JPH0389250A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enhance the developability of a planographic printing plate and to eliminate the remaining of diazo as well as to enhance the compatibility with a binder by using a compsn. contg. a specific cocondensed diazo resin. CONSTITUTION:The cocondensed diazo resin contg. an arom. compsn. (A) having at least either of a carboxyl group and hydroxyl group and an arom. diazo compd. (B) as its constituting component and an arom. sulfonate (C) having a long chain alkyl group as counter anion is incorporated into this compsn. This resin is obtd. by bringing, for example, p-hydroxy benzoic acid as the component A and 4-diazophenyl amine and aldehyde (e.g.: formaldehyde) as the component B into polycondensation and further bringing dodecyl benzene sulfonate as the component C into reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive composition, and particularly to a photosensitive composition useful for producing a photosensitive lithographic printing plate.

[Conventional technology]

Photosensitive printing plates are generally produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, polymerizing or crosslinking the irradiated areas, and turning the composition into a developer. Insolubilize and elute the non-irradiated areas into a developer, making each area an image area that repels water and accepts oil-based ink, and a non-image area that accepts water and repels oil-based ink. It is obtained by

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

However, conventionally known diazo resins generally do not have alkali solubility, so when developing a photosensitive composition containing it with an alkaline developer after exposure, it is difficult to develop the diazo resin, especially under under conditions. There are also problems such as poor developability at the bottom, and furthermore, a so-called diazo residue, in which the diazo resin remains in the form of a film on the surface of the support after development, resulting in a decrease in printability.

Therefore, we made the diazo resin contain an alkali-soluble group,
A method for making diazo resin solubilized in alkali is disclosed in JP-A-1-10
2456 and JP-A-1-102457.

However, even when these alkali-soluble diazo resins are used, the developability with fatigued developers or developers with low organic solvent content is not good, and diazo residues are produced.

[Problem to be solved by the invention]

Therefore, the main object of the present invention is to provide a novel photosensitive composition that is alkali-soluble, has excellent developability, has no diazo residue, and has excellent compatibility with a binder.

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

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 to solve the problem]

As a result of intensive studies to achieve the above object, the present inventor discovered that the above object could be achieved by using a new diazo resin, and thus arrived at the present invention.

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

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

Preferable examples of the aromatic ring include aryl groups, such as phenyl and naphthyl groups.

Furthermore, the carboxyl group or hydroxyl group described above may be bonded directly 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 preferably 1 to 3. Further, as a linking group, for example, carbon number is 1 to 4.
Examples include alkylene groups.

In order for the above aromatic compound to be condensed with aldehydes or ketones, it is necessary to have at least two unsubstituted sites on the aromatic ring of one or more aryl groups substituted with at least one hydroxyl group. It is.

Specific examples of aromatic compounds 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-propyl salicylic acid, 6-propyl salicylic acid,
-Laurylsalicylic acid, 6-styarylsalicylic 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-Ihydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxy Benzoic acid, gallic acid, phloroglucincarboxylic acid, 2.4.5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p-)ruyl) gallic acid, proto Catechoyl-gallic acid, 4,6-cyhydroxyphthalic acid, (2,4-dihydroxyphenyl) vinegar L (2,
6-dihydroxyphenyl>acetic acid, (3,4,5-)dihydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4-(p-hydroxyphenyl)methylbenzoic acid, 4-(0 -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-hydroxyphenylsulfonyl)
Examples include benzoic acid, 4-(p-hydroxyphenylthio)benzoic acid, etc., and among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, gallic acid, and 70-loglucine 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-
Examples include (p-methoxybenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, etc. Among these, particularly preferred are 2,4-dimethoxybenzoic acid, p- These are 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, resorcinol, 2-methylresorcinol, (o, p.

m) Methoxyphenol, m-ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p
-Hydroxybenzyl alcohol, 4-chlororesorcinol, biphenyl 4,4'-diol, 1.2.4-benzenetriol, bisphenol A, 2.4-dihydroxybenzophenone, 2.3.4-)lihydroxybenzophenone, p- Hydroxyacetophenone, 4,4-
These include dihydroxydiphenyl ether, 4.4'-dihydroxydiphenyl ether, amine, 4.4'-dihydroxysulfone, 4.4'-dihydroxydiphenyl sulfide, cumylphenol, etc. 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 an aromatic diazo compound represented by the following formula (1).

