JPH0369955A - Photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To ensure satisfactory developability after storage over a long period of time, satisfactory printing resistance and ink retentivity by incorporating two kinds of high molecular compds. each contg. specified structural units in the molecule. CONSTITUTION:A high molecular compd. having structural units represented by formula I and a high molecular compd. contg. structural units represented by formula II and structural units represented by formula III in the molecule are incorporated into a photosensitive planographic printing plate. In the formula I, J is a divalent combining group and n is 0 or 1. In the formula II, R<16> is H, methyl, ethyl, methoxy, ethoxy or aryl. In the formula III, R<17> is H, methyl or ethyl and R<18> is alkyl or aryl. The high molecular compd. contg. structural units represented by the formula I in the molecule functions as a binder and the high molecular compd. contg. structural units represented by the formulae II, III functions as a sensitizer. Superior developability especially after storage over a long period of time, superior printing resistance and ink retentivity are ensured.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a photosensitive lithographic printing plate.

[Background of the invention]

Various photosensitive lithographic printing plates have been proposed in the past.

Some conventional photosensitive lithographic printing plates contain an acrylic resin containing a carboxylic acid group as a binder. However, such a photosensitive lithographic printing plate has a problem in that, when it is used, for example, in a negative 28 plate, its developability, particularly when stored for a long period of time, is insufficient. In addition, in recent years, printing using UV ink (ultraviolet curable ink) has been increasing, but the photosensitive planographic printing plate described above is
When printing with V ink, the rigidity is insufficient,
There is a problem that ink receptivity is poor.

[Purpose of the invention]

The present invention solves the problems of the prior art described above, and improves developability and
In particular, it has sufficient developability after long-term storage, and
An object of the present invention is to provide a photosensitive planographic printing plate that has sufficient printing durability and ink receptivity even when printing with ink.

[Means and effects for solving the problems] The photosensitive lithographic printing plate of the present invention comprises a polymer compound containing a structural unit represented by the following formula [I] in its molecule, and a polymer compound containing the following formula (Vl).
A photosensitive lithographic printing plate characterized by containing a polymer compound containing a structural unit represented by the following general formula [VII] and a structural unit represented by the following general formula [VII] in the molecule, and with this structure, the above object can be achieved. This has been achieved.

General formula (1) %formula% However, J represents a divalent linking group, and n is 0 or 1.

General formula (Vl) where RIk represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or an aryl group.

General formula [VII] where R1'l represents a hydrogen atom, a methyl group or an ethyl group, and R11' represents an alkyl group or an aryl group.

The present invention will be further explained below.

First, the photosensitive layer of the photosensitive lithographic printing plate of the present invention contains:
- A polymer compound containing a structural unit represented by formula [I] in its molecule will be explained.

In formula (I) above, J represents a divalent linking group, and preferably J is a linear or branched alkylene group or arylene group. More preferably, n=1
So, J is -〇Hz- or -GHz CHt
− This is the case.

- The structural unit represented by formula [I] may be contained in the molecule in the form of a derivative. For example, it may have a substituent. In this way, derivatives of the structure represented by general 2 [I] or those containing substituted structural units in the molecule are also included in the present invention.

The polymer compound having the structural unit represented by the general formula [I] in the molecule as described above will be appropriately referred to as "component (A)" hereinafter.

Component (A) is capable of functioning as a binder in the photosensitive layer of the photosensitive lithographic printing plate of the present invention. Component (A) can act as an alkali-soluble (or swellable) resin.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention contains, as a binder,
Containing polymer compounds other than component (A) is not prohibited.

In the present invention, component (A) and other polymer compounds contained as a binder if necessary preferably have a weight average molecular weight of 20.000 or more and 500.
．． 000 or less, and is preferably a lipophilic polymer compound.

More preferably, the weight average molecular weight is 30.000 or more.
00,000 or less.

Note that the above molecular weight is based on a polystyrene standard determined by GPC.

That is, the weight average molecular weight can be measured by GPC (gel permeation chromatography). Calculation of number average molecular weight iMN and weight average molecular weight MW is based on Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan” 8.
By the method described on pages 00 to 805 (1972),
The test shall be performed by leveling the peaks of the oligomer region (by connecting the center lines of the peaks and valleys).

More preferred component (A) is the following formula (
It has a structural unit obtained from the monomer represented by n) in its molecule.

-Formula (n) However, in general formula (II), X is a divalent linking group.

