JPH0418559A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve developability at the time of developing a nonimage part in alkali after imagewise exposure and to prevent occurrence of printing stains by using a diazo resin having specified repeating units. CONSTITUTION:The photosensitive composition contains a polymer soluble in organic solvents and the diazo resin having at least one kind of repeating units each represented by formula I in which R<1> is H, alkyl, alkoxy, OH, COOH, or carboxy-ester; R<2> is COOH or a group having at least one cooh; each of R<3> and R<4> is H, alkyl, or alkoxy; X is an anion; and Y is -NH-, -O-, or -S-, thus permitting the obtained photosensitive composition to be superior in solubility in organic solvents, and the photosensitive composition in the nonexposed part to be fully removed without adversely affecting the exposed part after coating, drying, and imagewise exposure.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a photosensitive composition, and particularly to a photosensitive composition suitably used in a photosensitive lithographic printing plate. More particularly, the present invention relates to photosensitive compositions containing novel diazo resins that are print-free. [Prior art and problems to be solved] Conventionally, printing materials that have been given photosensitivity in advance (so-called P
The majority of materials used as photosensitive materials for photosensitive materials (S version) are diazonium compounds, particularly polymeric diazonium salts (so-called diazo resins) in which two or more diazonium salt skeletons are linked. When such a diazo resin is coated on a suitable support such as paper, plastic or metal and exposed to actinic light through a transparent negative, the diazo resin in the exposed areas decomposes and becomes insoluble, Changes to lipophilicity. On the other hand, the surface of the support is exposed by dissolving and removing the unexposed areas with water. If a support having a surface that has been previously subjected to a hydrophilic treatment is used, the hydrophilic layer will be exposed in the unexposed areas through development. Therefore, when performing offset printing, this portion receives water and repels ink. On the other hand, the decomposed portion of the diazo resin exhibits lipophilic properties, repelling water and accepting ink. Such printing materials thus give so-called negative-positive printing plates. Conventionally, the method for linking diazonium salt skeletons in such diazo resins is to condense an aromatic diazonium compound and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes or acetals such as formaldehyde and acetaldehyde, in an acidic medium. The method was used to The most typical example is a formaldehyde condensate of p-diazodiphenylamine. A method for producing a diazo resin using the coupling method is described, for example, in U.S. Pat. No. 2,679,498.
No. 3,050,502, No. 3,311,60
No. 5, and No. 3,277.074. In the diazo resin linked by the reactive carbonyl group, when the counter anion of the diazonium salt is a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid, or an inorganic anion such as a double salt with zinc chloride, water-soluble There is a problem that it becomes unstable against moisture and its storage stability deteriorates. Therefore,
In order to improve storage stability, there is a method in which a water-soluble diazo resin is reacted with an organic coupling agent such as a phenolic hydroxyl group-containing aromatic compound, an acidic aromatic compound, or an acidic aliphatic compound and used as a water-insoluble resin. Special Public Service 1977-
No. 1167 and US Pat. No. 3,300,309. However, this type of diazo resin does not have sufficient solubility in organic coating solvents such as alcohols, ketones, and glycol ethers. Therefore, in order to make the diazo resin water-insoluble and organic solvent-soluble, halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid,
and JP-A-54-98 on the use of diazo resins with perhalogen acids such as perchloric acid and periodic acid as counter anions.
It is described in the specifications of Publication No. 613 and Publication No. 56-121031. Further, regarding the use of anionic surfactants, that is, diazo resins in which a sulfonic acid containing a long-chain alkyl group is used as a counter-anion, JP-A-58-209733 and JP-A-62
It is described in the specifications of JP-175731 and JP-63-262643. However, since these diazo resins are essentially insoluble in alkaline water, the diazo resins are not sufficiently removed during alkaline development, resulting in a residual film in unexposed areas. the result,
There was a problem that printing stains occurred. [Object of the Invention] Therefore, an object of the present invention is to provide a photosensitive composition containing a novel diazo resin that does not cause printing stains. That is, an object of the present invention is to improve the developability when developing a non-image area with alkali after image exposure, and to prevent printing stains from occurring.
An object of the present invention is to provide a photosensitive composition containing a diazo resin. Another object of the present invention is to provide a photosensitive composition containing a diazo resin that can be manufactured at low cost and has excellent manufacturing suitability. Yet another object of the present invention is to improve solubility in organic solvents;
Another object of the present invention is to provide a photosensitive composition containing a diazo resin with improved storage stability. [Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present invention has been made.
The inventors have discovered that the above objects can be achieved by using a new diazo resin, and have arrived at the present invention. That is, the present invention provides a photosensitive composition containing a diazo resin and an organic solvent-soluble polymer compound, in which the diazo resin has at least one repeating unit represented by the following general formula (r). The present invention provides a photosensitive composition having the following characteristics. N'X In the formula, R1 represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyester group, or a carboxyl group, R2 represents a carboxyl group or a group having at least one carboxyl group, and R3 represents a hydrogen atom , represents an alkyl group or an alkoxy group, R4 represents a hydrogen atom, an alkyl group or an alkoxy group, X- represents an anion, and Y represents -NH--0- or -S-. The present invention will be explained in detail below. R' in the above-mentioned formula (I) represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy ester group, or a carboxyl group, preferably a hydrogen atom, an argyl group having 1 to 5 carbon atoms, or a carbon number 1 to 5. Indicates three alkoxy or hydroxy groups. R2 represents a carboxyl group or a group having at least one carboxyl group, preferably a carboxyl group or a group having at least one carboxyl group and having 15 or less carbon atoms. R3 represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably, it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms. R4 represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably, it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms. X- represents an anion, preferably an anion of an inorganic or organic acid having a pKa of 4 or less. Specifically, the anions include hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, and hydrobromic acid; sulfuric acid;
nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid, inorganic iso- and heteropolyacids such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters, arsonic acids, phosphinic acids, Fluorocarboxylic acids such as trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoroboric acid, hexafluorophosphoric acid, perhydrochloric acid, as well as aliphatic and aromatic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, etc. Fluoroalkanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutyl Phenoxy-3-propanesulfonic acid, cyamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-
Butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, Hensensulfonic acid, toluenesulfonic acid,
Mesitylene sulfonic acid, p-chlorobenzenesulfonic acid, 2.5 dichlorobenzenesulfonic acid, sulfosalicylic acid, 2.5-dimethylbenzenesulfonic acid, p-acetylhenzenesulfonic acid, 5-nitro-〇-toluenesulfonic acid, 2-Nitrobenzenesulfonic acid, 3-chlorohenzenesulfonic acid, 3-promohenzenesulfonic acid, 2
-Chloro-5-nitrobenzenesulfonic acid, butylhenzenesulfonic acid, octylhenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid,
Dodecyloxybenzenesulfonic acid, 2-methoxy-4
~Hydroxy~5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid,
Dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-5-sulfonic acid,
Naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid, 4,4-diazidostilbene-3,3'-disulfonic acid, 1.2-naphthoquinone-2 -diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-1-diazide 4-
Included are sulfonic acid anions or mixtures of these anions. Particularly preferred among these anions are those of hexafluorophosphoric acid, methanesulfonic acid, dodecylbenzenesulfonic acid or 2-methoxy-4-hydroxy-5-henzoylhenzenesulfonic acid. Y represents -NH--1 or -8-, preferably -NH-. Examples of methods for synthesizing the diazo resin used in the present invention include:
A diazo monomer having a 4-diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl sulfide skeleton and an aldehyde or its acetal having a carboxyl group in a molar ratio of preferably 1:10, respectively. More preferably 1:2-1
:0.2 in an acidic medium. When performing the condensation reaction, in order to adjust the carboxylic acid value and molecular weight of the diazo resin produced, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, iso-butyraldehyde, henzaldehyde, acetone, methyl ethyl ketone, or acetophenone is used. Active carbonyl compounds having no carboxyl group or their acetals can be used in combination as condensing agents. As the active carbonyl compound having no carboxyl group, formaldehyde is most preferable, and the molar ratio thereof to the diazo monomer is preferably 0 to 5, more preferably 0.1 to 1. It is. Note that when an aldehyde having a carboxyl group and an active carbonyl compound not having a carboxyl group are used together, the diazo monomer and the aldehyde having a carboxyl group are first condensed in an acidic medium, and then a more reactive Higher molecular weight diazo resins can be obtained if the post-condensation is carried out using active carbonyl compounds without carboxyl groups, such as formaldehyde, or their acetate. In addition, instead of the above-mentioned active carbonyl compounds having no carboxyl group or their acecurs, methylol derivatives as described in Japanese Patent Publication No. 49-45322 and No. 49-45323, or It is also possible to use olefinically unsaturated compounds such as those described in Japanese Patent Publication No. 187925/1983. Specific examples of the diazo monomer include 4-diazodiphenylamine, 4'-hydroxy-4-diazodiphenylamine, 4'-methoxy-4-diazodiphenylamine, 4'-ethoxy-4-diazodiphenylamine, 4'- 〇-Propoxy 4-diazodiphenylamine 1. sl = -propoxy-4-diazodiphenylamine, 4'methyl-4-diazodiphenylamine, 4'
Ethyl-4-diazodiphenylamine, 4'-n-propyl-4-diazodiphenylamine, 4'-1-propyl-4-diazodiphenylamine, 4'-〇-butyl-4-diazodiphenylamine, 4'-hydroxymethyl-4- Diazodiphenylamine, 4'-β-hydroxyethyl-4-diazodiphenylamine, 4'-T-hydroxypropyl-4-diazodiphenylamine, 4'-
Methoxymethyl-4-diazodiphenylamine, 4'ethoxymethyl-4-diazodiphenylamine, 4'-β
-methoxyethyl-4-diazodiphenylamine, 4'
-β-ethoxyethyl-4-diazodiphenylamine,
4'-carbomethoxy-4-diazodiphenylamine,
4'-carboethoxy-4-diazodiphenylamine,
4'-hydroxy-4-diazodiphenylamine, 4-
Diazo 3-methoxy-diphenylamine, 4-cyaso-2-methoxydiphenylamine, 2'-methoxy-4-
Diazodiphenylamine, 3-methyl-4-diazodiphenylamine, 3-ethyl-4-diazodiphenylamine,
3'-Methyl-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3-hexyloxy-4-diazodiphenylamine, 3-β-hydroxyethoxy-4-diazodiphenylamine, 2-methoxy-
5'-Methyl-4-diazodiphenylamine, 4-diazo-3-methoxy-6-methyldiphenylamine, 3,
3'-dimethyl-4-diazodiphenylamine, 3'-
〇-Butoxy4-thia〉diphenylamine, 3,4'
-dimethoxy-4-diazodiphenylamine, 2'-poxy-4-diazodiphenylamine, 4-diazodiphenyl ether, 4'-methoxy-4-diazodiphenyl ether, 4'-methyl-4-diazodiphenyl ether, 3.4' -dimethoxy-4-diazodiphenyl ether, 4'-hydroxy-4-diazodiphenyl ether, 3.3'-dimethyl 4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl-4
-diazodiphenyl sulfide, 4'-methyl-2,5
-dimethoxy-4-diazodiphenyl sulfite and the like. The aldehyde or acetal thereof having a carboxyl group preferably includes an aldehyde having a structure represented by the following formula (II) or an acetal thereof. OOH (If) HO [In the formula, R5 may have a single bond or a substituent 2
It represents an organic group having a valence of 1 to 14 carbon atoms (for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group). R5
Examples of groups that can be substituted with include an alkyl group, a teryl group, an alkoxy group, an aryloxy group, a halogen atom, a hydroxy group, a substituted or unsubstituted amino group, a carboxyl ester group, or a carboxyl group. ] Specific examples of these carboxyl group-containing aldehydes or their acecules include glyoxylic acid, malonaldehydic acid, succinic aldehydic acid, 2-methylsuccinic aldehydic acid, 2-methoxysuccinic aldehydic acid, and 2-hydroxysuccinic acid. Aldehydic acid, 2-chlorosuccinic aldehydic acid, 2-aminosuccinic aldehydic acid, glutaraldehydic acid, 2-methylglucuraldehydic acid, 2-methylglucuraldehydic acid, 2-hydroxyglutaraldehydic acid, 2-chlorosuccinic acid taraldehydic acid, adipinaldehydic acid, pimelic aldehydic acid,
Succinic aldehydic acid, azelaic aldehydic acid, sebacinaldehyde' 62.2-formylmethylsuccinic acid, 2-formylethylsuccinic acid, formylmethylmalonic acid, formylethylmalonic acid, N-(2-formyl-2
-hydroxyethyl)glycine, N-(2-formyl 2
-hydroxyvinyl)glycine, 486-thioxohexanoic acid, 6-oxo-2,4-hexadienoic acid, 3-
Formylcyclohexanecarboxylic acid, 4-formylphenylacetic acid, malealdehydic acid, fumaraldehydic acid, dibromomalaldehydic acid, glucuronic acid, galactronic acid, mannuronic acid, idronic acid, guluronic acid, phthalaldehydic acid, 3,4-dimethoxyphthalaldehyde acid,
Isophthalaldehydic acid, terephthalaldehydic acid, 3
-Formyl-4-methoxybenzoic acid, 4-formyl phthalic acid, 4-formyl isophthalic acid, 4-formylmethyl phthalic acid, 4-formylethyl phthalic acid, 4-formylethoxyphthalic acid, 5-formylethoxyisophthalic acid, 4 -carboxymethylphthalic acid, 3-formyl-1-
Examples include naphthoic acid, 6-formyl-1-naphthoic acid, and acetals thereof. Specific examples of the acidic medium used when synthesizing the diazo resin used in the present invention include strong acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, or sulfuric acid. These media contain at least 30% by weight, preferably 70-1
Used at a concentration of 0.00% by weight. Generally the remainder is water, but partially or completely organic solvents, such as methanol,
It may also consist of acetic acid, N-methylpyrrolidone, etc. Good results are achieved, for example, with 85-93% phosphoric acid, 80% sulfuric acid or 90% methanesulfonic acid or mixtures of these acids. The temperature during condensation is about 0 to 70°C, preferably about 70°C. Approximately 5
~50°C. The weight average molecular weight of the diazo resin used in the present invention is approximately 5
00 to 100,000, preferably about 1.00 to 100,000.
