly preferable.

The aromatic diazonium compound constituting the constitutional unit of the aforementioned co-condensed diazo resin includes, for example, JP-B-49-4.
Although diazonium salts such as those described in JP-A-8001 can be used, diphenylamine-4 is particularly preferred.
-Diazonium salts are preferred. Diphenylamine-4
-Diazonium salts are derived from 4-amino-diphenylamines, such 4-amino-diphenylamines include 4-amino-diphenylamine,
4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4
-Methoxy-diphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine, 4-amino-3-β-hydroxy-ethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4- Amino-diphenylamine-2
-Carboxylic acid, 4-amino-diphenylamine-2'-
Examples thereof include carboxylic acids, and particularly preferred are 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine.

The above-mentioned co-condensed diazo resin can be prepared by a known method, for example, Photographic Science and Engineering (Photo, Sci., Eng.) No. 1
7, p. 33 (1973), U.S. Pat.
No. 631, No. 2,679,498, diazonium salts, aromatic compounds having a carboxyl group and / or a hydroxyl group and aldehydes such as paraformaldehyde in sulfuric acid, phosphoric acid or hydrochloric acid. , Acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

The aromatic compound having a carboxyl group and / or a hydroxyl group in the molecule, the aromatic diazo compound and the aldehydes or ketones can be freely combined with each other. It is also possible. The charged molar ratio of the aromatic compound having at least one of the carboxyl group and the hydroxyl group to the aromatic diazo compound is 1: 0.1 to
0.1: 1, preferably 1: 0.5 to 0.1: 1, more preferably 1: 1 to 0.15: 1. In this case, the total of the aromatic compound having at least one of the carboxyl group and the hydroxyl group and the aromatic diazo compound and the aldehydes or ketones are usually in a molar ratio of 1: 1.
A co-condensed diazo resin can be obtained by charging at 0.6 to 1.2, preferably 1: 0.7 to 1.5, and reacting at a low temperature for a short time, for example, about 3 hours.

The counter anion of the diazo resin used in the present invention includes an anion which forms a salt with the diazo resin stably and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, and organic phosphoric acids and sulfonic acids such as phenylphosphoric acid. Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dotecansulfonic acid, and benzenesulfonic acid. acid,
Toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5
Aliphatic and aromatic sulfonic acids such as sulfoisophthalate, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,2,3-trihydroxybenzophenone,
Hydroxyl-containing aromatic compounds such as 2,2 ', 4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, ClO ₄ , IO
Examples include perhalic acids such as _4, but are not limited thereto. Among these, particularly preferred are hexafluorophosphoric acid, tetrafluoroboric acid, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

The molecular weight of the above co-condensed diazo resin can be obtained as an arbitrary value by variously changing the molar ratio of each monomer and the condensation conditions, but it is effectively used for the intended purpose of the present invention. For this purpose, those having a molecular weight of about 400 to 10,000 can be used.
About 800 to 5,000 are suitable. The ratio of the above diazo resin contained in the photosensitive composition of the present invention is 1
It is preferably from 70 to 70% by weight, particularly preferably from 3 to 60% by weight.

Next, the polymerizable ethylenically unsaturated monomer used simultaneously with or instead of the diazo resin as a photosensitive material in the present invention is not particularly limited as long as it exhibits a chain polymerization reaction to active free radicals. Not limited. In addition,
The meaning of the monomer is a concept corresponding to a so-called macromolecular substance, and therefore includes not only a monomer in a narrow sense but also a dimer, a trimer, and an oligomer.

Examples of the polymerizable ethylenically unsaturated monomer include unsaturated carboxylic acids, esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and esters of an aromatic polyhydroxy compound and an unsaturated carboxylic acid. ester;
Esters obtained by an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and the above-mentioned polyvalent hydroxy compound such as the aliphatic polyhydroxy compound and the aromatic polyhydroxy compound are exemplified.

Specific examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritol diacrylate. Acrylates such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylates in which the acrylate of these exemplified compounds is replaced with methacrylate Similarly, itaconic acid esters and crotonates were substituted for itaconates. And there is a maleic acid ester or the like in place of crotonic acid ester or maleate.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polycarboxylic acid and the polyhydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid, and ethylene glycol. Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of the ethylenically unsaturated monomer used in the present invention include urethane acrylates such as an addition reaction product of toluene diisocyanate and hydroxyethyl acrylate; an addition reaction product of diepoxy compound and hydroxyethyl acrylate Epoxy acrylates; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.