-i Preferred specific examples of the compound represented by formula (II) include itaconic acid, 1-butene-2,4-dicarboxylic acid, 1-butene-2,3-dicarboxylic acid, and 1-pentene-dicarboxylic acid.
Examples include 2,5-dicarboxylic acid, 1-pentene-2,4-dicarboxylic acid, 1-pentene-2,3-dicarboxylic acid, and 1-hexene-2,6-dicarboxylic acid.

It is essential that component (A) contains a structural unit represented by (1)-formula CI) in the molecule, and any structure containing such a structural unit can be used, but particularly preferably , - 2 to 20 mol% of the structural unit represented by formula [I] in the molecule
It is better to use the one that contains it. - Preferred examples of monomers that provide structural units other than those represented by formula CI) include those shown in (2) to (13) below.

(2> Monomers having aromatic hydroxyl groups, such as N-(4
-Hydroxyphenyl〉acrylamide or N-(4
-hydroxyphenyl) methacrylamide, o -, m
-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or -methacrylate.

(3> Monomers having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.

(4) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, and N-dimethylaminoethyl acrylate.

(5) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-
(Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate.

(6) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,
Acrylamides such as N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylamide, N-ethyl-N-phenylacrylamide, etc. Or methacrylamide.

(7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.

(8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(9) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.

(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, methacrylateril, etc.

(13) Carboxylic acids having unsaturated bonds such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid.

Furthermore, by copolymerizing a monomer that can be copolymerized with the above-mentioned monomer, it may be made to contain a constituent unit other than the structural unit of formula CI).

In addition, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, etc. are also included in the scope of those that provide structural units other than those of general formula (1), but are not limited to these. It's not something you can do.

More specifically, it is preferable to use a copolymer having a hydroxyl group containing the monomers listed in (2) and (3) above as a unit other than the structural unit of the formula CI), and having an aromatic hydroxyl group. More preferred are copolymers having the following.

Further, polyvinyl butyral resin, polyurethane resin, boria≧do resin, epoxy resin, novolak resin, natural resin, etc. may be added to the above copolymer as necessary.

The following copolymers are particularly preferred as those that provide a structure other than the structural units of general formula (1).

That is, in the molecular structure, (a) 1 to 50 mol% of a structural unit having an alcoholic hydroxyl group and/or a structural unit having a phenolic hydroxyl group; . ) 5 to 40 mol% of the structural unit represented by (c) the following formula (IV) I2 -CH2-C-... (IV) COOR" represents an atom, a methyl group or an ethyl group, and R13 represents an alkyl group having 2 to 12 carbon atoms or an alkyl W-substituted aryl group.

A copolymer containing 25 to 60 mol % of structural units represented by the formula is preferred, and a copolymer having a weight average molecular weight of 30,000 to 300,000 is more preferred.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group in (a) above include Japanese Patent Publication No. 52-736
As described in No. 4, as in the compound shown in the following formula (V) (meth)acrylic acid ester-722R CHHz C-・・・・・・・・・(V)Coo
(CH2CHO), HIS In the formula, RI4 represents a hydrogen atom or a methyl group, R1% represents a hydrogen atom, a methyl group, an ethyl group, or a chloromethyl group, and n represents an integer of 1 to 10.

Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-bitroxypentyl (meth)acrylate, and examples of acrylamides include , N-methylol (meth)acrylamide,
Examples include N-hydroxyethyl (meth)acrylamide and the like.

Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming the structural unit having a phenolic hydroxyl group (a) include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(
2-hydroxyphenyl)-(meth)acrylamide,
(meth)acrylamide monomers such as N-(4-hydroxynaphthyl)-(meth)acrylamide; o-,
Examples include m- or p-hydroxyphenyl (meth)acrylate monomers; o-, m- or p-hydroxystyrene monomers. Preferably, O-m- or p-hydroxyphenyl (meth)acrylate monomer, N-(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-(meth) It is an acrylamide monomer.

The structural unit having an alcoholic hydroxyl group and/or the structural unit having a phenolic hydroxyl group is selected from the range of 1 to 50 mol%, preferably 5 to 30 mol%, in the polymer compound.

- forming a structural unit represented by formula (II[);
Monomers having a cyano group in their side chains include acrylonitrile, methacrylonitrile, 2-pentenenitrile,
Examples include 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-1-cyanostyrene, and the like. Preferred are acrylonitrile and methacrylonitrile.

The proportion of the structural unit having a cyano group in the side chain contained in the molecule of the polymer compound is preferably selected from the range of 5 to 40 mol%, more preferably 15 to 35 mol%.