The range is from 000 to 10,000. The content of the diazo resin contained in the photosensitive composition of the present invention is 1 to 50% by weight, preferably 3 to 20% by weight. The diazo resin of the present invention can also be used in combination with a diazo resin that does not have a carboxyl group. Representative examples include, for example, U.S. Patent No. 2.679.498,
There are condensates of p-diazodiphenylamine and formaldehyde as described in the specifications of 3.050.502, 3.311.605, and 3.277,074. The weight ratio of the diazo resin of the present invention and the condensate of p-diazodiphenylamine and formaldehyde when used together is preferably 1:9 to 9:
11, more preferably l:9 to 1:2. Although the diazo resin of the present invention has excellent developability, its sensitivity is somewhat low. On the other hand, a condensate of p-diazodiphenylamine and formaldehyde has high sensitivity but poor developability. Therefore, by using both together, the sensitivity is high,
Moreover, a photosensitive composition with excellent developability can be provided. Next, examples of the "organic solvent soluble polymer compound" used in the present invention include acrylic resin, methacrylic resin, polyvinyl acecool resin, polyurethane resin,
Polyamide resin, epoxy resin, polystyrene resin,
Examples include polyether resin, polyester resin, polycarbonate resin, and phenol resin. These polymer compounds are used in a form that is soluble or at least swellable in an alkaline developer. Examples of these polymer compounds include the following (I) to (
Examples include copolymers of the monomers listed in I51. (I) N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide,
N-(4-hydroxynaphthyl)methacrylic 7mide. f2) o-1m- or p-hydroxystyrene. (3) o-1m- or p-hydroxyphenyl methacrylate, 0-1m- or p-hydroxyphenyl acrylate. (4) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N-(P-chlorobenzoyl)methacrylamide. (5) m-aminosulfonylphenyl methacrylate,
Unsaturated sulfonamides such as N-(P-aminosulfonylphenyl)methacrylamide and N-(P-toluenesulfonyl)methacrylamide. (6) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid. (7) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid 2
-chloroethyl, 2-hydroxyethyl acrylate,
Alkyl acrylates such as glycidyl acrylate and N-dimethylaminoethyl acrylate. (8) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate-I, 4-hydroxybutyl methacrylate, glycyl methacrylate, N-dimethylaminoethyl methacrylate , alkyl methacrylates such as Hensyl methacrylate. (9) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylamide, N-hydroxyethylacrylamide, N-phenylacrylamide,
N-nitrophenyl acrylamide, N-ethyl-N-
Acrylamides and methacrylamides such as phenylacrylamide. (I01 Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ethers. 0D vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate. Styrenes such as αa styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. αJ Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene. 05) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. Furthermore, a copolymer that can be copolymerized with the above-mentioned copolymer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with, for example, glycidyl methacrylate, glycidyl acrylate, and the like. Suitable organic polymer compounds include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component, such as 2-hydroxyethyl acrylate or A multicomponent copolymer of 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile, acrylic acid or methacrylic acid, and optionally other copolymerizable polymers, as described in JP-A-53-120903. Acrylic acid or methacrylic acid esterified with a group having a hydroxyl group at the end and containing a dicarboxylic acid ester residue, acrylic acid, or methacrylic acid and, if necessary, other copolymerizable monomers. multi-component copolymers, monomers having aromatic hydroxyl groups as described in JP-A No. 54-98614 (e.g.
N(4-hydroxyphenyl) methacrylamide, etc.)
, a multicomponent copolymer of acrylic acid or methacrylic acid and optionally other copolymerizable monomers, JP-A-56-4
Examples include multi-component copolymers of alkyl acrylate, acrylonitrile or methacrylonitrile, and unsaturated carboxylic acids as described in Japanese Patent No. 144. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. In addition, JP-B No. 54-19773, JP-A No. 57-94747, JP-A No. 6, which solubilized polyvinyl acetal and polyurethane with alkali.
No. 0-182437, No. 62-58242, No. 62-
Also useful are the polymer compounds described in No. 123453. Further, particularly preferred polymer compounds of the present invention include sulfonamide F group-containing polymer compounds. Such a sulfonamide F group-containing polymer compound is usually 10,000 to 200,000, preferably 20,000 to 150,000, and contains a monomer represented by the following formula (I[I), <rv>, or (V) as a constituent unit. It is a copolymer having a molecular weight, or a polyurethane resin containing a sulfonamide group, which will be described later. (I) (TV) [In the formula, R6 represents a hydrogen atom or a methyl group, and R7 represents a C1 to C1□ alkylene group, cycloalkylene group, arylene group, or aralkylene group that may have a substituent, -W- represents -〇- or -N(-R”)-, and R
11 and R10 each represent a hydrogen atom, an alkyl group from 01 to CI2 which may have a substituent, a cycloalkyl group, an aryl group, or an aralkyl group, and R9 represents an alkyl group from C to CI2 which may have a substituent. group, cycloalkyl group, aryl group or aralkyl group. Preferably, R7 represents a 02-C8 alkylene group, a cycloalkylene group, a phenylene group which may have a substituent, or a naphthylene group, and R11 represents a hydrogen atom, a C2-C6 alkyl group, or a substituent-containing alkyl group. R9 is a C2-C6 alkyl group, a phenyl group or naphthyl group which may have a substituent, and RIO is a hydrogen atom]. Examples of copolymerization components used in combination with these sulfonamide group-containing monomers include monomers shown in (I) to a3) below. (I) Acrylamides, methacrylamides, acrylic esters, methacrylic esters, and droxystyrenes having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)acrylamide or N-(4-hydroxyphenyl)methacrylate Amide, 0-1m-1p-
hydroxystyrene, o-2m-1p-hydroxyphenyl-acrylate or methacrylate, (2) acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic acid Hexyl, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-
(Substituted) alkyl acrylates such as dimethylaminoethyl acrylate, +5] Methyl meccrylate, ethyl methacrylate, propyl methacrylate, butyl meccrylate,
Amyl methacrylate, cyclohexyl methacrylate, 4-hydroxyethyl acrylate, glycidyl methacrylate-1-1N dimethylaminoethyl methacrylate-1
(Substituted) alkyl methacrylates such as (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N- - Acrylamides or methacrylamides such as phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxydiethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether , vinyl ethers such as phenyl vinyl ether,

[8] Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (9) Styrenes such as styrene, α-methylstyrene, methylstyrene, and tetraromethylstyrene; aω methyl vinyl ketone; , vinyl ketones such as ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, OD olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, @ N-vinylpyrrolidone, N-vinylcarbasol, 4-vinylpyridine, acrylonitrile , methacrylateryl, etc., OJ maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N-(p-chlorohendiyl)methacrylamide, etc. Furthermore, it can be copolymerized with the above monomers. Monomers may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like. If necessary, polyvinylfutisol resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added to the above copolymer. Among the above-mentioned polymer compounds, the following copolymers are particularly preferred as binders. That is, in the molecular structure, (al below - Funazura (Vl) [wherein Rl l represents a hydrogen atom or a methyl group,
represents 10- or -NH-, preferably NH-. ] 1 to 40 mol% of the structural unit represented by (bi below - Funazo (■)) and/or a structural unit having an alcoholic hydroxyl group CH2-C
-(■) N [In the formula, R12 represents a hydrogen atom or a methyl group] from 5 to
40 mol%, (C) 0 to 40 mol% of structural units formed from methacrylic acid and/or acrylic acid, (dl Below - Shipyard (■) CH2-C- (■) COOR"R"" is carbon It contains 20 to 70 mol% of the structural unit represented by [representing an alkyl group, an aryl group, or an aryl group-substituted alkyl group having 1 to 2 atoms], and has a weight average molecular weight of 20,000 to 150,000. A specific example of a monomer having a sulfonamide group forming the structural unit represented by -Funazura (VT) is a certain copolymer.