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

R2 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.

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.

X- represents an anion, preferably an anion of an inorganic or organic acid having a pKa of 4 or less.

Specifically, hydrohalic acids such as 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 acids or their half esters, arsonic acids, phosphinic acids, fluorocarboxylic acids such as triple oroacetic acid, amidosulfonic acids, selenic acids , hydrofluoroboric acid, hexafluorophosphoric acid, perchloric acid, and further anions such as aliphatic and aromatic sulfonic acids.

Y represents -NH--〇-1 or -S-, preferably -
Indicates NH-.

Specific examples of the aromatic diazo compound represented by the above-mentioned formula (I) include 4-diazodiphenylamine, 4'
-Hydroxy-4-diazodiphenylamine, 4'-methoxy-4-diazodiphenylamine, 4'-ethoxy-4-diazodiphenylamine, 4'-n-propoxy-4-diazodiphenylamine, 4'-1-propoxy-4-diazo diphenylamine, 4'-methyl-4-
Diazodiphenylamine, 4'-ethyl-4-diazodiphenylamine, 4'-n-propyl-4-diazodiphenylamine, 4'-i-propyl-4-diazodiphenylamine 4/, -butyl-4-diazodiphenylamine, 4'- Hydroxymethyl-4-diazodiphenylamine, 4'β-hydroxyethyl-4-diazodiphenylamine, 4'-r-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'-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-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-
Examples include 2,5-dimethoxy-4-diazodiphenyl sulfide.

Among these, particularly preferred aromatic diazo compounds include:
Examples include 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-4'-ethoxydiphenylamine, and 4-thia/-3-methoxydiphenylamine.

In the present invention, the condensation type resin with aldehydes (hereinafter referred to as diazo cocondensation 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 can be produced by a known method. ,
For example, Photographic Science and Engineering (Photo, Sci, Bng,
) Volume 17, Page 33 (1973), U.S. Patent No. 2.0
According to the methods described in No. 63.631, No. 2, and No. 679.498, diazonium salts, aromatic compounds having carboxyl groups and/or hydroxyl groups, and aldehydes, e.g. It can be obtained by polycondensation with paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

Furthermore, these aromatic compounds, aromatic diazo compounds, and aldehydes or ketones having carboxyl groups and/or hydroxyl groups in their molecules can be freely combined with each other, and two or more of each can also be mixed and co-condensed. It is possible. Furthermore, co-condensation can be carried out by adding a co-condensable phenol having no carboxyl group.

At that time, the charging molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazo compound is 1:0.1 to 0.1:l; preferably l:0.2 to 0. .2:1, more preferably 1:0.5
~0.2:1. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazo compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually 1:0.6 to 1.2.
A diazo cocondensation resin can be obtained by mixing preferably at a ratio of 1:0.7 to 1.5 and reacting at a low temperature for a short time, for example, 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 anions other than the aromatic sulfonic acid having a long-chain alkyl group, 50 mol% or more, preferably 80 mol% or more of the counter anions contained in the co-condensed diazo resin of the present invention are long-chain. An anion of an aromatic sulfonic acid having an alkyl group is preferable.

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

More preferred is benzenesulfonic acid or naphthalenesulfonic acid having a straight or branched alkyl group having 8 or more carbon atoms.

Even more preferred is benzenesulfonic acid or naphthalenesulfonic acid having a straight chain or monobranched alkyl group having 8 or more and 20 or less carbon atoms. The long chain alkyl group is more preferably a straight 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 other linking groups.