The monomer having a carboxy ester group in its side chain and forming the structural unit represented by formula CIV) is as follows:
Formed from the monomers such as ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, etc. The unit preferably accounts for 25 to 60 mol% in the polymer compound.
, preferably from the range of 35 to 60 mol%.

Note that each of the above structural units is not limited to units formed from the monomers listed as specific examples.

In the present invention, it is preferable to use, for example, a component having the following composition as component (A). That is, p-hydroxyphenylmethacrylamide (HYPMA) and/or 2-hydroxyethylmethacrylate-1-(HEMA
) is 3 to 30 mol%, the monomer providing the structural unit represented by formula (I) is 5 to 20 mol%, ethyl acrylate is 30 to 70 mol%, and acrylonitrile is 5 to 30 mol%. can be preferably used. This composition can act as an alkali-soluble resin.

In carrying out the present invention, a polymer compound other than the component (A) according to the present invention may be contained as a binder in the photosensitive layer of the photosensitive lithographic printing plate. However, in this case, component (A) is 10
It is preferably contained in an amount of 0 to 20 mol%.

Examples of the polymer compounds that can be used in combination with component (A) as a binder for the photosensitive layer include the above-mentioned (2) to (13).
Examples include polymers or copolymers of the monomers listed above, and polymers or copolymers having structural units represented by formulas (II[) to (V) above].

Component (A) contained in the photosensitive layer of the photosensitive lithographic printing plate of the present invention and other polymeric compounds contained as a binder if necessary are preferably added together in the solid content of the photosensitive layer. usually 40 to 99% by weight, more preferably 50 to 99% by weight
The weight content is 95%.

Next, the photosensitive layer of the photosensitive lithographic printing plate of the present invention contains:
- A polymer compound containing a structural unit represented by the formula (VI) and a structural unit represented by the general formula [■] in its molecule will be explained.

Hereinafter, such a polymer compound will be referred to as "component (B)."

Component (B) -a is a lipophilic polymer compound that can function as a liposensitizing agent in the photosensitive layer of a photosensitive lithographic printing plate.

Component (B) is a compound represented by the following formula [■],
The maleic anhydride portion is represented by the formula R''OH (in the formula, R11+ has the same meaning as in the general formula [■]).

It can be synthesized by reacting an alcohol and, if necessary, further reacting an alcohol represented by the formula R''OH (in the formula, R1? represents a methyl group or an ethyl group).

(In the formula, RI6 has the same meaning as in general formula [VI). ) Alternatively, it can also be obtained by copolymerizing the compound represented by the above formula [■] and the compound represented by the following formula (IXI).

(In the formula, RI? and RI8 have the same meanings as in the general formula [VII].) Component (B) is, for example, U.S. Patent No. 3,388.106
A person skilled in the art can easily determine the method according to the methods described in the specifications of No. 3,418,292.

In addition to the structural unit represented by formula (Vl) and the structural unit represented by [■], component (B) may further contain a third structural unit as a copolymerization component. Such a copolymerization component can be selected from the other addition polymerizable unsaturated compounds described in the copolymer of component (A).

The content of the structural unit represented by formula (Vl) in the copolymer of component (B) is preferably about 20 to 80% by weight, more preferably 40 to 70% by weight. Furthermore, the structural unit represented by general formula [VII] is approximately 20
It is preferably ~80% by weight, more preferably,
It is contained in an amount of 40 to 70% by weight.

The molecular weight of the polymer of component (B) is generally preferably about 5
A suitable range is from 00 to 50.000, more preferably from 750 to 30.000, and most preferably from 80.000 to 30.000.
0 to 10.000.

The polymer of component (B) is preferably present in the photosensitive layer in an amount of about 0.2
It is contained in an amount of up to 20% by weight, more preferably in an amount of 0.5 to 5% by weight.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention can contain various photosensitive compounds.

For example, a diazo resin can be preferably included.

Any diazo resin can be used in the present invention.

In the present invention, as the diazo resin, it is preferable to use a co-condensed diazo resin containing as a constituent unit an aromatic compound having one or more carboxyl groups or hydroxyl groups (whichever one is less) and an aromatic diazonium compound. can.

Such an aromatic compound having a carboxyl group and/or a hydroxyl group is one that contains an aromatic ring substituted with at least one carboxyl group and/or an aromatic ring substituted with at least one hydroxyl group in the molecule. In this case, the carboxyl group and the hydroxyl group may be substituted on the same aromatic ring, or may be substituted on different aromatic rings. This carboxyl group or hydroxyl group may be bonded directly to the aromatic ring or may be bonded via a bonding group.