Methacrylamides such as -(o-aminosulfonylphenyl)methacrylamide, N-(m-aminosulfonylphenyl)methacrylamide, N-(p-aminosulfonylphenyl)methacrylamide, and acrylamide having the same vA group as above. Examples include methacrylic acid esters such as 0-aminosulfonylphenyl methacrylate, m-aminesulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, and acrylic esters having the same substituents as above. Preferably, N-(p-aminosulfonylphenyl)methacrylamide, N(p-aminosulfonylphenyl)acrylamide [wherein R1+ represents a hydrogen atom or a methyl group, and examples thereof include]. Examples of the hexamer having a cyano group in its side chain, which forms the structural unit represented by formula (■), include acrylonitrile, methacrylatetrile, and the like. Acrylonitrile is preferred. Specific examples of the chemical compound forming the structural unit having an alcoholic hydroxyl group include (meth)acrylic acid esters such as the compound shown in the following formula (IX) as described in Japanese Patent Publication No. 527364. and acrylamides. [In the formula, R'' is a hydrogen atom or a methyl group, R'6 is a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n
represents an integer from 1 to 10. ] Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, etc.
In addition, examples of acrylamides include N-methylol (
meth)acrylamide, N-hydroxyethyl(meth)
Examples include acrylamide. Preferably it is 2-hydroxyethyl (meth)acrylate. The monomer having a carboxyester group in the side chain and forming the structural unit represented by formula (■) above is as follows:
Ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, benzyl acrylate, 2-chloroethyl acrylate,
Examples include phenyl acrylate, glycidyl acrylate, and diphenoxyethyl acrylate. The method for synthesizing the sulfonamide group-containing polymer compound as a binder in the photosensitive composition of the present invention includes -
i. Ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol using a known radical polymerization method or the like using an initiator (0.1 to 4.0 mol%) such as azoisobutyronitrile or benzoyl peroxide. , ethanol, ethylene glycol monomethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N
- Easily synthesized by solution polymerization in a solvent such as dimethylacetamide, toluene, ethyl acetate, methyl acetate, ethyl lactate, or methyl lactate. The organic solvent-soluble polymer compound used in the present invention may be used alone or in combination of two or more, and is usually 40 to 99% by weight in the solid content of the photosensitive composition.
, preferably 50 to 95% by weight. In addition, the photosensitive diazo resin used in the present invention is usually 1 to 60% by weight.
, preferably 3 to 30% by weight. The sulfonamide group-containing polyurethane resin used in combination with the photosensitive diazo resin is preferably a polyurethane resin containing sulfonamide groups in the side chain and/or main chain. The polyurethane resin having a sulfonamide group preferably used in the present invention is a polyurethane resin whose basic skeleton is a reaction product of a polyol compound having one or more sulfonamide groups in the molecule and a polyisocyanate compound. . The polyurethane resin having a sulfonamide group that is more preferably used in the present invention has the following formula: CX>~(X
It is a polyurethane resin whose basic skeleton is the reactivity of a diol compound having a sulfonamide group shown in III) and a diisocyanate compound. (X) )10-R"-A"-R"-011 Nl(80-(I-R"-5Oz-N)t +r R"+
NH-SOz-R” +0H(XI[) HO+ R”-NH-SOzsr R29-(-So□
-N)I-R"÷GO0H(XI) In the formula, R", R1IIXR1q% R"% R22 and R2 may be the same or different, and have a single bond or a substituent. It shows a divalent aliphatic or aromatic hydrocarbon group, which may be a divalent aliphatic or aromatic hydrocarbon group. Preferably a C1-C2 degree alkylene group, a 06-CI5 arylene group. If necessary, RI7, R18% R", R21R22 and R'' may have other functional groups that do not react with isocyanate groups, such as ester, urethane, amide, ureido, and ether groups.In addition, RI'?, RIfi, RI9
, R2+, R2Z and R23 may form a ring. Rza represents a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group, or an aralkyl group, preferably a hydrogen atom, a C4-C8 alkyl group, a C6-CIS aryl group, or an aralkyl group. show. Rza is an alkyl group which may have a substituent,
It represents a C, -CS alkyl group, an aralkyl group of 06 to CI5, and an aralkyl group. A1 and A2 each represent a nitrogen atom and a C3 to C2G trivalent aliphatic or aromatic group which may have a substituent. XI and ×2 are each a single bond or C, H, N, ○, S
A divalent linking group consisting of one or more selected atoms. R2S, R26, R2'+, RZII, R29 and R"
may be the same or different, and each represents a divalent hydrocarbon group which may have a substituent. Preferably C3
-C2° alkylene group, aralkylene group, and arylene group. If necessary, it may have other functional groups that do not react with isocyanate groups, such as ester, urethane, amide, ureido, and ether groups. k, l, s and t are each 0 or 1, and k+ji
! #Q, s+t≠0. -a Compounds represented by formula (X) or (XI) include:
For example, p-(I,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide, p-n
, N-ethyl form of i-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide, N-(
m-methylsulfonylaminophenyl)-2,2-bis(hydroxymethyl)propanamide, N-(p-methylsulfonylaminophenyl)-2,2-bis(hydroxymethyl)propanamide, N-(m-ethylsulfonyl) aminophenyl)-2,2-bis(hydroxymethyl)propanamide, N-(pethylsulfonylaminophenyl)-2,2bis(hydroxymethyl)propanamide, N(N'N'-bis(hydroxyethyl)
Aminocarbonylethyl) methanesulfonamide, N-
(N', N'-bis(hydroxyethyl)aminocarbonylethyl)benzenesulfonamide and the like. Examples of the compound represented by the general formula (Xn) or (X I[[) include compounds represented by the following structural formula. These diol compounds having a sulfonamide group are
They can be used alone or in combination of two or more. Further, a diol compound that does not have a sulfonamide group and may have other substituents that do not react with isocyanate can also be used in combination. Specifically, such diol compounds include those shown below. Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1.3-7" ethylene glycol, 1
, 6-hexanediol, 2-butene-1,4-diol, 2゜2.4-1-dimethyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, Tricyclodecane dimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct to bisphenol, propylene oxide adduct of bisphenol A,
Ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone , bis(2-hydroxyethyl)-2,4-h lylene dicarbamate, 2.4
1 rylene-bis(2-hydroxyethylcarbamide),
Bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl)isophthalate, 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis( 2-hydroxyethyl)propionic acid, 22-bis(3-hydroxypropyl)brobionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 4.
Examples include 4-bis(4-hydroxyphenyl)pentanoic acid and tartaric acid. Specifically, the diisocyanate compounds preferably used for producing the above-mentioned urethane resin include those shown below. i.e., 2.4-1-lylene diisocyanate, dimer of 24-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
- Aromatic diisocyanate compounds such as xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 33'-dimethylbiphenyl-4,4'-diisocyanate; Methylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate,
Aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4.4'
- Alicyclic diisocyanate compounds such as methylene bis(cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2.6) diisocyanate, 13-bis(isocyanatomethyl)cyclohexane, etc.; 1.3
Examples include diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of butylene gellicol and 2 mols of tolylene diisocyanate. The polyurethane resin used in the present invention is synthesized by heating the above-mentioned diisocyanate compound and diol compound in an aprotic solvent, adding a known catalyst having an activity corresponding to the reactivity of each compound. The molar ratio of diisocyanate and diol compound used is preferably 0.8
:1 to 1.2:1, and if an isocyanate group remains at the end of the polymer, it is finally synthesized in a form in which no isocyanate group remains by treating with alcohols, amines, etc. The polyurethane resin used in the present invention preferably has a weight average molecular weight of 2. OO0 or more and the number average is i,
It's more than ooo. More preferably, the weight average is 5. O
The range is OO~300,000, and the number average is 2,000~25
It is in the range of 10,000. The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, more preferably 1.1.