Of these, acrylate or methacrylate monomers are particularly useful. The proportion of the above ethylenically unsaturated monomer contained in the photosensitive composition of the present invention is 5 to 90 parts by weight, particularly preferably 10 to 50 parts by weight. As the photopolymerization initiation system, conventionally known ones can be used, and for example, any of benzoin, benzoin alkyl ether, benzophenone, anthraquinone, benzyl, Michler's ketone, and a complex system of biimidazole and Michler's ketone can be suitably used.

The amount of the photopolymerization initiation system in the photosensitive composition is 0.1 to 20% by weight, preferably 0.2 to 10% by weight. Next, the polymer contained in the photosensitive composition together with the diazo compound and / or the polymerizable ethylenically unsaturated monomer and the photopolymerization initiation system will be described. The polymer used in the present invention is a polymer mainly composed of the structural unit represented by the general formula (I), but is particularly preferably a copolymer, and the ratio of the structural unit represented by the general formula (I) is 2 ~
A copolymer having 50 mol%, preferably 3 to 45 mol%, particularly preferably 5 to 40 mol% is preferred. The monomer used as a raw material of the structural unit represented by the general formula (I) will be described. These monomers have a structure represented by the following general formula (II).

[0024]

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(In the formula, R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 3 to 10.) These monomers were copolymerized as the number of n in the formula increased. As a property of time, generally, n is 2 or less (for example, n =
(2, R ₁ = CH ₃ , 2-hydroxyethyl methacrylate) has improved abrasion resistance, lower elastic modulus, and improved flexibility. For this reason, when the copolymer is applied to the photosensitive composition, as the number of n increases, the relaxation force against stress improves, and the adhesion to the support improves.

However, if the number of n is too large, the melting point will be low and handling will be inconvenient. The range of n preferably used in the present invention is an integer of 4 to 10, depending on the balance with other performances (particularly, chemical resistance and sensitivity) when applied to the photosensitive composition. Specific examples of these monomers include, for example, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate.

The above monomer can be easily obtained by a known synthesis method. Known public law includes, for example, West German Patent No. 1518572, JP-A-50-08320, JP-A-63-237791, and West German Patent No.
No. 027444 and the method described in British Patent No. 832493. The copolymer as a preferred example of the polymer of the present invention can be obtained by copolymerizing an addition-polymerizable unsaturated compound polymerizable with the above-mentioned monomer. ) Acrylic acid, (meth)
It is selected from compounds having an addition-polymerizable unsaturated bond such as acrylamides, (meth) acrylates, vinyl ethers, vinyl ketones, styrenes, olefins, and the like.

Specifically, the following (1) to (9) are exemplified. (1) (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylacrylamide, N-
(Meth) acrylamides such as hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, and N-ethyl-N-phenylacrylamide. (2) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl acrylate, octyl acrylate, acrylic acid-2 (Substituted) (meth) alkyl methacrylates such as -chloroethyl, 2-hydroxyethyl acrylate, glycidyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and cyclohexyl methacrylate. (3) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether. (4) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate. (5) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (6) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone. (7) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (8) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, (meth) acrylonitrile. (9) (meth) acrylic acid and the like.

Other than the above, it is not limited as long as it can be copolymerized with the monomer of the general formula (II). Among these, particularly preferred addition-polymerizable unsaturated compounds include:
Examples thereof include ethyl (meth) acrylate, methyl methacrylate, acrylonitrile, and methacrylic acid. Such a vinyl polymer is contained in the photosensitive composition in an amount of 30 to 99% by weight, preferably 40 to 97% by weight.

The photosensitive composition of the present invention may further contain dyes, pigments, coatability improvers, plasticizers, stabilizers, and the like, if necessary, in addition to the above-described materials. As the dye, for example, “Victoria Pure Blue BO”
H "(made by Hodogaya Chemical Co., Ltd.)," Oil Blue @ 603 "
(Manufactured by Orient Chemical Co., Ltd.), "Patent Pure Blue"
(Sumitomo Sangoku Chemical Co., Ltd.), "Crystal Violet",
“Brilliant Green”, “Ethyl Violet”,
“Methyl green”, “Erythrosin B”, “Basic fuchsin”, “Malachite green”, “Oil red”, “m-cresol purple”, “Rhodamine B”, “Auramine”, Ap-diethylaminophenyliminonaphthoquinone, Examples include triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes such as cyano-p-diethylaminophenylacetanilide.

