JP2687018B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition, and more particularly to a photosensitive composition useful for producing a photosensitive lithographic printing plate.

[Conventional technology]

A photosensitive printing plate is generally prepared by coating a photosensitive composition on a support such as an aluminum plate and irradiating it with an actinic ray such as an ultraviolet ray through a negative image or the like to polymerize or crosslink the portion irradiated with light to form a developer. Insolubilize and elute the non-irradiated areas in the developer, and make each area an image area that repels water and receives oil-based ink, and a non-image area that receives water and repels oil-based ink. Is obtained by

As the photosensitive composition in this case, a diazo resin such as a condensate of p-diazodiphenylamine and formaldehyde has been widely used.

However, since conventionally known diazo resins generally do not have alkali solubility, for a photosensitive composition containing the same, after exposure, when developing with an alkali developer,
Developability, especially under under conditions is not good,
Further, there is a problem that a so-called diazo residue remains in the form of a film on the surface of the support after development, so-called diazo residue, which causes deterioration of printability.

Therefore, a method of incorporating an alkali-soluble group into the diazo resin to solubilize the diazo resin with an alkali is disclosed in Japanese Patent Laid-Open No.
No. 102456 and Japanese Patent Application Laid-Open No. 1-102457.

However, even when these alkali-soluble diazo resins are used, the developability with respect to a fatigue developing solution or a developing solution containing a small amount of an organic solvent is not good, and diazo residues are generated.

[Problems to be solved by the invention]

Therefore, the main object of the present invention is to have alkali-solubility, therefore excellent in developability, and free from diazo residue,
It is intended to provide a novel photosensitive composition having excellent compatibility with a binder.

Another object of the present invention is to provide a novel photosensitive composition capable of expanding the selection range of lipophilic polymer compounds (binder resins) that can be used in combination.

Yet another object of the present invention is to provide a photosensitive composition containing a diazo resin having improved solubility in an organic solvent and improved storage stability.

[Means for solving the problem]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that the use of a novel diazo resin achieves the above object, thereby achieving the present invention.

That is, the present invention is a co-condensed diazo resin containing an aromatic compound having at least one of a carboxyl group and a hydroxyl group and an aromatic diazo compound as a constituent unit, and having a long-chain alkyl group as a counter anion. A photosensitive composition comprising a co-condensed diazo resin containing an anion of an aromatic sulfonic acid.

The aromatic compound having at least one of the carboxyl group and the hydroxyl group according to the present invention is an aromatic ring substituted with at least one carboxyl group and / or an aromatic ring substituted with at least one hydroxyl group. A ring is included in the molecule, and in this case, the carboxyl group and the hydroxyl group may be substituted with an aromatic ring.

And as said aromatic ring, an aryl group, for example, a phenyl group and a naphthyl group, can be mentioned preferably.

The above-mentioned carboxyl group or hydroxyl group may be directly bonded to the aromatic ring, or may be bonded via a linking group.

In the present invention, the number of carboxyl groups bonded to one aromatic ring is preferably 1 or 2, and the number of hydroxyl groups bonded to one aromatic ring is 1 to 3
Is preferred. Further, examples of the linking group include an alkylene group having 1 to 4 carbon atoms.

In order to condense the above-mentioned aromatic compounds with aldehydes or ketones, it is necessary that they have at least two unsubstituted sites on the aromatic ring of one or more aryl groups substituted with at least one hydroxyl group. Is.

Specific examples of the aromatic compound having a carboxyl group and a hydroxyl group in the molecule used in the present invention include salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic 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-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 2,6-dihydroxybenzoic acid, 2,6-dihydroxy -4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucin carboxylic acid, 2,4,5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-
(P-Toluyl) gallic acid, protocatechuoyl-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl) acetic acid, (2,6-dihydroxyphenyl) acetic acid, (3,4,5- Trihydroxyphenyl) acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4- (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-hydroxy) Examples thereof include phenylsulfonyl) benzoic acid and 4- (p-hydroxyphenylthio) benzoic acid. Of these, salicylic acid, p-hydroxybenzoic acid and 2,4-
Dihydroxybenzoic acid, gallic acid, phloroglucin carboxylic acid, and 4- (p-hydroxyanilino) benzoic acid.