~10. The polyurethane resins of the present invention may be used alone or in combination. When the above polyurethane resin is used as the polymer compound used in the present invention, the polyurethane resin is usually contained in the solid content of the photosensitive composition in an amount of about 5 to 95% by weight, preferably about 10 to 85% by weight. In addition to the polyurethane resins having sulfonamide groups, phenol formaldehyde resins, cresol formaldehyde resins, phenol-modified xylene resins, polyhydroxystyrenes, polyhalogenated hydroxystyrenes, carboxyl group-containing epoxy resins, polyacetal resins, acrylic resins, methacrylic resins , a known alkali-soluble polymer compound such as carboxyl group-containing polyurethane resin. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition. [Organic solvent soluble polymer compound] used in the present invention
may be used alone or in combination. The content of these polymer compounds in the photosensitive composition is about 50 to 99.5% by weight, preferably about 55 to 95% by weight.
Weight%. Various additives can be further added to the photosensitive composition used in the present invention. For example, alkyl ethers (e.g. ethylcellulose, methylcellulose) to improve coating properties, surfactants (e.g. fluorosurfactants), plasticizers (e.g. tricres) to impart flexibility and abrasion resistance to the film. diluphosphate, dimethyl phthalate, dibutyl phthalate,
trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), acridine dye, cyanine dye, styryl dye, triphenylmethane dye, and phthalocyanine as coloring substances to visualize the image area after development. pigments such as and other common stabilizers for diazo resins (phosphoric acid,
Phosphorous acid, birophosphoric acid, oxalic acid, boric acid, p-)luenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, malic acid, tartaric acid , dipicolinic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene]-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl -Methyl-pyrazolone sulfonate, 2
-phosphonobutanetricarboxylic acid-1,2,4, l-phosphonoethanetricarboxylic acid-1,2,2,1-hydroxyethane-1,1-disulfonic acid, etc.) can be added. The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.1 to 30% by weight based on the total solid content of the photosensitive layer. The photosensitive composition of the present invention is dissolved in a suitable organic solvent and coated on a support having a hydrophilic surface at a dry coating weight of 0.2 to 10%.
g/m to obtain a photosensitive planographic printing plate. The concentration of the photosensitive composition during application is 1 to 5.
A range of 0% by weight is desirable. The coating solvent used is methyl cellosolve, ethyl cellosolve, 1
-methoxy-2-propatol, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, methyl lactate, ethyl lactate, ethylene dichloride, cyclohexanone, Dioxane, tetrahydrofuran, etc. can be mentioned. A mixed solvent of these or a mixed solvent obtained by adding a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or the polymer compound to these solvents or mixed solvents is also suitable. When a photosensitive liquid dissolved in these solvents is applied to a support and dried, it is desirable to dry at 50°C to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature. Examples of the support to which the photosensitive composition of the present invention is applied include paper,
Various materials such as plastics and metals can be used, but when used in photosensitive planographic printing plates, hydrophilic aluminum plates are particularly preferred. The surface of the aluminum plate can be prepared using mechanical methods such as wire brush graining, brush graining in which the surface is roughened with a nylon brush while pouring slurry of abrasive particles, ball graining, or HF, AlCl2. , chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining performed by combining these roughening methods. The aluminum surface is etched with acid or alkali, and then anodized in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid of these using a DC or AC power supply to form a strong coating on the aluminum surface. Those provided with a passive film are preferred. Although such a passive film itself makes the aluminum surface hydrophilic, if necessary, U.S. Patent No. 2,714
,066 and U.S. Pat. No. 3,181,461 (sodium silicate,
potassium silicate), potassium fluorozirconate treatment as described in U.S. Pat. No. 2,946.638, phosphomolybdate treatment as described in U.S. Pat. No. 3,201,247, UK Patent No. 1.108,
Alkyl titanate treatment as described in German Patent No. 559, polyacrylic acid treatment as described in German Patent No. LO 91,433, German Patent No. 1.134.093 and British Patent No. 1,230. Polyvinylphosphonic acid treatment described in , No. 447, Japanese Patent Publication No. 44-64
Phosphonic acid treatment described in No. 09, phytic acid treatment described in U.S. Patent No. 3,307,951, JP-A-58-16893 and JP-A-58-1
Composite treatment consisting of a hydrophilic organic polymer compound and a divalent metal described in each publication of No. 8291, JP-A-59-1
Particularly preferred are those which have been subjected to a hydrophilic treatment by undercoating with a water-soluble polymer having a sulfonic acid group as described in Japanese Patent No. 01651. Other hydrophilic treatment methods include silicate electrodeposition as described in US Pat. No. 3,658,662. Moreover, it is also preferable to perform a sealing treatment after graining and anodizing. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like. The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like, followed by development with an aqueous alkaline developer, provides a negative relief image on the original. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes,
Examples include ultraviolet laser beams. The developer used in the development of the photosensitive printing plate according to the present invention may be any known developer, but the following are preferred. That is, the developer for developing the photosensitive printing plate according to the present invention contains at least an alkaline agent and water as essential components. The alkaline agents contained as essential components in the developer include sodium silicate, potassium silicate, potassium hydroxide,
Inorganic alkaline agents such as sodium hydroxide, lithium hydroxide, sodium or ammonium salts of secondary or tertiary phosphoric acid, sodium metasilicate, sodium carbonate, ammonia, mono-, di-, or trimethylamine, mono-, di- or triethylamine, mono- or Diisopropylamine, n-butylamine, mono, di or triethanolamine, mono,
di- or triisopropanolamine, ethyleneimine,
Examples include organic amine compounds such as ethylenediimine. The content of these alkaline agents in the developer is 0.05
-10% by weight, preferably 0.5-5% by weight. If it is less than 0.05% by weight, development will be poor, and if it exceeds 10% by weight, it will have an adverse effect on the printing performance of the lithographic printing plate. The developer for developing the photosensitive printing plate according to the present invention may contain a specific organic solvent, if necessary. Particularly when the photosensitive layer contains a diazo resin having no carboxyl group, it is necessary to contain such an organic solvent in the developer. Such an organic solvent can dissolve or swell the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer when contained in the developer, and is resistant to water at room temperature (20°C). An organic solvent with a solubility of 10% by weight or less. Any organic solvent may be used as long as it has such characteristics, and examples include, but are not limited to, the following. For example, carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone;
Ketones such as methyl isobutyl ketone and cyclohexanone; Alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, and methyl amyl alcohol; xylene Alkyl-substituted aromatic hydrocarbons such as; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is generally 0 to 20% by weight, particularly 2 to 20% by weight.
More preferable results are obtained when the amount is 10% by weight. Further, the developer for developing the photosensitive printing plate according to the present invention may contain a water-soluble sulfite salt, if necessary. Such water-soluble sulfites are preferably alkali or alkaline earth metal sulfites, such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is 0 to 4%, preferably 0.1 to 1%.