Preferred examples of the aromatic group include aryl groups such as phenyl and naphthyl groups.

In the co-condensed diazo resin that can be used 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. When a carboxyl group or a hydroxyl group is bonded to an aromatic ring via a bonding group, examples of the bonding group include an alkylene group having 1 to 4 carbon atoms.

Specific examples of the aromatic compound containing a carboxyl group and/or hydroxyl group as a constitutional unit of the co-condensed diazo resin include benzoic acid, 〇-chlorobenzoic acid, m-
Chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4-(m-
Methoxyanilino)benzoic acid, 4-(p-methylbenzoyl)benzoic acid, 4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, phenol,
(o, m, p)-cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycin, p-hydroxyethylphenol, naphthol, pyrogallol, Hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcinol, biphenyl-4,4゛-diol, l,2゜4-benzenetriol, bisphenol A12゜4-dihydroxybenzophenone, 2.3.4-trihydroxybenzophenone, p -Hydroxyacetophenone, 4.4-dihydroxydiphenyl ether, 4. 4'-dihydroxydiphenylamine, 4,4''-dihydroxydiphenyl sulfide, cumylphenol, (o, m, p) -
Chlorophenol, (o, m, p)-bromophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, 6-stialylsalicylic acid, 4.6 -Simethylsalicylic 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, 26-dihydroxybenzoic acid, 2.6-dihydroxy-4-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4
-Methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2.4.5-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p -) gallic acid, protocatechoyl gallic acid, 4,6-cyhydroxyphthalic 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- Examples include 4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl)benzoic acid, and 4-(p-hydroxyphenylthio)benzoic acid. Particularly preferred among these are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid.

As the aromatic diazonium compound used as the structural unit of the above-mentioned co-condensed diazo resin, diazonium salts such as those listed in Japanese Patent Publication No. 49-48001 can be used, but diphenyla ξ-4-diazonium salts are particularly preferred. . Diphenylamine-4-diazonium salts are
These 4-amino-diphenylamines include 4-amino-diphenylamines.
-aminodiphenylamino, 4-amino-3-methoxydiphenylamino, 4-amino-2-methoxy-diphenylamine, 4'-amino-2-methoxydiphenylamino, 4'-amino-4- Methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4
-amino-3-ethoxydiphenylamine, 4-amino-3-β-hydroxynitoxydiphenylamine,
4-amino-diphenylamine-2-sulfonic acid, 4-
Examples include amino-diphenylamine-2-carboxylic acid, 4-amino-diphenylamine-2''-carboxylic acid, etc. Particularly preferred are 3-methoxy-4-aminodiphenylamine and 4-amino-diphenylamine.

The co-condensed diazo resin that can be used in the present invention is preferably one represented by the following formula (X).

General Formula (X) In General Formula (X), A is a group derived from an aromatic compound having at least one of a carboxyl group and a hydroxyl group, and examples of such aromatic compounds include those listed above. be able to.

In the formula, R8, R2 and R3 represent a hydrogen atom, an alkyl group or a phenyl group, R represents a hydrogen atom, an alkyl group or a phenyl group, and X represents a counter anion. n preferably represents a number from 1 to 200.

When a co-condensed diazo resin is used in the present invention, it is more preferable to use it in combination with a condensed diazo resin obtained by condensing an aromatic diazonium compound.

In this case, the co-condensed diazo resin is preferably used in an amount of 5% by weight or more in the diazo resin, and the condensed diazo resin is preferably used in an amount of 95% by weight or less in the diazo resin.

Furthermore, in this case, the weight % ratio of co-condensed diazo resin to condensed diazo resin is preferably 30 to 70: 70 to 30 in order to achieve both excellent sensitivity and developability.
It is.

The above-mentioned co-condensed diazo resins and condensed diazo resins used in combination with these or independently as diazo resins are:
Known methods such as Photographic Science and Engineering (Photo, Sci, E.
ng, Volume 17, Page 33 (1973), U.S. Patent No. 2,063,631, U.S. Patent No. 2,679,498. It is obtained by polycondensation of salts, aromatic compounds having carboxyl and hydroxyl groups, and aldehydes, such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones, such as acetone and acetophenone.

Furthermore, these aromatic compounds, aromatic diazo compounds, and aldehydes or ketones having carboxyl and/or hydroxyl groups in their molecules can be freely combined with each other, and two or more of each may be mixed and co-condensed. is also possible.

The molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazonium compound is preferably 1:0.1 to 0.1:1,
More preferably t:O,S~0.2=1, still more preferably 1:1~0.2:1.

In this case, the molar ratio of the sum of aromatic compounds and aromatic diazonium compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually preferably 1:0.6 to 1.2, more preferably 1:0.6 to 1.2. Prepare at i:o, 'y ~ 1.5, and cook at low temperature for a short time.
For example, by reacting for about 3 hours, a co-condensed diazo resin can be obtained.

The counter anion of the diazo resin includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. Those that form such anions include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids, and typical examples include methanesulfonic acid, chloroethanesulfonic acid, etc. , dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4
- Aliphatic and aromatic sulfonic acids such as acetylbenzenesulfonic acid and dimethyl-5-sulfoisophthalate, 2
．． 2', 4,4'tetrahydroxybenzophenone,
1.2.3-trihydroxybenzophenone, 2.2'
Examples include hydroxyl group-containing aromatic compounds such as 4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, and perhalogen acids such as C14 and IO4.

However, it is not limited to this. Among these, particularly preferred are hexafluorophosphoric acid and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

The above-mentioned co-condensed diazo resin can have an arbitrary molecular weight by varying the molar ratio of each monomer and the condensation conditions. In the present invention, in general, those having a molecular weight of about 400 to 10,000 can be effectively used, more preferably about 800 to 5,000.
is appropriate.

In addition, in the present invention, other than the above-mentioned co-condensed diazo resins, those that can be preferably used as diazo resins include, for example, the above-mentioned Photographic Science &
Engineering (Photo.

Sci, Eng.) Vol. 17, p. 33 (1973), and U.S. Pat.
No. 98, 3゜050.502 specifications, JP-A-59
A diazo resin obtained by condensing a diazo compound and an active carbonyl compound, such as formaldehyde, acetaldehyde or benzaldehyde, etc., in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid, the manufacturing method of which is described in Publication No. 78340, etc. Examples include diazo compounds and diphenyl resins whose production methods are described in Japanese Patent Publication No. 49-4001.

Among the above, the diazo resin that can be preferably used in the present invention is represented by the following formula (XI), and contains 20 mol% or more of the resin in which n in each formula is 5 or more, more preferably 20 mol% or more. It contains ~60 mol%. During the ceremony,
R3 to R, , R, and X+n have the same meanings as in formula (X) above. - In formula (XI), R,,R
Examples of the alkyl group and alkoxy group of 2 and R3 include an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and as the alkyl group of R,
Examples include alkyl groups having 1 to 5 carbon atoms.

- Formula (XI) Such a photosensitive diazo resin can be produced according to a known method, for example, the method described in the above-mentioned Photographic Science and Engineering and other U.S. patent specifications cited above. .

At that time, when polycondensing the diazonium salt and the aldehyde, the molar ratio of both is usually 1:0.6 to 1:
2. A high-sensitivity diazo resin can be obtained by charging preferably at a ratio of 1:0.7 to 1:1.5 and reacting at a low temperature for a short period of time, for example, 10° C. or less for about 3 hours.

As the counter anion of the diazo resin represented by the general formula (XI), the same counter anions as those mentioned for the co-condensed diazo resin can be mentioned.

In the practice of the present invention, the photosensitive layer of the photosensitive lithographic printing plate is
It is preferable that the photosensitive material contains 3 to 50% by weight, more preferably 3 to 30% by weight of diazo resin.

The photosensitive layer of the photosensitive lithographic printed matter of the present invention may contain any organic acid,
It can contain inorganic acids and acid anhydrides.

Although the iM is arbitrary, acids having at least one carboxyl group such as monocarboxylic acids and polycarboxylic acids are preferred, such as malic acid, tartaric acid, and polyacrylic acid (such as those commercially available under the trade name Jurimer). can be preferably used.

As the inorganic acid, phosphoric acid or the like can be used. Acid anhydrides are also optional, such as acetic anhydride, propionic anhydride, benzoic anhydride, those derived from aliphatic/aromatic monocarboxylic acids, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride. Examples include those derived from aliphatic/aromatic dicarboxylic acids.

The photosensitive layer of the photosensitive lithographic printing plate of the present invention can contain a dye, particularly a dye that changes color from colored to colorless or changes color upon processing. Preferably, a pigment that changes from colored to colorless is contained.

In carrying out the present invention, the following can be mentioned as dyes that can be preferably used.