Examples of aromatic compounds having a carboxyl group in the molecule include p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid and p-methoxyphenylacetic acid. , 4-anilinobenzoic acid, 4- (m-methoxyanilinobenzoic acid, 4-
(P-Methoxybenzoyl) benzoic acid, 4- (p-methylanilino) benzoic acid, 4-phenylsulfonylbenzoic acid and the like can be mentioned. Of these, 2,4-dimethoxybenzoic acid and p- are particularly preferred. Phenoxybenzoic acid, 4-anilinobenzoic acid, 4- (m-methoxyanilino) benzoic acid, and 4- (p-methylanilino) benzoic acid.

As the aromatic compound having a hydroxyl group in the molecule, an aromatic compound having a phenolic hydroxyl group is particularly preferable, and examples thereof include phenol, (o, m, p) cresol, xylenol, resorcin, 2-methylresorcin, (O, p, m) methoxyphenol, m-ethoxyphenol, catechol, phloroglucin, 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'-dihydroxysulfone , 4,4 ′
-Dihydroxydiphenyl sulfide, cumylphenol and the like, and among these, particularly preferred are p-cresol, resorcin, 2-methylresorcin, pyrogallol, p-methoxyphenol, 4,4'-dihydroxydiphenyl ether, 4,4 '. -Dihydroxydiphenylamine, 2,3,4-trihydroxybenzophenone.

On the other hand, the aromatic diazo compound according to the present invention is a compound having an aromatic ring substituted with at least one diazonium group, and preferably the aromatic diazo compound represented by the following general formula (I) can be mentioned.

In the formula, R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a hydroxyl group, a carboxyester group or a carboxyl group, preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms. , An alkoxy group having 1 to 3 carbon atoms or a hydroxyl group.

R ² 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.

R ³ 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, hydrohalic acid, for example, hydrofluoric acid,
Hydrochloric acid, hydrochloric acid-zinc chloride complex, 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 acid or its half ester, fluorocarboxylic acid such as arsonic acid, phosphinic acid, trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoric acid, hexafluorophosphoric acid, perchloric acid Further examples include anions such as aliphatic and aromatic sulfonic acids.

Y represents -NH-, -O-, or -S-, and preferably represents -NH-.

Specific examples of the aromatic diazo compound represented by the general formula (I) include, for example, 4-diazodiphenylamine,
4'-hydroxy-4-diazodiphenylamine, 4 '
-Methoxy-4-diazophenylamine, 4'-ethoxy-4-diazodiphenylamine, 4'-n-propoxy-4-diazodiphenylamine, 4'-i-propoxy-4-diazodiphenylamine, 4'-methyl-4-
Diazodiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-propyl-4-diazodiphenylamine, 4'-i-propyl-4-diazodiphenylamine, 4'-n-butyl-4-diazodiphenylamine, 4 ′ -Hydroxymethyl-4-diazodiphenylamine, 4′-β-dihydroxyethyl-4-diazodiphenylamine, 4′-γ-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'-carbethoxy-4-diazo Diphenylamine, 4'-carboxy-4-diazodiphenylamine, 4-diazo-3-methoxy-diphenylamine, 4-diazo-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'-n-butoxy- 4-diazodiphenylamine, 3,4'-dimethoxy-
4-diazodiphenylamine, 2'-carboxy-4-
Diazodiphenylamine, 4-diazodiphenylether, 4'-methoxy-4-diazodiphenylether,
4'-methyl-4-diazodiphenyl ether, 3,4 '
-Dimethoxy-4-diazodiphenyl ether, 4'-
Carboxy-4-diazodiphenyl ether, 3,3'-
Dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4'-methyl-4-diazodiphenyl sulfide, 4'-methyl-2,5-dimethoxy-
4-diazodiphenyl sulfide and the like.

Among them, particularly preferred aromatic diazo compounds include 4-diazodiphenylamine and 4-diazo-4'-.
Examples include methoxydiphenylamine, 4-diazo-4'-ethoxydiphenylamine, and 4-diazo-3-methoxydiphenylamine.