Specific examples include octylbenzenesulfonic acid, dioctylbenzenesulfonic acid, nonylbenzenesulfonic acid, dinonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, bis-dodecylbenzenesulfonic acid,
Tridecylbenzenesulfonic acid, undecyloxybenzenesulfonic acid, bis-undecyloxybenzenesulfonic acid, dobyloxybenzenesulfonic acid, bis-dobucyloxybenzenesulfonic acid, dodecyltoluenesulfonic acid, tetradecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid , hexadecylbenzenesulfonic acid, heptadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid, eicosadecylbenzenesulfonic acid, octylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid, dininolnaphthalenesulfonic acid acid, decylnaphthalenesulfonic acid, bis-decylnaphthalenesulfonic acid, undecylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, tridecylnaphthalenesulfonic acid, and the like.

Among these, particularly preferred are dodecylbenzenesulfonic acid and dioctylnaphthalenesulfonic acid.

Specific examples of the diazo cocondensation resin in the present invention include p
-Cresol-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, resorcin-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 2-methylresorcin-4-diazodiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, p-methoxyphenol-4-diazodiphenylamine dioctylnaphthalene sulfonate-acetaldehyde resin,
Pyrogallol-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, phloroglucin-4-diazodiphenylamine dodecylbenzenesulfonate-acetone resin, 4,4'-dihydroxydiphenyl ether-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-
Methoxydiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin, gallic acid-4-diazo-4'-ethoxydiphenylamine dodecylbenzenesulfonate, formaldehyde resin, 2,4-dihydroxybenzoic acid-4-diazo-4'-methoxy Diphenylamine dodecylbenzenesulfonate - formaldehyde 1m fat, 4-(p-hydroxyanilino)benzoic acid-4-diazo-4'-methoxydiphenylamine dioctylnaphthalenesulfonate - formaldehyde resin, p-cresol-4-diazo- 3-methoxydiphenylamine/hexafluorophosphate/dodecylbenzenesulfonate (20/80 molar ratio) mixed salt-benzaldehyde resin, resorcinol-4-diazo-4'-methoxydiphenylamine/dioctylnaphthalenesulfonate-formaldehyde 4fltllL 2-Methylresorcin-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, pyrogallol-4-diazo-3-methoxydiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, pyrogallol-4-diazo- 4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde FMt1M, 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 dodecylbenzenesulfonate-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 dodecylbenzene sulfonate -Formaldehyde resin, p-hydroxybenzene fF
Acid-4-diazo-3-methyldiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin,
Gallic acid-4-diazo-4'-ethyldiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, 2,4-dihydroxybenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4-(p-hydroxy Anilino) 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-7enoxybenzoic acid-4-diazo-3-methoxydiphenylamine.
Dodecylbenzenesulfonate-formaldehyde resin, 2,4-diaminobenzoic acid-4-diazodiphenylamine/dioctylnaphthalenesulfonate-formaldehyde resin, 2,4-dimethoxybenzoic acid-4-diazodiphenylamine-4'-methyldiphenylamine. Dioctylnaphthalene sulfonate-formaldehyde resin, 4゜carboxydiphenylamine-4-diazo-4'-ethyldiphenylamine dodecylbenzesulfonate-formaldehyde resin, 2,4-dimethoxybenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonic acid Salt-formaldehyde resin, 4-anilinobenzoic acid-4-diazo-4'-methyldiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p-phenoxybenzoic acid-4-diazodiphenylamine dioctylnaphthalenesulfonate-formaldehyde Among these compounds, particularly preferred are 4-diazodiphenylamine salicylate/dioctylnaphthalenesulfonate-formaldehyde resin, and 4-diazodiphenylamine p-methoxybenzoate/dodecylbenzenesulfonate-formaldehyde resin. , 2.4-dimethoxybenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 4-
Anilinobenzoic acid-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, p
-Phenoxybenzoic acid-4-diazo-4'-methyldiphenylamine dodecylbenzenesulfonate -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 dodecylbenzenesulfonic acid Salt-formaldehyde resin, salicylic acid-4-diazo-4'-
Methoxydiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin, p-hydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin,
2.4-dihydroxybenzoic acid-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, resorcin-4-diazo-
4'-methoxydiphenylamine dioctylnaphthalenesulfonate-formaldehyde resin, pyrogallol-4-diazo-4'-methoxydiphenylamine dodecylbenzenesulfonate-formaldehyde resin, 2
．． 4-dihydroxybenzophenone-4-diazo-4'
-Methoxydiphenylamine dioctylnaphthalene sulfonate-formaldehyde resin.