That is, for example, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue 1603 (manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.)
, crystal violet, brilliant green, ethyl violet, methyl violet, methyl green, erythrosin B1 basic tsuksin, malachite green, oil red, m-cresol purple, rhodamine B1 aura ξ, 4-p-dimethylaminophenyl imino naphthoquin , triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based pigments such as cyano-p-diethylaminophenyl acetanilide change color from colored to colorless or to a different color. Examples of pigments include:

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, more preferably triphenylmethane-based dyes, and Victoria Viewer Blue BOH is particularly preferred.

The above-mentioned color changing agent is usually added in the photosensitive composition from about 0.5 to about 10
It is preferable to contain the amount by weight, more preferably about 1% by weight.
Contain up to 5% by weight.

Various additives can be further added to the photosensitive layer of the photosensitive lithographic printing plate of the present invention.

For example, alkyl ether RC to improve coating properties.
For example, ethyl cellulose, methyl cellulose>, fluorine surfactants, nonionic surfactants [e.g., Bluronic L-64 (manufactured by Asahi Denka Corporation)], plasticizers to impart flexibility and abrasion resistance to the coating film. (e.g. butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid) oligomers and polymers).

Further, an oil-sensitizing agent (for example, a half-ester of styrene-maleic anhydride copolymer with alcohol described in JP-A No. 55-527) is added to improve the oil-sensitivity of the image area. The function of component (B) as an oil sensitizing agent in the present invention can be further enhanced by using the component (B) in combination. In addition, as other additives,
Stabilizers [e.g. phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5
-sulfonic acid, tartaric acid, etc.). The amount of these additives added varies depending on the object and purpose of use, but it is generally preferable to add 0 to the total solid content.
．． 01 to 30% by weight.

Next, the photosensitive lithographic printing plate of the present invention can be constructed by providing a photosensitive layer as described above on a support.

The photosensitive layer can be provided by coating a photosensitive composition etc. on a support, but in this case, a predetermined amount of the above-mentioned polymer compound and other additives constituting the photosensitive m-parabolite may be appropriately applied. Prepare a coating solution of the photosensitive composition by dissolving it in a suitable solvent (such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate/acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water or a mixture thereof) and support it. Means for applying and drying on the body can be used. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 5 (l%). In this case, the coating amount of the photosensitive composition is preferably about 0.2 to 10 g/rrr. And it is sufficient.

In the photosensitive lithographic printing plate of the present invention, various supports can be used to form the photosensitive layer. Particularly preferred is an aluminum plate. However, if an aluminum plate is used without treatment, there are problems in that the adhesion of the photosensitive composition is poor and the photosensitive composition decomposes. In order to eliminate this problem, various proposals have been made in the past.

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (US Pat. No. 2.714.066), a method in which the surface of an aluminum plate is treated with an organic acid salt (US Pat. No. 2.714.
No. 066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2
, 946.683), a method of anodizing, and a method of treating with an aqueous solution of alkali metal silicate after anodizing (US Pat. No. 3,181,461).

In a preferred embodiment of the present invention, the surface of the aluminum plate (including the alumina laminate; the same applies hereinafter) is degreased and then grained by a brush polishing method, a pole polishing method, a chemical polishing method, an electrolytic etching method, etc. The grain is preferably grained using an electrolytic etching method which produces deep and uniform grains. The anodizing treatment is carried out, for example, in an aqueous solution of an inorganic salt such as phosphoric acid, chromic acid, boric acid, or sulfuric acid, or an organic acid such as oxalic acid, or a mixture of two or more of these acids, preferably in an aqueous sulfuric acid solution. This is done by passing an electric current through an aluminum plate as an anode. The amount of anodic oxide film is preferably 5 to 60 μ/d, more preferably 5
~30■/drrf.

When carrying out the pore sealing treatment in carrying out the present invention, it is preferable to add a sodium silicate aqueous solution with a concentration of 0.1 to 3% at a temperature of 8.
This treatment is carried out by immersion at 0 to 95°C for 10 seconds to 2 minutes.

More preferably, it is then soaked in water at a temperature of 40 to 95°C for 10 seconds to 2
Soak and process for a minute.

The photosensitive lithographic printing plate of the present invention can be exposed and developed by conventional methods. That is, for example, a negative leaf image can be obtained with respect to the original image by exposing the transparent original image having a line image, halftone image, etc. to light, and then developing with an aqueous developer.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

Any developer can be used to develop the photosensitive lithographic printing plate of the present invention as long as it can develop the plate.