Condensation-type resins with aldehydes (hereinafter referred to as diazo co-condensation resins) containing an aromatic compound having at least one of a carboxyl group and a hydroxyl group and an aromatic diazo compound as constituent units in the present invention are known methods. , For example, Photographic Science and Engineering (Photo, Sci., Eng.) Volume 17, 33
Page (1973), U.S. Pat. Nos. 2,063,631 and 2,679,498, and aromatic compounds and aldehydes having a diazonium salt, a carboxyl group and / or a hydroxyl group in sulfuric acid, phosphoric acid or hydrochloric acid, according to the methods described in the respective specifications. , For example paraformaldehyde, acetaldehyde,
Benzaldehyde or ketones such as acetone,
It is obtained by polycondensation with acetophenone.

In addition, aromatic compounds having a carboxyl group and / or a hydroxyl group in these molecules, aromatic diazo compounds and aldehydes or ketones can be freely combined with each other, and two or more kinds of them can be mixed and co-condensed. It is possible. Further, cocondensable phenols having no carboxyl group can be added for cocondensation.

At that time, the charged molar ratio of the aromatic compound and the aromatic diazo compound having at least one of a carboxyl group and a hydroxyl group is 1: 0.1 to 0.1: 1; preferably 1: 0.2 to
0.2: 1, more preferably 1: 0.5 to 0.2: 1. In this case, the total amount of the aromatic compound and the aromatic diazo compound having at least one of a carboxyl group and a hydroxyl group and the aldehydes or ketones is usually 1: 0.6 to 1.2, preferably 1: 0.7 to 1.5. The diazo co-condensation resin is obtained by charging and reacting at a low temperature for a short time, for example, for about 3 hours.

The co-condensed diazo resin used in the present invention contains an anion of an aromatic sulfonic acid having a long chain alkyl group as a counter anion. Although it may contain an anion other than the aromatic sulfonic acid having a long-chain alkyl group,
It is desirable that 50 mol% or more, preferably 80 mol% or more, of the counter anions contained in the co-condensed diazo resin of the present invention is an anion of an aromatic sulfonic acid having a long-chain alkyl group.

The aromatic sulfonic acid having a long-chain alkyl group is preferably benzenesulfonic acid or naphthalenesulfonic acid having a linear or branched alkyl group having 4 or more carbon atoms.

More preferably, it is benzenesulfonic acid or naphthalenesulfonic acid having a linear or branched alkyl group having 8 or more carbon atoms.

Furthermore, benzene sulfonic acid or naphthalene sulfonic acid having a linear or branched alkyl group having 8 or more and 20 or less carbon atoms is more preferable. The long-chain alkyl group is more preferably a straight-chain alkyl group than a branched alkyl group. These long-chain alkyl groups may be directly substituted on the aromatic ring, or may be bonded via another linking group.

Specific examples include octylbenzene sulfonic acid,
Dioctylbenzenesulfonic acid, nonylbenzenesulfonic acid, dinonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, bis-dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, undecyloxybenzenesulfonic acid , Bis-undecyloxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, bis-dodecyloxybenzenesulfonic acid, dodecyltoluenesulfonic acid, tetradecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, heptadecyl Benzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid, eicosadecylbenzenesulfonic acid, octylnaphthalenesulfonic acid, diocty Naphthalenesulfonic acid, nonyl naphthalene sulfonic acid, Gini nor naphthalenesulfonic acid, decyl naphthalenesulfonic acid, bis - decyl naphthalenesulfonic acid, undecyl naphthalenesulfonic acid, dodecyl naphthalene sulfonic acid, tridecyl naphthalenesulfonic acid.

Particularly preferred among these are dodecylbenzene sulfonic acid or dioctylnaphthalene sulfonic acid.