The diazo cocondensation resin of the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions; however, in order to effectively serve the purpose of the present invention, has a molecular weight of about 400 to 100,
000 can be used, but preferably about 80
A value of 0 to 8,000 is suitable.

Next, a typical synthesis example of the diazo cocondensation resin according to the present invention will be shown.

(Synthesis Example 1) 3.5 g (0,025 mol) of p-hydroxybenzoic acid and 22.0 g (0,075 mol) of 4-diazo-4'-methoxydiphenylamine sulfate were mixed into 90 g under water cooling.
of concentrated sulfuric acid. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) were added slowly. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was poured into 11 ethanol under water cooling, and the resulting precipitate was filtered.

After washing with ethanol, this precipitate was dissolved in 200+y1 pure water, and to this solution was added a cold concentrated aqueous solution in which 10.5 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and then washed with 300mj! was dissolved in pure water.

A cold concentrated aqueous solution containing 31.4 g of sodium dodecylbenzenesulfonate (soft type) was added to this liquid. The resulting precipitate was filtered, washed with water, and then dried at 30° C. for one day and night to obtain diazo cocondensation resin-1.

When the molecular weight of this diazo cocondensation resin-1 was measured by GPC, the weight average molecular weight was about 2.300.

Regarding the other diazo cocondensation resins mentioned above, Synthesis Example 1
It can be synthesized by the same method as .

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

As this lipophilic polymer compound, the following (1) to (14)
Examples include copolymers whose structural units are the monomers shown in ) and usually have a molecular weight of 20,000 to 200,000.

(1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters, and hydroxystyrenes having an aromatic hydroxyl group, e.g., tlfN-(
4-hydroxyphenyl)acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o -, m
-, p-hydroxyphenyl-acrylate or methacrylate-+-10-m+, p-hydroxystyrene, (2) Acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2- Hydroxyethyl methacrylate, (3) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, (4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic (Substituted) alkyl acrylates such as hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclo (Substituted) alkyl methacrylates such as hexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide , N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, and other acrylamides or methacrylamides, (7) Ethyl vinyl ether , vinyl ethers such as 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and hinyl benzoate; (9) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) ethylene, propylene , olefins such as isobutylene, butadiene, isoprene, (12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc., (13) maleimide, N-acryloyl acrylamide, N-acetyl methacryl unsaturated imides such as amide, N-propionylmethacrylamide, N-(p-chlorobenzoyl)methacrylamide, (14) m-aminosulfonylphenyl methacrylate, N-(p-aminosulfonylphenyl)methacrylamide, N-(p unsaturated sulfonamides such as -aminosulfonylphenyl)acrylamide, N-(p-)luenesulfonyl)methacrylamide;

Furthermore, a monomer that can be copolymerized with the above monomer 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.

Particularly suitable lipophilic polymer compounds include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component, such as 2-hydroxyethyl as described in JP-A-50-118802. Acryle-14ft2-4-Droxyethyl methacrylate, acrylonitrile or methacrylonitrile, multi-component copolymer with acrylic acid or methacrylic acid and other copolymerizable monomers as necessary, JP-A-53-120903
Acrylic acid or methacrylic acid, which has a hydroxyl group at the end and is esterified with a group containing a dicarboxylic acid ester residue, as described in the publication, acrylic acid, or methacrylic acid, and other co-acrylic acid as necessary. Multi-component copolymers with polymerizable monomers, monomers having aromatic hydroxyl groups as described in JP-A No. 54-98614 (for example, N-(4-hydroxyphenyl) methacrylamide, etc.) , acrylic acid or methacrylic acid and optionally other copolymerizable monomers, alkyl acrylates, acrylonitriles or methacrylates as described in JP-A-56-4144, and unsaturated Examples include multicomponent copolymers made of carboxylic acids. In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. In addition, JP-B No. 54-19773 and JP-A No. 57-947 which solubilized polyvinyl acetal and polyurethane with alkali are also available.
No. 47, No. 60-182437, No. 62-58242
The polymer compounds described in No. 62-123453 are also useful.