Weight%. Further, instead of the water-soluble sulfite, a hydroxy aromatic compound such as an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or methylresorcinol may be contained. Of course, these compounds and water-soluble sulfites can also be used together. Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water. As such a solubilizer, in order to achieve the desired effects of the present invention, it is preferable to use alcohols and ketones that are more water soluble and have lower molecular weight than the organic solvent used. Furthermore, anionic activators, amphoteric activators, etc. can also be used. Examples of such alcohols and ketones include methanol, ethanol, propatool, butanol,
Acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-
It is preferable to use methoxy-4-methylbutanol, N-methylpyrrolidone, and the like. In addition, examples of the activator include sodium isopropylnaphthalene sulfonate,
Preferred are sodium n-butylnaphthalenesulfonate, sodium N-methyl-N-pentadecylaminoacetate, sodium lauryl sulfate, and the like. The amount of solubilizers such as alcohols and ketones used is generally preferably about 30% by weight or less based on the entire developer. <Effects of the Invention> The photosensitive composition of the present invention has excellent solubility in organic coating solvents when coated on a support, and after coating, drying, and image exposure, it can be brought into contact with the above-mentioned developer, or If rubbed, the photosensitive composition in the non-exposed areas of the photosensitive composition layer will be completely removed after 10 to 60 seconds at room temperature to 40''C without adversely affecting the exposed areas of the photosensitive composition layer. In this case, the developing ability is high, and the development performance over time (storage stability) and printing durability are also good. [Examples] The present invention will be explained in more detail below using synthesis examples and examples. , the content of the present invention is not limited thereby. Kinboku ■ Tsu 1 4-diazodiphenylamine hydrogen sulfate 29.3 g
(0,100 mo+) was dissolved in 70 mB of 85% phosphorus M. Add to this glyoxylic acid monohydrate (97%) 4.7
4 g (0,0500 mol) was added and stirred for 20 hours at 40"C. Next, 1.58 g (0,05%) of paraformaldehyde (95%) was added to the reaction mixture.
00 mol) was added thereto, and the mixture was further stirred at 40°C for 20 hours. After that, the reaction solution was diluted with 80% isopropyl alcohol.
0- with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain a dihydrogen phosphate of a condensate of 4-diazodiphenylamine and glyoxylic acid/formaldehyde. The above condensate was dissolved in 400 mN of water, and 41.8 g (0,120
A 600-mol solution of water was added with stirring. The produced yellow precipitate was collected by filtration and dried to obtain 44 g of n-dodecylbenzenesulfonic acid salt of a condensate of 4-diazodiphenylamine and glyoxylic acid/formaldehyde (diazo resin (a) of the present invention). The carboxylic acid value of the obtained diazo resin was 0.98 meq
/g. Further, after coupling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 1,950. 32.3 g (0,100 mol) of 4'-methoxy-4-diazodiphenylamine hydrogen sulfate was dissolved in 85% phosphoric acid 70-. This is added to glyoxylic acid monohydrate (
97%) 6.64 g (0,0700 mol) was added and stirred at 40°C for 20 hours. Next, 3.96 g of acetaldehyde (0,0900
mol) was added thereto, and the mixture was further stirred at 40°C for 20 hours. After that, the reaction solution was mixed with 80% inbucopyl alcohol.
0- with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain a dihydrogen phosphate of a condensate of 4-methoxy-4-diazodiphenylamine and glyoxylic acid/acetaldehyde. 4. The above condensate. 39.6 g (0,120 mol) of sodium 2-methoxy-4-hydroxy-5-hendiylsulfonate were dissolved in 60 ml of water.
○ - The solution was added with stirring. The produced yellow precipitate was collected by filtration and dried to obtain 2-methoxy-, a condensate of 4-diazodiphenylamine and glyoxylic acid/acetaldehyde.
39 g of 4-hydroxy-5-benzoylbenzenesulfonate was obtained (diazo resin (b) of the present invention). The carboxylic acid value of the obtained diazo resin was 1.10 meq
/g. Furthermore, after cambling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 1,730. 29.3g of 4-diazodiphenylamine hydrogen sulfate (
0,100 mol) was dissolved in 70 ml of 96% sulfuric acid. To this was added 16.5 g of terephthalaldehydic acid (0,11
0 mol) was added thereto and stirred at 5° for 3 hours. Thereafter, the reaction solution was poured into 800 g of isopropyl alcohol with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain a hydrogen sulfate salt of an acid condensate of 4-diazodiphenylamine and terephthalaldehyde. The above condensate was suspended in a mixture of 200 ynl of water and 500 ml of MEK, and to this was added 41.8 g (0,120 mol) of sodium n-dodecylbenzenesulfonate and 6 ml of water.
00 ml solution was added with stirring. (After continued stirring, it separated into two layers when left to stand still. This upper layer was poured into water 21 with stirring, and the yellow precipitate formed was collected by filtration.
By drying, 46 g of n-F decylhenzenesulfonate of a condensate of 4-diazodiphenylamine and terephthalaldehyde acid was obtained (diazo resin (C) of the present invention).
). The carboxylic acid value of the obtained diazo resin was 0.89 meq
/g. Further, after coupling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 1,450. 32.3 g (0,100 mo+) of 4-diazo-3-methoxydiphenylamine hydrogen sulfate was dissolved in 96% sulfuric acid 1
Dissolved at 00mE. This is combined with rose formaldehyde (9
5%) 3.1.6 g (0,100 mol) was added and stirred at 5°C for 2 hours. Next, 7.50 g of terephthalaldehydic acid (0,0500
mol) was added thereto, and the mixture was further stirred at 5°C for 2 hours. After that, the reaction solution was mixed with isopropyl alcohol 80++
+F while stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain a hydrogen sulfate salt of a condensate of 4-diazo-3-methoxydiphenylamine and formaldehyde/terephthalaldehydic acid. The above condensate was dissolved in 400 rnl of water, and 22.1 g (0.120 m
A 600 ml solution of ol) in water was added with stirring. The produced yellow precipitate was collected by filtration and dried to give 28 g of hexafluorophosphate of a condensate of 4-diazo-3methoxydiphenylamine and formaldehyde/terephthalaldehyde acid.
was obtained (diazo resin (d) of the present invention). The carboxylic acid value of the obtained diazo resin was 0.54 meq
/g. Further, after coupling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 2,300. Hill bottom ■1 37.4 g (0,100 m
ol,) was dissolved in 70 liters of 96% sulfuric acid. This includes glutaraldehyde acid (4-formylbutanoic acid)
Add 4.64 g (0,0400 mol),
The mixture was stirred at ℃ for 2 hours. Next, 1.90 g (0,0600 g) of rose formaldehyde (95%) was added to the reaction mixture.
mol) was added thereto, and the mixture was further stirred at 5°C for 2 hours. After that, the reaction solution was poured into ice water 1°5β with stirring,
Furthermore, 260 g of a 50% zinc chloride aqueous solution was added to precipitate a yellow precipitate. This yellow precipitate was filtered and 4'-methyl-
A zinc chloride double salt of a condensate of 2,5-dimethoxy-4-diazodiphenyl sulfide and glutaraldehyde acid/formaldehyde was obtained. The above condensate was dissolved in 800 g of water, and 22.1 g (0,120 mol) of potassium hexafluorophosphate was added thereto.