Specific examples of the diazo co-condensation resin in the present invention,
p-cresol-4-diazodiphenylamine dodecylbenzene sulfonate-formaldehyde resin, resorcin-4-diazodiphenylamine dodecylbenzene sulfonate-formaldehyde resin, 2-methylresorcin-4-diazophenylamine dioctylnaphthalene sulfonate -Formaldehyde resin, p-methoxyphenol-4-diazodiphenylamine dioctylnaphthalene sulfonate-acetaldehyde resin,
Pyrogallol-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, phloroglucin-4-diazodiphenylamine dodecylbenzenesulfonate-acetone resin, 4,4'-dihydroxydiphenylether-4-diazodiphenylamine
Dioctylnaphthalenesulfonate-acetaldehyde resin, p-hydroxyethylphenol-4-diazodiphenylamine dodecylbenzenesulfonate-benzaldehyde resin, 2,4-dihydroxybenzophenone-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4,4′-Dihydroxydiphenylamine-4-diazodiphenylamine / dioctylnaphthalenesulfonate / formaldehyde resin, salicylic acid-4-diazo-4′-methoxydiphenylamine / dodecylbenzenesulfonate / formaldehyde resin, 4-methylsalicylic acid-4- Diazo-4 '
-Methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-hydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, p-hydroxybenzoic acid-4-diazo-3-methoxy Diphenylamine / dioctylnaphthalene sulfonate-formaldehyde resin, gallic acid-4-diazo-
4'-ethoxydiphenylamine dodecylbenzene sulfonate, formaldehyde resin, 2,4-dihydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzene sulfonate-formaldehyde resin, 4- (p-hydroxyanilino) Benzoic acid-4-
Diazo-4'-methoxydiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin, p-
Cresol-4-diazo-3-methoxydiphenylamine / hexafluorophosphate / dodecylbenzenesulfonate (20/80 molar ratio) mixed salt-benzaldehyde resin, resorcin-4-diazo-4'-methoxydiphenylamine / dioctylnaphthalene Sulfonate-formaldehyde resin, 2-methylresorcin-4-diazo-4'-methoxydiphenylamine-dodecylbenzenesulfonate-formaldehyde resin, pyrogallol-4-diazo-3-methoxydiphenylamine-dioctylnaphthalenesulfonate-formaldehyde resin , Pyrogallol-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 2,
4-dihydroxybenzophenone-4-diazo-4'-
Methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4,4'-dihydroxydiphenylamine-4-diazo-4'-ethoxydiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, 2,4-dimethoxybenzoic acid-4-diazo -4'-Methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4-anilinobenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-phenoxybenzoic acid-4-diazo -4'-Methoxydiphenylamine dodecylbenzene sulfonate-formaldehyde resin, salicylic acid-4-diazodiphenylamine dioctylnaphthalene sulfonate-
Formaldehyde resin, 4-methylsalicylic acid-4-diazo-4'-methyldiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-hydroxybenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-hydroxy Benzoic acid-4-diazo-3-methyldiphenylamine / dioctylnaphthalenesulfonate / formaldehyde resin, gallic acid-4-diazo-4′-ethyldiphenylamine / dioctylnaphthalenesulfonate / formaldehyde resin, 2,4-dihydroxybenzoic acid -4
-Diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4- (p-hydroxyanilino) benzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 3
-Methoxy-1,2-benzenedicarboxylic acid-4-diazo-3-methyldiphenylamine dioctylnaphthalenesulfonate-benzaldehyde resin, p-methoxybenzoic acid-4-diazodiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, 2 -Methylbenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-phenoxybenzoic acid-4-diazo-3-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 2,4-diaminobenzoic acid -4-diazodiphenylamine / dioctylnaphthalene sulfonate-formaldehyde resin, 2,4-dimethoxybenzoic acid-4-diazo-4'-methyldiphenylamine / dioctylnaphthalene sulfonate-pho Formaldehyde resin, 4, - carboxy diphenylamine-4-diazonium-4'-ethyl-diphenylamine-dodecyl benzene sulfonate - formaldehyde resin, 2,4-dimethoxybenzoic acid 4-diazo diphenylamine-dodecylbenzenesulfonate -
Formaldehyde resin, 4-anilinobenzoic acid-4-diazo-4'-methyldiphenylamine dodecylbenzene sulfonate-formaldehyde resin, p-phenoxybenzoic acid-4-diazodiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin, etc. Of these compounds, particularly preferred are salicylic acid-4-diazodiphenylamine / dioctylnaphthalenesulfonate / formaldehyde resin, p-methoxybenzoic acid-4-diazodiphenylamine / dodecylbenzenesulfonate / formaldehyde resin, 2,4 -Dimethoxybenzoic acid-4-diazodiphenylamine dodecylbenzene sulfonate-formaldehyde resin, 4-
Anilinobenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p
-Phenoxybenzoic acid-4-diazo-4'-methyldiphenylamine dodecylbenzene sulfonate-formaldehyde resin, 2,4-dihydroxybenzoic acid-4-diazodiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin, 4-carboxydiphenylamine -4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4-carboxy-4'-methoxydiphenylamine-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, salicylic acid-4-diazo-4'-methoxydiphenylamine -Dioctylnaphthalene sulfonate-formaldehyde resin, p-hydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzene sulfo Salts - formaldehyde resin, 2,
4-Dihydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzene sulfonate-
Formaldehyde resin, resorcin-4-diazo-4 '
-Methoxydiphenylamine / dioctylnaphthalene sulfonate-formaldehyde resin, pyrogallol-4
-Diazo-4'-methoxydiphenylamine dodecylbenzene sulfonate-formaldehyde resin, 2,4-
It is a dihydroxybenzophenone-4-diazo-4'-methoxydiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin.