These lipophilic polymer compounds may be used alone or in combination.

Further, if necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added.

The lipophilic polymer compound used in the present invention is usually 40 to 99% by weight, preferably 50 to 99% by weight in the solid content of the photosensitive composition.
Contains 95% by weight. Further, the photosensitive diazo resin used in the present invention is usually 1 to 60% by weight, preferably 3 to 3% by weight.
Contains 0% by weight.

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

(Synthesis of lipophilic polymer compound 1) N-(4-hydroxyphenyl) methacrylamide 18
g1 acrylonitrile 13g1 ethyl acrylate) 66
g, 8.6 g of methacrylic acid and 1.642 g of azobisisobutyronitrile in a 1:1 acetone-methanol mixed solution of 112 mj! After dissolving in and purging with nitrogen, heat at 60℃ for 8 hours.
heated for an hour.

After the reaction is completed, the reaction solution is stirred and poured into water 51, and the resulting white precipitate is filtered 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 (e.g. ethyl cellulose, methyl cellulose) to improve coating properties, surfactants (e.g. fluorosurfactants), plasticizers (e.g. tricresyl) to impart film flexibility and abrasion resistance. phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), acridine dye, cyanine dye, styryl as a coloring substance to visualize the image area of the developer. Dyes, pigments such as triphenylmethane dyes and phthalocyanines, and other common stabilizers for diazo resins (phosphoric acid, phosphorous acid, pyrophosphoric 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, polyvinylsulfone Acids and copolymers thereof, 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 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/m2 to obtain a photosensitive planographic printing plate. The concentration of the photosensitive composition during application is 1 to
A range of 50% by weight is desirable. The coating solvents used are methyl cellosolve, ethyl cellosolve,
1-methoxy-2-propertool, dimethoxyethane,
Examples include 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, and tetrahydrofuran. 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 applying a photosensitive liquid dissolved in these solvents to a support and drying it, the temperature is 50°C to 120°C.
It is preferable to dry it.

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, and pole graining. After graining the surface using chemical graining as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining that combines these roughening methods, acid or alkali treatment is applied as necessary. Etching treatment with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid,
Preferably, the aluminum is anodized in sulfamic acid or a mixed acid thereof using a direct current or alternating current power source to form a strong passive film on the aluminum surface. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary, the aluminum surface is further hydrophilized as described in US Pat. No. 2.714.066 and US Pat. No. 3.181.461. silicate treatment (sodium silicate, potassium silicate), potassium fluorozirconate treatment as described in U.S. Pat. No. 2.946.638, U.S. Pat. No. 3.201
．． 247, alkyl titanate treatment as described in British Patent No. 1.108.559, German Patent No. 1.091.4.
The polyacrylic acid treatment described in Specification No. 33, German Patent No. 1.134.093 and British Patent No. 1.
Polyvinylphosphonic acid treatment as described in No. 230.447, phosphonic acid treatment as described in Japanese Patent Publication No. 44-6409, U.S. Patent No. 3.307.951
Phytic acid treatment described in the specification, JP-A-58
-16893 and JP-A No. 58-18291, a composite treatment consisting of a hydrophilic organic polymer compound and a divalent metal, and a sulfonic acid described in JP-A-59-101651. Particularly preferred are those which have been subjected to hydrophilic treatment by undercoating with a water-soluble polymer having groups. Other hydrophilic treatment methods include U.S. Patent No. 3.658.6
Mention may also be made of the silicate electrodeposition described in No. 62.