Preferably, a developer containing a specific organic solvent, an alkaline agent, and water as necessary components can be used.

The specific organic solvent herein refers to one that can dissolve or swell the non-exposed area (non-image area) of the layer made of the photosensitive composition of the present invention when contained in the developer.
Furthermore, the solubility in water at room temperature (20°C) is 10.
% or less of organic solvent is preferred. Such organic solvents only need to have the above characteristics, and are not limited to the following:
Examples of these include 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, methylphenyl carbinol, n-amyl alcohol, methylalkyl alcohol; such as xylene alkyl-substituted aromatic hydrocarbons; 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. Further, the content of these organic solvents in the developer is preferably about 1
-20% by weight, and particularly preferable results are obtained when the content is 2-10% by weight.

On the other hand, preferred alkaline agents contained in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium di- or tri-phosphate, and sodium carbonate; , inorganic alkali agents such as ammonium, (B) mono-, di- or trimethylamine, mono.

Examples include organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanol, ethyleneimine, ethylenediamine, and the like.

The content of these alkaline agents in the developer is usually 0.
It is preferably 0.05 to 4% by weight, more preferably 0.5 to 2% by weight.

Further, in order to further improve storage stability, printing durability, etc., it is preferable to include a water-active sulfite in the developer. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, magnesium sulfite, and the like. The content of these sulfites in the developer composition is usually preferably 0.05 to 4% by weight, more preferably 0.1 to 1% by weight.

If such a developer is brought into contact with the photosensitive composition after development and exposure, or is rubbed with the developer, the temperature will be approximately room temperature to 4.
After 10 to 60 seconds at 0[deg.] C., the exposed area of the photosensitive layer was not exposed to light without any adverse effect [Example] Examples of the present invention will be described below. As a matter of course, the present invention is not limited to the following examples.

Prior to specific descriptions of Examples, the polymer compounds and diazo resins used in each Example and Comparative Example will be described.

Under a nitrogen stream, p-hydroxyphenylmethacrylamide (
IIyPMA) 17.7g, ethyl acrylate (E
A) 57.0g, acrylonitrile (AN) 12.7g
11.7 g of itaconic acid (IA) and 1.64 g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60° C. for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was collected by filtration and vacuum-dried at 50°C overnight.

The obtained polymer compound was diluted with tetrahydrofuran (TIF).
When measured by gel permeation chromatography (CGPC: polystyrene standard),
The weight average molecular weight was 80.000.

Under a nitrogen stream, 2-hydroxyethyl methacrylate (HE) was added to a mixed solvent of 65 g of acetone and 65 g of methanol.
MA) 13.3g, ethyl acrylate) (EA)5
0.0g, acrylonitrile (AN) 15.9g,
11.7 g of Itacon M (IA) and 1.64 g of azobisisobutyronitrile were dissolved, and the mixture was refluxed at 60°C for 6 hours without stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. This was collected by filtration and vacuum-dried at 50°C overnight.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
Dissolve in gel permeation chromatography (
As measured by GPC (polystyrene standard), the weight average molecular weight was 75.000.

(9 people) Under a nitrogen stream, add p-hydroxyphenylmethacrylamide (HyPM) to a mixed solvent of 65 g of acetone and 65 g of methanol.
A) 17.7g, ethyl acrylate (HA) 57
．． 0 g, acrylonitrile (AN) 12.7 g, methacrylic acid (MAA) 7.7 g, and azobisisobutyronitrile 1.64 g were dissolved, and the mixture was refluxed at 60° C. for 6 hours with stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound. Filter this out,
It was vacuum-dried at 50° C. for one day and night.

The obtained polymer compound was dissolved in tetrahydrofuran (THF).
i9 and measured by gel permeation chromatography (GPC: polystyrene standard),
The weight average molecular weight of diazo 1b (
1) A p-diazodiphenylamine sulfate 14.5 g (
50 mmol) was dissolved in 40 g of concentrated sulfuric acid under water cooling.

1.05 g (35 mmol) of paraformaldehyde was slowly added dropwise to this reaction solution. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. after that,
Stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered off. After washing the precipitate with ethanol, it was dissolved in 100To1 pure water, and an aqueous solution in which 6.8 g of zinc chloride was dissolved was added to this solution. The resulting precipitate was filtered off, washed with ethanol, and dissolved in 150-pure water. In this liquid, add 8
An aqueous solution in which ammonium hexafluorophosphate (g) was dissolved was added, and the resulting precipitate was filtered off, washed with water and ethanol, and then dried at 25° C. for 3 days to obtain diazo resin (1).