The diazo co-condensation resin of the present invention can be obtained as an arbitrary value for its molecular weight by variously changing the molar ratio of each monomer and the condensation conditions, but in order to effectively serve the intended purpose of the present invention. The molecular weight of about 400 to 100,000 can be used, but preferably about 800 to 8,000.
Is appropriate.

Next, a typical synthesis example of the diazo co-condensation resin according to the present invention will be described.

(Synthesis Example 1) 3.5 g (0.025 mol) of p-hydroxybenzoic acid and 4
-Diazo-4'-methoxydiphenylamine sulfate 22.0
g (0.075 mol) was dissolved in 90 g of concentrated sulfuric acid under water cooling. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) was slowly added. At this time, the reaction was added so that the reaction temperature did not exceed 10 ° C. Thereafter, stirring was continued under ice cooling for 2 hours. The reaction mixture was poured into 1 ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 200 ml of pure water, and 10.5 g of this solution was added.
A cold concentrated aqueous solution in which zinc chloride was dissolved was added. The resulting precipitate was filtered, washed with ethanol, and dissolved in 300 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 31.4 g of sodium dodecylbenzenesulfonate (soft type) was dissolved. The resulting precipitate was filtered off and washed with water, then at 30 ° C,
It was dried for one day and night to obtain diazo co-condensation resin-1.

When the molecular weight of this diazo co-condensed resin-1 was measured by GPC, the weight average molecular weight was about 2,300.

Regarding the other diazo co-condensation resins, Synthesis Example 1
Can be synthesized by a method similar to.

The above-mentioned photosensitive diazo co-condensation resin is desirably used in combination with an alkali-soluble or swellable lipophilic polymer compound as a binder resin.

As the lipophilic polymer compound, the following (1) to (1)
Copolymers having a molecular weight of usually from 20,000 to 200,000 using the monomer shown in 4) as a structural unit are exemplified.

(1) Acrylamides, methacrylamides, acrylic acid esters, methacrylic acid esters and hydroxystyrenes having aromatic hydroxyl groups, such as N- (4-
Hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m-, p-hydroxyphenyl-acrylate or methacrylate,
o-, m-, p-hydroxystyrene, (2) acrylic acid ester having an aliphatic hydroxyl group, and methacrylic acid ester such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, methacrylic acid Unsaturated carboxylic acids such as acids, maleic anhydride, itaconic acid, etc. (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4
(Substituted) alkyl methacrylates such as -hydroxybutyl methacrylate, glycidyl methacrylate and N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-hexyl methacryl Amides, acrylamides or methacrylamides such as N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, etc. (7) Ethyl vinyl ether, 2-chloroethyl Vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether Vinyl ethers such as vinyl ether and phenyl vinyl ether, (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate, (9) styrene, α-methyl styrene, methyl styrene, chloromethyl styrene, etc. Styrenes, (10) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (12) N-vinylpyrrolidone , N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (13) Maleimide, N-acryloylacrylamide,
Unsaturated imides such as N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide, (14) m-aminosulfonylphenyl methacrylate,
Unsaturated sulfonamides such as N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide.

Further, a monomer copolymerizable with the above monomer may be copolymerized. Further, a copolymer obtained by copolymerization of the above monomers, for example, glycidyl methacrylate,
Examples include those modified with glycidyl acrylate and the like, but are not limited thereto.