The dye is generally used in the photosensitive composition in an amount of about 0.5 to 0.5.
About 10% by weight is preferable, and especially about 1 to
It is preferable to contain 5% by weight. Alkyl ethers (for example, ethyl cellulose,
Methylcellulose), carbitols (eg, methyl carbitol, ethyl carbitol), fluorine-based surfactants and nonionic surfactants (eg, “Pluronic L-64” (manufactured by Asahi Denka Co., Ltd.)). Examples of the plasticizer for imparting flexibility and abrasion resistance to the film include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, and phosphoric acid Tributyl, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers of acrylic acid or methacrylic acid, and examples of stabilizers include
Polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (acrylic acid, methacrylic acid, citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, etc. ) And the like. Other development accelerators include higher alcohols and acid anhydrides. The amount of these additives varies depending on the purpose of use, but is generally preferably 0.01 to 30% by weight based on the total solid content.

The photosensitive composition of the present invention is dissolved in a solvent in which the above-mentioned components are dissolved, and the resulting solution is applied to the surface of a support and dried to form, for example, a photosensitive lithographic printing plate material or a photoresist (eg, a resin relief plate material). , For a printed wiring base plate, etc.), but usable solvents include methyl cellosolve, methyl cellosolve acetate,
Examples include cellosolves such as ethyl cellosolve and ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone, methyl carbitol, and methyl lactate. These solvents are
Used alone or as a mixture of two or more.

The form of the photosensitive material produced using the photosensitive composition can be appropriately selected according to the purpose of use. For example, a sheet without solvent or diluted with a suitable solvent, for example, a polymer sheet, paper, coated on a metal sheet,
A form in which an overcoat layer or a polymer sheet layer for blocking oxygen is further provided as an upper layer when dried, a form in which the present photosensitive composition is encapsulated in microcapsules and applied on a sheet, a liquid photosensitive resin. Various selections such as a form used as it is can be made.

The exposure light source applicable to the photosensitive composition of the present invention is not particularly limited. Examples thereof include a carphone arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, and a helium cadmium laser. , An argon ion laser, a helium neon laser and the like can be particularly preferably used.

[0035]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.

Synthesis of Copolymer 1 Under a nitrogen stream, 4-hydroxybutyl acrylate (4HB) was added to a mixed solvent of 24 g of acetone and 24 g of methanol.
A) 3.2 g, methyl methacrylate (MMA) 6.4
g, acrylonitrile (AN) 7.2 g, methyl acrylate (MA) 4.8 g, ethyl acrylate (EA)
15.6 g, 2.8 g of methacrylic acid and 0.9 g of azobisisobutyronitrile were dissolved and refluxed at 60 ° C. for 6 hours with stirring. After the reaction is completed, throw the reaction solution into water,
The copolymer was precipitated. This is collected by filtration, and is
Vacuum dried for days.

Synthesis of Copolymers 2 to 6 Copolymers 2 to 6 were synthesized in the same manner as in Copolymer-1. Table 1 shows the monomer composition ratio of each copolymer. Table-
In 1, the copolymers of the present invention are copolymers 1, 2, and 5.

[0038]

[Table 1] 4HBA: 4-hydroxybutyl acrylate, MM
A: methyl methacrylate, AN: acrylonitrile MA: methyl acrylate, EA: ethyl acrylate, MAA: methacrylic acid, HEMA: 2-hydroxyethyl methacrylate

Synthesis of diazo resin-1 3.5 g (25 mmol) of p-hydroxybenzoic acid and 21.75 g of p-diazodiphenylamine sulfate (7
5 mmol) was dissolved in 90 g of concentrated sulfuric acid under ice-cooling.
To this solution 2.7 g (90 mmol) of paraformaldehyde were slowly added. At this time, the reaction temperature is 10
It was added not to exceed ° C. After stirring the reaction solution for 2 hours, it was added dropwise to 1 liter of ethanol, and the resulting precipitate was filtered off and washed with ethanol. The precipitate was dissolved in 200 ml of pure water, and an aqueous solution in which 10.5 g of zinc chloride was dissolved was added. The resulting precipitate was filtered, washed with ethanol,
Dissolved in 300 ml of pure water. To this solution, an aqueous solution in which 13.7 g of ammonium hexafluorophosphate was dissolved was added. The resulting precipitate was collected by filtration, washed with water and ethanol, and dried at 25 ° C. for one day to obtain diazo resin-1.

Hereinafter, the photosensitive composition of the present invention is applied to a photosensitive lithographic printing plate, and alkali developability, printing durability and sensitivity are measured.

Preparation of aluminum plate for lithographic printing plate The aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at 25 ° C. and a current density of 30 A / dm ² , and washed with water. In a 30% sulfuric acid bath
Anodizing treatment was performed for 2 minutes at 6.0 ° C. and 6.0 A / dm ² . Next, using an aqueous 1% sodium metasilicate solution at 85 ° C., 3
After sealing for 0 second, washing with water and drying, an aluminum plate for a photosensitive lithographic printing plate was obtained. Examples 1 to 4 and Comparative Examples 1 to 4
Photosensitive solution having the composition shown in Example 2 (Methyl cellosolve solution having a solid concentration of 10% by weight (Junsei Chemical Co., Ltd.)
Was applied using a wire bar so that the coating weight after drying was 20 mg / dm ² .