3.5 g (25 mmol) of p-hydroxybenzoic acid
, and p-diazodiphenylamine sulfate 21.75
g (75 mmol) was dissolved in 90 g of concentrated sulfuric acid under water cooling. To this solution, 2.7 g (90 mmol) of paraformaldehyde was slowly added. At this time, the addition was made so that the reaction temperature did not exceed 10°C. After stirring the reaction solution for 2 hours, it was added dropwise to 1N ethanol, and the resulting precipitate was filtered out and washed with ethanol. Precipitate 200
An aqueous solution containing 10.5 g of zinc chloride dissolved in Wi pure water was added. The resulting precipitate was filtered, washed with ethanol, and then dissolved in 300-pure water. Add 1 to this solution
An aqueous solution containing 3.7 g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and then dried at 25°C for - days to obtain a diazo resin (2).

A of Diazo 15 (3) In the synthesis of diazo resin (2), 4.2 g of p-methoxybenzoic acid (25
In the same manner, a diazo resin (3) was obtained.

Next, examples will be described together with comparative examples.

Examples 1-3. Comparative Examples 1 and 2 A grained and anodized aluminum plate was used as a support, and a photosensitive solution (a) or (b) having the following composition was placed on the support.
was coated at a coating weight of 1.8 g/m'' solid content and dried to obtain a photosensitive lithographic printing plate sample.

Photosensitive liquid (a) (photosensitive liquid containing component (B)) 90g Photosensitive liquid (b) (photosensitive liquid not containing component (B)) 190g ethylene glycol monomethyl ether Constituting each example (and comparative example) The photosensitive liquid used for
and Table 1 of polymer compounds shown in the composition of the photosensitive solution A negative transparent original image was placed on the obtained sample, exposed for 30 seconds from a distance of 60a++ with a 2kW metal halide lamp, and then exposed to Konica PS plate developer 5DN-21 for 27 seconds. ℃ for 20 seconds, and then rubbed lightly with absorbent cotton and developed.

The resulting plate was printed on a Heidelberg GTO printing press and
Developability was evaluated based on the amount of dirt on the paper surface.

In addition, the sample after coating was forcibly stored (temperature: 55°C, humidity: 20°C).
%RH for 15 days), then in the same manner as above,
Exposure, development, and printing were performed to evaluate storage developability.

In addition, printing was performed using UV ink (Kasai Best Cure BF Beni, manufactured by Kasai Shiki), and the number of printable sheets of each sample was compared.

In addition, after exposure and development, the solid area of the plate was rubbed with a sponge containing UV ink cleaning oil (Solfit, manufactured by Kuraray) for 1 minute, and the density of the solid area of the plate was measured with a densitometer (red light). Compare the density difference before and after rubbing with UV ink cleaning oil, and
V ink washing oil resistance was evaluated.

Further, ink receptivity was evaluated as follows.

That is, a sample exposed and developed in the same manner as above was coated with Konica PS version gum solution 5GQ-3 (diluted twice), and after drying, printing was performed. The number of sheets required to remove the gum in the image area and obtain normal inking was compared.

Table 2 From Table 2, it can be seen that Examples 1 to 3 are excellent in both the developability immediately after application and unstored, as well as the storage developability after forced storage. Furthermore, it has good UV ink stiffness resistance, good UV washing oil resistance, and is excellent in UV ink suitability. Furthermore, the ink receptivity is also good.

On the other hand, Comparative Example 1, which contains component (A) but does not contain component (B), has excellent developability and suitability for UV ink, but is poor in ink receptivity.

In addition, Comparative Example 2, which does not contain either components (A) or (B),
The suitability for UV inks is also quite poor, and the ink receptivity is also poor.

〔Effect of the invention〕

As mentioned above, the photosensitive lithographic printing plate of the present invention has excellent developability, particularly after long-term storage, and also has excellent stiffness resistance and ink adhesion when printing with UV ink. has.

Claims (1)

[Scope of Claims] 1. A polymer compound containing a structural unit represented by the following general formula [I] in its molecule, and a structural unit represented by the following general formula [VI] and the following general formula [VII] 1. A photosensitive lithographic printing plate, comprising a photosensitive layer containing a polymer compound containing a structural unit in its molecule. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ However, J represents a divalent linking group, and n is 0 or 1. General formula [VI] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R^1^6 represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or an aryl group. General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R^1^7 represents a hydrogen atom, methyl group, or ethyl group, and R^1^8 represents an alkyl group or an aryl group.