Particularly preferred lipophilic polymer compounds are acrylic acid,
Copolymer containing methacrylic acid, crotonic acid or maleic acid as an essential component, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, acrylonitrile or methacrylonitrile as described in JP-A-50-118802 A multi-component copolymer of acrylic acid or methacrylic acid and, if necessary, another copolymerizable monomer, a terminal having a hydroxy group as described in JP-A-53-120903, and a dicarboxylic acid A multi-component copolymer of acrylic acid or methacrylic acid, acrylic acid, or methacrylic acid esterified with a group containing an ester residue and optionally other copolymerizable monomers, JP-A-54-98614 (E.g., N- (4-hydroxyphenyl) methacrylic monomer having an aromatic hydroxyl group as described in Amide), acrylic acid or methacrylic acid and, if necessary, a multi-component copolymer with other copolymerizable monomers, alkyl acrylate, acrylonitrile or methacryloyl as described in JP-A-56-4144. A multi-component copolymer comprising a nitrile and an unsaturated carboxylic acid can be mentioned. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. JP-B-54-19773, JP-A-57-94747, JP-A-60-1882437, JP-A-62-58242, and JP-A-62-58242 in which polyvinyl acetal or polyurethane is alkali-solubilized.
The polymer compounds described in the specification of -123453 are also useful.

These lipophilic polymer compounds may be used alone or as a mixture.

If necessary, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, or the like may be added.

The lipophilic polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition at 40 to 99% by weight, preferably 50 to 95% by weight. The photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

 Next, a synthesis example of the lipophilic polymer compound will be described.

(Synthesis of Lipophilic Polymer Compound 1) N- (4-hydroxyphenyl) methacrylamide 18
g, acrylonitrile 13 g, ethyl acrylate 66 g, methacrylic acid 8.6 g and azobisisobutyronitrile 1.64
Dissolve 2 g of acetone-methanol 1: 1 mixed solution 112 ml,
After purging with nitrogen, the mixture was heated at 60 ° C. for 8 hours.

After the reaction was completed, the reaction solution was poured into water 5 with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 88 g of lipophilic polymer compound 1.
Obtained.

When the molecular weight of this lipophilic polymer compound 1 was measured by gel permeation chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was 75,000.

Various additives can be further added to the photosensitive composition used in the present invention.

For example, alkyl ethers (eg, ethylcellulose, methylcellulose) for improving coatability, surfactants (eg, fluorine-based surfactants), film flexibility,
Plasticizer for imparting abrasion resistance (for example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), and the image area of the developer are visible Pigments such as acridine dyes, cyanine dyes, styryl dyes, triphenylmethane dyes and phthalocyanines and other general stabilizers for diazo resins (phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, Boric acid, p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5
-Benzoyl-benzenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and copolymers thereof,
Polyvinylphosphonic acid and its copolymer, polyvinylsulfonic acid and its copolymer, 5-nitronaphthalene-1
-Phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutanetricarboxylic acid-1,2,4,1,
-Phosphonoethanetricarboxylic acid-1,2,2,1-hydroxyethane-1,1-disulfonic acid, etc.) can be added. The amount of these additives varies depending on the intended use, but is generally based on the total solid content of the photosensitive layer.
0.1 to 30% by weight.

The photosensitive composition of the present invention is dissolved in a suitable organic solvent, and a dry coating weight on a support having a hydrophilic surface is 0.2 to 10 g / m2.
² to obtain a photosensitive lithographic printing plate. The concentration of the photosensitive composition at the time of application is desirably in the range of 1 to 50% by weight. The coating solvent used is methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, dimethoxyethane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethylformamide, dimethylacetamide, dimethyl. Examples thereof include sulfoxide, methyl lactate, ethyl lactate, ethylene dichloride, cyclohexanone, dioxane and tetrahydrofuran. A mixed solvent obtained by adding a small amount of water or a solvent that does not dissolve the diazo resin or polymer compound such as toluene to the mixed solvent of these solvents is also suitable. When a photosensitive solution dissolved in these solvents is applied to a support and dried, it is preferable to dry at 50 ° C to 120 ° C. The drying may be carried out at a low temperature at the beginning, followed by preliminary drying, followed by drying at a high temperature. Alternatively, drying may be carried out directly at a high temperature by selecting an appropriate solvent and concentration.