600mj of water! Solution i was added with stirring. The produced yellow precipitate was collected by filtration and dried to obtain 50 g of hexafluorophosphate of a condensate of 4'-methyl-2.5-dimethoxy-4-diazodiphenyl sulfide and glutaraldehyde acid/formaldehyde. Diazo resin of the invention (e
)). The carboxylic acid value of the obtained diazo resin was 0.77 meq
/g. In addition, the obtained diazo resin was
After coupling with phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 2,130. (Synthesis of sulfonamide group-containing polymer compound 1) In a 1μ Mitsuro flask equipped with a stirrer, a cooling tube, and a dropping funnel.
-Aminobenzenesulfonamide 170.2 g (I
, 0 mol) and 7001 nl of tetrahydrofuran were added thereto, and the mixture was stirred under an ice-water tower. 52.3 g (0.5 mol) of methacrylic acid chloride was added dropwise to this mixture using a dropping funnel over about 1 hour. After the dropwise addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and further stirred for 1 hour while heating to 60° C. using an oil bath. After the reaction is complete,
This reaction mixture was poured into water 31 with stirring, and PR was carried out for 30 minutes.
After stirring and filtering, a white solid of N-Cp-aminosulfonylphenyl) methacrylamide was obtained. This white solid was purified by recrystallization from a mixed solvent of ethanol and acetone (yield: 39.3 g).
. Next, 4.57 g (0,0192 mol) of N-(p-aminosulfonylphenyl) methacrylamide and 2.55 g (0,0480 mol) of acrylonitrile.
, methacrylic fa1.66 g (0,0192 mo
l) Ethyl acrylate 1 1.3 6 g
(0,1136 mol), 0.41 g of α,α′ azobisisobutyronitrile and 25 g of N,N dimethylformamide were placed in a 1001 tube equipped with a stirrer and a cooling tube.
The mixture was placed in a Mitsuro flask (No. 111) and stirred for 5 hours while warming to 64°C. This reaction mixture was poured into water 21 with stirring,
After stirring for 30 minutes, 16 g of polymer compound 1 was obtained by filtering and drying. The weight average molecular weight (polystyrene standard) of this polymer compound 1 was measured by GPC and found to be 35,000. Bean charcoal twisting (synthesis of sulfonamide group-containing polymer compound 2) N-(
p-Aminosulfonylphenyl) methacrylamide 4.
57 g (0,0192 mo+), 2-hydroxyethyl methacrylate 6.25 g (0,0480 mo+)
l), methacrylic acid 1.66 g (0,0192 mo
l), ethyl acrylate 1 ], 36 g (0
. Stir for hours. This reaction mixture was poured into water 2i with stirring, stirred for 30 minutes, filtered, and dried to obtain 20 g of polymer compound 2. When the weight average molecular weight (polystyrene standard) of this polymer compound 2 was measured by GPC, it was found to be 44,
It was 000. i Base construction (synthesis of sulfonamide group-containing polyurethane resin (a)) 40 g (0,298 mol) of 2,2-bis(hydroxymethyl)propionic acid was placed in a 500 ml three-way flask equipped with a stirrer, cooling tube, and dropping funnel. ) and 100 mZ of acetic anhydride were added, and the mixture was stirred in an ice-water bath. Pyridine 100- was added dropwise to this mixture using a dropping funnel over a period of about 30 minutes. After the addition was completed, the ice water bath was removed, and the mixture was stirred for 2 hours while being heated to 60° C. in an oil bath. After the reaction was completed, hydrochloric acid was added to make the mixture acidic, and the mixture was extracted with RI00 form using a separating funnel. After washing the chloroform layer with water, it was dehydrated with anhydrous sodium sulfate. By distilling off the solvent from this chloroform solution under reduced pressure, 57 g of a white solid of 2,2-bis(acetoxymethyl)propionic acid was obtained. Next, 30 g (0,137 mol) of 2,2-bis(acetoxymethyl)propionic acid and 20 ml of thionyl chloride were added to a 300-ml tube equipped with a stirrer, a cooling tube, and a dropping funnel.
- The mixture was placed in a Mitsuro flask and stirred for 2 hours while heating to 80°C. After the reaction was completed, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and then an ice water bath was placed to sufficiently cool the reaction product. This reaction product contains 46.6 g (0,274 mol) of p-aminobenzenesulfonamide and 150 ml of tetrahydrofuran! The mixture was added dropwise over about 1 hour using a dropping funnel. After the addition was completed, the mixture was stirred in an oil bath for 2 hours while being heated to 60°C. After the reaction, the reaction mixture was poured into water 21 with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of p-(I,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide. Obtained. This white solid is purified by recrystallization from ethanol, yielding 2
6g). Next, 22 g of pm (I,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide
(0.06 mol) and 4.8 g of sodium hydroxide
(0.12 mol) and 50 ml of ethanol 50-1 water were placed in a 300 ml Mitsuro flask equipped with a stirrer and a cooling tube, and heated under reflux for 2 hours. This reaction mixture was mixed with 11 parts of water.
After stirring for 30 minutes, the mixture was filtered to obtain a white solid of p-(I,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide. This white solid was purified by recrystallization from ethanol (yield: 11 g). Next, 3.44 g of p-(I,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide
(0,012 mol) and 1.07 g (0,008 mo!) of 2,2-dihydroxymethylpropionic acid.
>,4.4'-diphenylmethane diisocyanate5.
26 g (0,021 mol) and 1.8 g of N,N-dimethylacetamide were placed in a 100-liter tube equipped with a stirrer and a cooling tube.
-Pour into a Mitsuro flask and heat to 100°C while
Stir for hours. The reaction mixture was cooled and methanol 5
After stirring for a while, the mixture was poured into 500 g of water with stirring and stirred for 30 minutes. The precipitate was filtered and dried to obtain 9 g of white solid. When the weight average molecular weight (polystyrene standard) of this polyurethane resin was measured by GPC, it was found to be 64,000.
Met. (Polyurethane resin (a)). Plan I (sulfonamide group-containing polyurethane resin (bl~fe)
) Synthesis) A diisocyanate compound and a diol compound as shown in Table 1 below are reacted to produce the corresponding polyurethane resin fbl~
synthesized tel. In addition, the molecular weights are all weight average molecular weights (polystyrene standard) of 25,000 to 70,00.
It was 0. Xiaxi Charcoal Master (Synthesis of sulfonamide group-containing polyurethane resin ()) Into a 1z three-way flask equipped with a stirrer, cooling tube, and dropping funnel, 98.5 g of 0-aminobenzyl alcohol (
0.8 mol) and acetone 500- were added, and NaC (
! - Stirred in an ice water bath. A solution of 27.5 g (0.1 mo+) of m-henzenedisulfonyl chloride dissolved in 200 - of acetone was added dropwise into the flask using a dropping funnel over about 1 hour. After the dropwise addition was completed, the NaCl water bath was removed and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, most of the acetone was distilled off under reduced pressure, and the mixture was poured into water 11 with stirring.
The mixture was further acidified with hydrochloric acid. The precipitate was collected by filtration and dissolved in an aqueous sodium hydroxide solution. After filtering off insoluble materials, the filtrate was placed in a separating funnel and washed twice with ethyl acetate. The aqueous layer was made acidic by adding hydrochloric acid, and the precipitate was collected by filtration. By thoroughly washing with water and drying, a solid of NN'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide was obtained (yield: 30.6 g). Next, 6.28 g of N,N'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide (
0,014 mol), 2,2-dihydroxymethylpropionic acid 0.80 g (0,OO6'mol), 44
'-Diphenylmethane diisocyanate 5.26 g
(0,021 mol) and 18 g of N,N-dimethylacetamide were added, and the mixture was stirred for 3 hours while heating to 100°C. After the reaction was completed, 10 g of methanol was added and stirred for a while, and the mixture was poured into 500 ml of water with stirring, and the mixture was stirred for 30 minutes.