Since Examples 3 and 4 and Comparative Examples 3 and 4 used a photopolymerization initiator, the polyvinyl alcohol aqueous solution was dried on the photosensitive layer prepared above so that the film thickness became 3 μm. The overcoat layer was provided with a wire bar.

[0043]

[Table 2]

3) PETA: pentaerythritol triacrylate monomer (Biscoat # 300): manufactured by Osaka Organic Co., Ltd. 4) Polyacrylic acid: manufactured by Nippon Pure Chemical Co., Ltd. 5) Dye: "Victoria Pure Blue BOH": manufactured by Hodogaya Chemical Co., Ltd.

A negative original film was placed on each of the samples obtained as described above, brought into close contact with each other in a vacuum, exposed with a 2 kW metal halide lamp from a distance of 100 cm for 30 seconds, and then alkali-developed with the composition shown in Table 3 below. After immersion in the solution at 27 ° C. for 20 seconds, development was performed by rubbing lightly with absorbent cotton while washing with water.

Table 3 Developer composition Potassium silicate 1160 g 50% potassium hydroxide 266 g Water 6430 g pH (at 25 ° C.) 12.8

Each of the samples thus obtained was printed by a “Heidelberg GTO” printing machine, and the printing durability with an alkaline fountain solution used in newspaper printing and the like, and the non-image quality as an alkaline water developability were evaluated. The lines were examined for contamination. The results are shown in Table 2. The fact that the photosensitive lithographic printing plate exhibits excellent printing durability means that the photosensitive composition used has excellent mechanical properties and adhesion to a support. In Table 2, 5) Developability: Good: no stain is formed on the non-image area. Bad: 状態 Stain is generated. 6) Printing durability High: Number of printings of 100,000 or more. Medium: 60,000 or more. Less than 10,000 Low: Less than 60,000.

Example 5 and Comparative Example 5 A photosensitive solution having a composition shown in Table 4 below (a methylcellosolve solution (solid solution having a solid concentration of 10% by weight) was prepared on an aluminum plate produced by the above method). Chemical Co., Ltd.
Was applied using a wire bar so that the weight of the coated film after drying was 15 mg / dm ² .

Table 4 Composition of Example 5 (all parts by weight) Copolymer-5 100 parts Diazo resin 9 parts Polyacrylic acid 6 parts Dye ("Victoria Pure Blue BOH": Hodogaya Chemical Co., Ltd.) 2 Part Comparative Example 5 had the same composition as Example 5 except that copolymer-6 was used instead of copolymer-5. On each of the samples obtained as described above, the amount of light was increased by 1 / √
Step tablet that attenuates by 2 (made by Konica Corporation)
Was exposed at 300 mJ / cm ² , developed using an automatic developing machine manufactured by Dainippon Screen Co., Ltd., and evaluated for sensitivity. In Example 5, 5.9 steps and Comparative Example 5, 4.6. It was a step. At the time of development, the automatic developing machine was changed to a developer "SDN-
Each sample was set to be immersed in 21 "(manufactured by Konica Corporation) at 25 ° C for 20 seconds.

[0048]

As can be seen from the above results, the photosensitive composition of the present invention is excellent in alkali developability and excellent in mechanical properties, sensitivity and adhesion to a support.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI H05K 3/06 H01L 21/30 502R (58) Investigated field (Int.Cl. ⁷ , DB name) G03F 7/033 G03F 7 / 00 503 G03F 7/021 G03F 7/027 H01L 21/027 H05K 3/06

Claims (5)

(57) [Claims] 1. A photosensitive composition containing a photosensitive material and a polymer, wherein the polymer contains 3 to 50 mol% of a hydroxyalkyl (meth) acrylate structural unit represented by the following general formula (I). A photosensitive composition characterized by containing: Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and n is 4
Is an integer of 10 to 10. ) 2. The photosensitive composition according to claim 1, wherein in the general formula (I), R ₁ is a hydrogen atom . 3. The photosensitive composition according to claim 1, wherein the photosensitive composition contains a diazo resin. 4. The photosensitive composition according to claim 1, wherein the photosensitive composition contains a polymerizable ethylenically unsaturated monomer and a photopolymerization initiation system. 5. The photosensitive composition according to claim 1, wherein the photosensitive material contains (1) a diazo compound, (2) a polymerizable ethylenically unsaturated monomer, and a photopolymerization initiation system. .