As a support on which the photosensitive composition of the present invention is applied,
Various materials such as paper, plastic, and metal are used, but when used in a photosensitive lithographic printing plate, an aluminum plate subjected to hydrophilic treatment is particularly preferable. The surface of the aluminum plate is mechanically treated with wire brush graining, brush graining in which a slurry of abrasive particles is poured and roughened with a nylon brush, ball graining, HF or Al.
To etchant C _3, HCl, after the surface was grained by chemical grain training, electrolytic graining and composite graining went by combining these surface roughening method using nitric acid or hydrochloric acid and the electrolyte solution, optionally Etching with acid or alkali, followed by sulfuric acid, phosphoric acid,
It is preferable to perform anodic oxidation with a direct current or an alternating current power source in oxalic acid, boric acid, chromic acid, sulphamic acid, or a mixed acid thereof to provide a strong passivation film on the aluminum surface. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, US Patent No. 2,714,
Silicate treatment (sodium silicate, potassium silicate) described in US Pat. No. 066 and US Pat. No. 3,181,461, potassium zirconate fluoride treatment described in US Pat. No. 2,946,638, US Patent No. 3,201,24
No. 7, phosphomolybdate treatment,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent 1,091,433, German Patent 1,134,093 and British Patent 1,230,447 Polyvinylphosphonic acid treatment, phosphonic acid treatment described in JP-B-44-6409, phytic acid treatment described in British Patent No. 3,307,951, JP-A-58-16.
No. 893 and the combined treatment of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-18291,
Particularly preferred is a water-soluble polymer having a sulfonic acid group, which is described in JP-A-59-101651, and which has been hydrophilized by undercoating. As another hydrophilic treatment method, silicate electrodeposition described in US Pat. No. 3,658,662 can also be mentioned.

Further, after graining treatment and anodic oxidation, sealing treatment is also preferable. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic salt or an organic salt, a steam bath, or the like.

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

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

The developer used for the development of the photosensitive printing plate according to the present invention may be any of known ones, but preferably the following are preferred. That is, the developer for developing the photosensitive printing plate according to the present invention contains at least one alkali agent and water as essential components.

As the alkaline agent contained as an essential component in the developer, sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium salt of secondary or tertiary phosphate, sodium metasilicate, Inorganic alkaline agents such as sodium carbonate, ammonia, etc., mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triethanolamine, mono, di or triisopropanolamine, ethyleneimine And organic amine compounds such as ethylenediimine.

The content of these alkali agents in the developer is 0.05 to
It is 10% by weight, preferably 0.5 to 5% by weight. If the amount is less than 0.05% by weight, the development becomes poor, and if it exceeds 10% by weight, the printing performance as a lithographic printing plate is adversely affected.

The developer for developing the photosensitive printing plate according to the present invention may contain a specific organic solvent, if necessary.

Such an organic solvent is capable of dissolving or swelling the non-exposed portion (non-image portion) of the above-described photosensitive composition layer when contained in a developer, and at the same time, at room temperature (20 ° C.). An organic solvent having a solubility of 10% by weight or less. Any organic solvent may be used as long as it has such properties, and examples thereof include, but are not limited to, the following. That is, 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, methyl isobutyl ketone; Ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenylcarbinol, n-amyl alcohol and methyl amyl alcohol; alkyls such as xylene Substituted aromatic hydrocarbons; methylene dichloride,
Examples include halogenated hydrocarbons such as 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, and more preferably 2 to 10% by weight.

Further, the developer for developing the photosensitive printing plate according to the present invention may contain a water-soluble sulfite, if necessary. As such a water-soluble sulfite, an alkali or alkaline earth metal of sulfite is preferable, and examples thereof include sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is 0 to 4% by weight, preferably 0.1 to 4% by weight.
1% by weight.

Further, instead of the water-soluble sulfite, an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or a hydroxy aromatic compound such as methylresorcin may be contained. Of course, these compounds can be used in combination with a water-soluble sulfite.

In addition, a certain solubilizing agent may be included to assist the dissolution of the above-mentioned organic solvent in water. As such a solubilizing agent, in order to realize the predetermined effect of the present invention, it is preferable to use low molecular alcohols and ketones which are more soluble in water than the organic solvent used.

Further, an anionic activator, an amphoteric activator and the like can also be used. Such alcohols and ketones include, for example, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol,
It is preferable to use 4-methoxy-4-methylbutanol, N-methylpyrrolidone and the like. As the activator, for example, sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, N-
Sodium methyl-N-pentadecylaminoacetate, sodium lauryl sulfate and the like are preferred. Generally, the amount of the solubilizing agent such as alcohol and ketone used is preferably about 30% by weight or less based on the whole developer.

〔The invention's effect〕

The photosensitive composition of the present invention has excellent solubility in an organic coating solvent when coated on a support, compatibility with a binder, excellent developability, and no diazo residue.

Example 1 A 0.24 mm thick aluminum plate was coated with a nylon brush and 400
The surface was grained using an aqueous suspension of mesh pumicestone, and then thoroughly washed with water. This was etched by immersing it in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water and neutralized and washed with 20% nitric acid.
No. 67507, the electrochemical surface roughening method, that is, _VA = 12.
Using a sinusoidal alternating waveform current of 7 V and V _C = 9.1 V, the electrolytic surface roughening treatment was performed in a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² . Continue to soak in 30% sulfuric acid aqueous solution,
After desmutting at 55 ° C. for 2 minutes, anodizing treatment was performed in a 7% aqueous sulfuric acid solution so that the coating amount of aluminum oxide was 2.0 g / m ² . Then 3% of sodium silicate at 70 ℃
It was immersed in an aqueous solution for 1 minute, washed with water and dried. The following photosensitive solution was applied to the aluminum plate obtained as described above using a wheeler and dried at 80 ° C. for 2 minutes. The dry amount is
It was 2.0 g / m ² .

 The diazo resins used in the following photosensitive solutions are shown in Table 1.

Next, as a comparative example, a photosensitive solution using the following diazo resin was applied to the above photosensitive solution and dried. Dry weight 2.0 g / m ²
Met.

(Diazo Resin Used in Comparative Examples 1 and 2) Comparative Example 1 Pyrogallol-4-diazodiphenylamine / hexafluorophosphate-formaldehyde resin (condensed as in Synthesis Example 1, weight average molecular weight about 2100) Comparative Example 2 p-Hydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine-hexafluorophosphate-formaldehyde resin (condensed in the same manner as in Synthesis Example 1, weight average molecular weight about 2300) [Print stain Evaluation] Each photosensitive lithographic printing plate thus obtained was image-lighted with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m for 1 minute, and immersed in a developing solution shown below for 1 minute at room temperature. After that, the surface was lightly rubbed with absorbent cotton to remove the unexposed portion to obtain planographic printing plates (I) to (VII) having a bright blue image.

Each of the printing plates was used to print on high-quality paper with a commercially available ink using a KOR printing machine manufactured by Heidelperg.

When the printing stains of the planographic printing plates (I) to (VII) were examined, it was as shown in Table I.

As can be seen from Table 1, the lithographic printing plates (I) to (V) using the photosensitive composition of the present invention were obtained by comparing (V) in Comparative Examples 1 and 2.
Compared with (I) and (VII), there is no print stain at the time of printing, and it is very excellent. This indicates that the composition of the present invention has excellent developability and does not cause diazo residue.

Example 2 Each of the photosensitive lithographic printing plates used in Example 1 was imagewise exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. from a distance of 1 m for 1 minute, and immersed in a developing solution shown below at room temperature for 1 minute. After that, the surface was lightly rubbed with absorbent cotton to remove the unexposed portion, and planographic printing plates (VIII) to (XIV) having bright blue images were obtained.

In the same manner as in Example 1, printing was performed on high quality paper using commercially available inks with a KOR type printing machine manufactured by Heidelberg Co. using each printing plate.

The printing stains of the lithographic printing plates (VIII) to (XIV) were examined, and the results were as shown in Table 2.

As can be seen from Table 2, planographic printing plates (VIII) to (XII) using the photosensitive composition of the present invention are (XIII) and (XI
Compared with V), there is no print stain when printing and it is very excellent. This indicates that the composition of the present invention is excellent in developability and does not cause diazo residue.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-59-196325 (JP, A) JP-A-53-33116 (JP, A) JP-A-1-102456 (JP, A) JP-A-1- 102457 (JP, A) JP 62-17573 (JP, A) JP 53-120903 (JP, A) JP 62-169154 (JP, A) JP 63-285537 (JP, A) JP 63-157144 (JP, A)

Claims (1)

(57) [Claims] 1. A co-condensed diazo resin containing an aromatic compound having a carboxyl group and an aromatic diazo compound as constitutional units, the benzene sulfone having a linear alkyl group having 8 to 20 carbon atoms as a counter anion. A photosensitive composition comprising a co-condensed diazo resin containing an anion of an acid or naphthalene sulfonic acid.