Stir for a minute. By filtering and drying the precipitate, 12
g of a white solid was obtained. When the weight average molecular weight (polystyrene standard) of this polymer compound was measured by GPC, it was 55.000 (polyurethane resin ()). (i
(Synthesis of l) The following diisocyanate compounds and diol compounds as shown in Table 1 are reacted to produce the corresponding polyurethane resin (g) ~
(I1 was synthesized.The molecular weights are all weight average molecular weights (polystyrene standard) of 32.000 to 88.00.
It was 0. Actual drawing and 0.241 thick aluminum plate with nylon braso 4
After the surface was grained using an aqueous suspension of 0.00 mS bumistone, it was thoroughly washed with water. 10% of this
After etching by immersion in an aqueous sodium hydroxide solution at 70°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, the electrochemical surface roughening method described in JP-A-53-67507 was carried out. VA=12.7V, Vc=9. Using an IV (D sine wave alternating waveform current), electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution with an anode special electricity amount of 160 corons/dm2. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and heated to 55°C. After desmutting for 2 minutes in a 7% aqueous sulfuric acid solution, anodization treatment was performed so that the coating amount of aluminum oxide was 2.0 g/tri.Then, the material was desmutted in a 3% aqueous solution of sodium silicate at 70°C for 1 minute. 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 2.0g/m. Table 2 also shows the diaso resins used in the following photosensitive solutions. (Photosensitive liquid) Resin (Table 2) 0.5
g Comparative Example 2 Hexafluorophosphate of condensate of 4-diazo-3-methoxydiphenylamine and formaldehyde L Malic acid □ Ll-Methoxy-2-propatol methyl ethyl ketone 0.05 g 0g 0g [Evaluation of printing stains] This Each of the photosensitive lithographic printing plates thus obtained was image-exposed for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■, and after being immersed in the following developer for 1 minute at room temperature, the surface was cleaned with absorbent cotton. The unexposed areas were removed by light rubbing to obtain lithographic printing plates (I) to (■) with bright blue images. (Developer) Sodium sulfite 5g Each printing plate was printed on high-quality paper with commercially available ink using a Heidelberg KOR printing machine. When the printing stains of the lithographic printing plates N) to (■) were examined, it was found that: Table 2 As shown in Table 2, the lithographic printing plates (I) to (V) using the photosensitive composition of the present invention were prepared in Comparative Example 1.2 ( VI)
, Compared to (■), there was no printing stain during printing, and the print was very sharp. ! Hemostasis I A photosensitive lithographic printing plate (
(2) to (XIII) were obtained, exposed and developed in the same manner as in Example 1, and further printed to examine printing stains on the lithographic printing plates. The results are shown in Table 3. Evaluation A: Not at all C: Slightly high B: Not at all D = High No. 3 Topsoil Image exposure for 1 minute from a distance of 1 m using the PS light made on the photographic film side, and 1 min at room temperature using the developer shown below. After being immersed for a minute, the surface was lightly rubbed with absorbent cotton to remove the unexposed areas, yielding lithographic printing plates (XIV) to (XX) with bright blue images. (Developer) Evaluation A: Not at all C: Slightly high B: Rarely D = High As can be seen from Table 3, lithographic printing plates using the photosensitive composition of the present invention (■) ~ (XI) was very superior to the comparative examples (Xn) and (XI[I), with no printing stains during printing. Example 1: Rich in lithographic printing plate
In the same manner as above, each printing plate was used to print on high-quality paper using a commercially available ink using a Heidelherk KOR type printing machine. When the printing stains of the lithographic printing plates (X IV) to (XX) were examined, the results were as shown in Table 4. The lithographic printing plate (X
. The results are shown in Table 5. Evaluation in Table 5 A: Not at all C: Slightly high B: Rarely D: High As can be seen from Table 4, lithographic printing plates (XrV) using the photosensitive composition of the present invention - ( X■) is the comparative example (XIX
) and (XX), there was no printing stain during printing, which was very good. Evaluation A: Not at all C: Slightly high B: Very little D: High As can be seen from Table 5, lithographic printing plates (XXI) to (XXIV) using the photosensitive composition of the present invention ) is the comparative example (
Compared to (XXV) and (XXV), the printing stain was much more smudged during printing. Indeed, Zettai 5 A photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that the following photosensitive liquid was used. (Photosensitive liquid) Diazo resin (Table 6) 0.5
g copolymer of 2-hydroxyethyl methacrylate/acrylonitrile/ethel methacrylate/methacrylic acid = 35/25/3515 in molar ratio 5.0 g malic acid 0.05 gll-
Methoxy-2-propertool 50g Methyl ethyl ketone 50g [Evaluation of sensitivity and printing stains] The photosensitive lithographic printing plate thus obtained was tested with a negative translucent original and a stencil wedge (optical density increased in steps of 0 and 150). The film was placed in close contact with the film, and an image was taken at a distance of 1 m for 1 minute using a PS light manufactured by Fuji Photo Film@, and the number of solid steps was measured using the following developer for 30 seconds at room temperature. (Developer) 1 Sodium sulfite 5g Benzyl alcohol 30g Sodium carbonate
5g isopropylnaphthalene sulfonic acid, sodium 12g”*
l 000 g On the other hand, each photosensitive lithographic printing plate was coated with PS manufactured by Fuji Photo Film ■.
The image was exposed for 1 minute from a distance of 1 m using a light, and after being immersed in the developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed areas to obtain a lithographic printing plate with a bright blue image. Furthermore, using each printing plate, KO manufactured by Heidelberg
Printing was performed on high-quality paper using commercially available ink using R printing machine, and the printing stains were examined. Table 6 shows the results of the hexafluorophosphate sensitivity of the proboscis and the printing stains. Table 6 Diazo resin 1: Diazo resin without carboxyl group, condensation of 4-cyanodiphenylamine and formaldehyde/carboxylic acid (direct weight average molecular weight 1900) Diazo resin 2. Diazo resin without carboxyl group , Condensate of 4-diasodiphenylamine and formaldehyde (7) Totenlebenzenesulfonic acid salt Mecarboxylic acid value O 1'ゝ゛Weight average molecular weight 1900', H: Not at all C: Slightly high B: Not at all D :As can be seen from Table 6, lithographic printing plates (X■) to (XX) in which a diazo resin having a carboxyl group and a diazo resin not containing a carboxyl group were used in combination were those in which either one was used alone ( It can be seen that compared to XXI) to (XXIV), the sensitivity is higher and the printing results are excellent without staining during printing.

Claims (1)

[Scope of Claims] In the photosensitive composition containing a diazo resin and an organic solvent-soluble polymer compound, the diazo resin has at least one repeating unit represented by the following general formula (I). A photosensitive composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R^1 is a hydrogen atom, an alkyl group, an alkoxy group,
It represents a hydroxy group, a carboxy ester group, or a carboxyl group, R^2 represents a carboxyl group or a group having at least one carboxyl group, R^3 represents a hydrogen atom, an alkyl group, or an alkoxy group, and R^4 represents a , represents a hydrogen atom, an alkyl group or an alkoxy group, X^- represents an anion, and Y represents -NH-, -O- or -S-
shows.