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 rays and 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 one 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.

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 favorable results are obtained when IO wt%.

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% by weight, preferably 0.1 to 1% by weight.
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 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 solubilizing agent, in order to achieve the desired effect of the present invention, it is preferable to use low-molecular alcohols and ketones that are more water-soluble 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.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent solubility in organic coating solvents and compatibility with binders when coated on a support, has excellent developability, and does not cause diazo residue.

Example 1 The surface of an aluminum plate having a thickness of 0.24 [+1111 mm] was grained using a nylon brush and an aqueous suspension of 400 mesh pumice stone, and then thoroughly washed with water.

(10% hydroxide)) 6.
After immersion for 0 seconds and etching, after washing with running water, 20%
After neutralization and cleaning with nitric acid, electrochemical surface roughening method described in JP-A-53-67507, that is, VA=12.7V, Vc
=9. Using an IV sinusoidal alternating wave current, electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution with an anode special electricity amount of 160 corons/dm''.Subsequently, it was immersed in a 30% sulfuric acid aqueous solution, and After desmutting for 2 minutes at ℃, anodization treatment was performed in a 7% aqueous sulfuric acid solution so that the coating amount of aluminum oxide was 2.0g/m'. The aluminum plate obtained in the above manner was coated with the following photosensitive solution using a wheeler and dried for 2 minutes at 80°C.The dry weight was 2.0g/m2. there were.

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

(Photosensitive liquid) Next, as a comparative example, a photosensitive liquid using the following diazo resin was applied to the above photosensitive liquid and dried. Dry weight is 2.0g/
It was m'.

(Diazo resin used in Comparative Example 1.2) Comparative Example 1 Pyrogallol-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin (condensed in the same manner as Synthesis Example 1, weight average molecular weight approximately 2100) Comparative Example 2 p-hydroxybenzoic acid-4-diazo-4'methoxydiphenylamine/hexafluorophosphate-formaldehyde resin (condensed in the same manner as Synthesis Example 1, weight average molecular weight approximately 2300) [Printed] Evaluation of stains] Each photosensitive lithographic printing plate obtained in this way was coated with Fuji Photo Film@! I! After exposing the image to PS light for 1 minute from a distance of 1 m, and immersing it in the following developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed areas, and a lithographic printing plate with a bright blue image was prepared. (I) to (■) were obtained.

(Developer) Each printing plate was printed on high-quality paper with a commercially available ink using a KOR printing machine manufactured by Heidelberg.

When we examined the printing stains on the lithographic printing plates (I) to (■), we found that
The results were as shown in Table ■.

As can be seen from Table 1, the lithographic printing plates (I) to (V) using the photosensitive composition of the present invention are the (VI
) and (■), there is no printing stain during printing, which is very good. This shows that the composition of the present invention has excellent developability and does not leave diazo residue.

Example 2 Each of the photosensitive lithographic printing plates used in Example 1 was image-exposed for 1 minute from a distance of 1 m using Fuji Photo Film@mPS Light, immersed in the following developer for 1 minute at room temperature, and then exposed to absorbent cotton. The surface was lightly rubbed with a cloth to remove the unexposed areas, and lithographic printing plates (■) to (XIV) with bright blue images were obtained.

(Developer) In the same manner as in Example 1, each printing plate was used to print on high-quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg.

lithographic printing plate (■) (XIV) was examined for printing stains. However, It was as shown in Table 2.

As can be seen from Table 2, the lithographic printing plates (■) to (Xll) using the photosensitive composition of the present invention are (Xllll) (X
Compared to IV), there is no printing stain during printing, which is very superior. This shows that the composition of the present invention has excellent developability and does not leave diazo residue.

Claims (1)

[Claims] 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, the counter anion of which is an anion of an aromatic sulfonic acid having a long-chain alkyl group. A photosensitive composition comprising a co-condensed diazo resin containing: