JPH035759A - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Background of the invention]

BACKGROUND OF THE INVENTION Various photosensitive compositions have heretofore been proposed, and these are used, for example, as photosensitive lithographic printing plates by being coated on a support.

BACKGROUND ART Compositions containing diazo resins and alkali-soluble/swellable polymers, or photosensitive lithographic printing plates having such compositions as photosensitive layers have been proposed.

It is desired that photosensitive compositions and photosensitive lithographic printing plates have good developability.

Therefore, as mentioned above, various attempts have been made to improve the developability even in the conventional techniques using diazo resins and alkali-soluble/swellable polymer compounds. For example, organic acids such as malic acid, tartaric acid, and polyacrylic acid, and inorganic acids such as phosphoric acid and phosphorous acid are added.

It is thought that such an acid acts as a stabilizer for the diazo resin.

However, in the case of technologies using diazo resins and alkali-soluble/swellable polymer compounds, the above conventional technologies alone cannot
It is still insufficient.

In particular, it has not always been possible to sufficiently improve the developability of the above compositions and printing plates after long-term storage.

Further, in conventional photosensitive lithographic printing plates containing diazo resin, a so-called Marangoni phenomenon occurs, which sometimes causes coating unevenness. Due to the Marangoni phenomenon, when the coating solvent dries during printing plate production, uneven film thickness may occur in the resulting coated bundle, which may form spirals, waves, or other complex patterns. be. Such non-uniformity in film thickness is unfavorable in terms of performance, for example, it deteriorates visible image quality after exposure. Moreover, the appearance of the photosensitive lithographic printing plate itself is unsightly, and its commercial value is significantly impaired in terms of appearance.

[Purpose of the invention]

The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a photosensitive composition and a photosensitive lithographic printing plate using a diazo resin and an alkali-soluble/swellable polymer compound. In addition to significantly improving developability after long-term storage,
The objective is to provide something that can eliminate uneven coating.

[Means and effects for solving the problem 3 The invention according to claim 1 of the present application is a photosensitive material containing a diazo resin, an alkali-soluble/swellable polymer compound, and a nonionic surfactant. With this composition, the above object is achieved.

The invention according to claim 2 of the present application is a photosensitive lithographic printing plate having a diazo resin, an alkali-soluble/swellable polymer compound, and a nonionic surfactant on a support. The purpose has been achieved.

In the present invention, the alkali-soluble/swellable polymer compound refers to an alkali-soluble and/or swellable polymer compound, and includes an alkali-soluble polymer compound, an alkali-swellable polymer compound, and an alkali-soluble and alkali-swellable polymer compound. This is a general term for the concept that includes chemical polymer compounds.

Further, in the present invention, any nonionic surfactant can be used, and it is preferable to select it appropriately depending on the type of other components, such as the diazo resin.

The inventors of the present invention have conducted various studies and experiments from among a huge group of substances, and have found a substance that meets the purpose of the present invention, resulting in the present invention.The above structure has achieved the purpose of the present invention. What happened was unexpected even for the inventors.

The present invention will be further explained below.

First, the diazo resin contained in the photosensitive composition of the present invention and included in the photosensitive lithographic printing plate of the present invention will be described.

The above diazo resin is used as a photosensitive substance.

Any diazo resin can be used in the present invention.

In the present invention, as the diazo resin, a co-condensed diazo resin containing an aromatic compound having one or more of at least one of a carboxyl group or a hydroxyl group and an aromatic diazonium compound as a constituent unit can be preferably used.

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, O-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-methy)Lianilino)benzoic acid M, 4- Phenylsulfonylbenzoic acid, phenol, (
o, m, p)-cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycine, 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 )-7' Lomophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, 6-methialylsalicylic acid, 4.6-dimethylsalicylic acid, p- Hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,6-cymethyl-4-
Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid,
2.4-dihydroxy-6-methylbenzoic acid, 2゜6-
Dihydroxybenzoic acid, 2,6-cyhydroxy-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-toluyl) gallic acid,
Protocatechuyl-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl)acetic acid, 2,6-dihydroxyphenyl)acetic acid, (3,4,5-
1-hydroxyphenyl)acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4-(p-
Hydroxyphenyl)methylbenzoic acid, 4-(O-hydroxybenzoyl)benzoic acid, 4-(2,4-dihydroxybenzoyl)benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid, 4-(p-hydroxyanilino) )
Benzoic acid, bis(3-carboxy-4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl)benzoic acid, 4-(p-hydroxyphenylthio)
Examples include benzoic acid. Among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid, p-
Methoxybenzoic acid and metachlorobenzoic acid.

As the aromatic diazonium compound used as the structural unit of the co-condensed diazo resin, diazonium salts such as those listed in Japanese Patent Publication No. 49-48001 can be used, but diphenylamine-4-diazonium salts are particularly preferred. -4-diazonium salts are
Although derived from 4-amino-diphenylamines, such 4-amino-diphenylamines include 4-amino-diphenylamines.
-Amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4''-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxydiphenylamine, 4-amino- 3-methyldiphenylamine, 4
-amino-3-ethoxy-diphenylamine, 4-amino-3-β-hydroxy-ethoxydiphenylamine,
4-amino-diphenylamine-2-sulfonic acid, 4-
Examples include amino-diphenylamine-2-carboxylic acid and 4-amino-diphenylamine-2°-carboxylic acid. Particularly preferred are 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine.

As the co-condensed diazo resin that can be used in the present invention, those represented by -formation CI) below are preferred.

In one-formation CI), 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 exemplified above.

In the formula, R, R, and R1 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 percent ratio of co-condensed diazo resin to condensed diazo resin is particularly preferably 30-70, nia 0-30, from the viewpoint of providing excellent sensitivity and developability.

The above-mentioned co-condensed diazo resins and condensed diazo resins used in combination with these or independently as diazo resins are:
Known methods, for example, Photo, Sci, f.
ing, Vol. 17, No. 33 (1973), U.S. Patent Nos. 2,063,631 and 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,
The ratio is more preferably 1:0.5 to 0.2:11, and even more preferably 1:1 to 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. A co-condensed diazo resin can be obtained by mixing the components at a ratio of 1:0.7 to 1.5 and reacting at a low temperature for a short period of time, for example, about 3 hours.

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; typical examples include methanesulfonic acid, Chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, Aliphatic and aromatic sulfonic acids such as dimethyl-5-sulfoisophthalate, 2°2',4.4'-tetrahydroxybenzophenone, 1.2.3-)lihydroxybenzophenone, 2.2',4 -) Hydroxyl group-containing aromatic compounds such as lyhydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, C
Examples include perhalogen acids such as 110 and 04. However, it is not limited to this.

Among these, particularly preferred are hexafluorophosphoric acid and tetrafluoroboric 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 which can be preferably used as diazo resins include, for example, the above-mentioned Photographic Ink Science & Co., Ltd.
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 -formation (II) 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 Rs, R, X, and n have the same meanings as in the above-mentioned -formation (1). - in formation (n) R,,
As the alkyl group and alkoxy group of Rg and R3,
For example, an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms may be mentioned, and the alkyl group for R may have a carbon number (n). It can be manufactured according to the method described in the above-mentioned US patent specifications of Photographic Ink Science and Engineering and others 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. Preferably, the ratio is 1:0.7 to 1:1.5, and three culms can be obtained at a low temperature for a short time, for example, 10°C or less.

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

Next, the alkali-soluble/swellable polymer compound contained in the photosensitive composition of the present invention and that the photosensitive lithographic printed matter of the present invention has will be explained. This polymer compound can function as a binder when forming a photosensitive composition.

In the present invention, the alkali-soluble/swellable polymer compound is one that is alkali-soluble, alkali-swellable, or has both properties. One or more kinds of such polymer compounds can be arbitrarily used.

In the present invention, the term "alkali-soluble" refers to a substance that dissolves into an alkaline solution, for example, an alkaline solution having a pH of 12.0 or higher at 25°C. In addition, the term "alkali swelling property" refers to a property in which the volume expands when a liquid permeates in an alkaline solution, and when it is coated on a support, it becomes easy to peel off from the support.

Any alkali-soluble/swellable polymer compound as described above can be used in the present invention.

In addition, in carrying out the present invention, in order to specify the molecular weight of the polymer compound used, the value of the molecular weight measured by GPC using a polystyrene standard can be used.

That is, the weight average molecular weight can be measured by GPC (gel vermini-silane chromatography method), and the number average molecular weight Mn and weight average molecular weight MW can be calculated according to the "Journal of the Chemical Society of Japan" written by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka. "8
By the method described on pages 00 to 805 (1972),
This can be done by leveling the peaks of the oligomer region (connecting the center lines of the peaks and valleys of the peaks).

The polymer compound that can be used in the present invention may be of any type as long as it is alkali-soluble and swellable as described above, and for example, the following compounds can be used. That is, the polymer compounds that can be used include polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane, polyvinyl chloride and its copolymers, polyvinyl butyral resin, polyvinyl formal resin, shellac, epoxy resin, phenol resin, acrylic resin, etc. can be mentioned.

Preferably, it is a copolymer of the monomers shown in (1) to (12) below, which is an alkali-soluble/swellable monomer (1) having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)acrylamide or N -(4-hydroxyphenyl)methacrylamide, o-, m-, p-hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or monomethacrylate.

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

(3) α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride.

(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, N
-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide,
Acrylamides or methacrylamides such as N-nitrophenylamide and N-ethyl-N-phenylacrylamide.

(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-bi-nylpyridine, acrylonitrile, methacrylatel, etc.

Furthermore, a heptamer that can be copolymerized with the above monomer may be copolymerized. Further, the copolymerization pair obtained by copolymerization of the above monomers may be, for example, glycidyl methacrylate,
It also includes, but is not limited to, those modified with glycidyl acrylate and the like.

More specifically, a hydroxyl group-containing copolymer containing the monomers listed in (1) and (2) above is preferred, and an aromatic hydroxyl group-containing copolymer is even more preferred.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added to the above copolymer as necessary.

Particularly preferred as the copolymer which is the alkali-soluble/swellable polymer compound used in the present invention are the following copolymers.

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, (b) the following -formation IA R -CH, -C-.・・・・・・・・・5 to 40 mol% of the structural unit represented by IAN (in the formula, 11711 represents a hydrogen atom or an alkyl group), (c) the following general 2 mA 12 -CIl□-C -・・・・・・・・・I[ACOOR'
3 (wherein R12 represents a hydrogen atom, a methyl group, or an ethyl group, and R'' represents an alkyl group having 2 to 12 carbon atoms or an alkyl-substituted aryl group) with 25 to 60 Preferred are polymeric compounds containing mol %. and its weight average molecular weight is from 20,000 to
Even more preferred are copolymers with a molecular weight of 200.000.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group in (a) above include Japanese Patent Publication No. 52-736
(meth)acrylic acid ester I4 CHt -C- COQ 1,000 GHzcHO-+T-H R1% In the formula, R14 is a hydrogen atom or a methyl group, 171 % 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-hydroxypentyl (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)・・・・・・・・・mA (meth)acrylamide monomer such as (meth)acrylamide, N-(4-hydroxynaphthyl)-(meth)acrylamide; o-, m- or p -Hydroxyphenyl (meth)acrylate monomer; o-, m- or p-hydroxystyrene monomer and the like. Preferably, 〇-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 preferably 1 to 50 mol%, more preferably 5 to 50 mol%, in the polymer compound.
It is selected from a range of 30 mol%.

Examples of the heptamers having a cyano group in the side chain that form the structural unit represented by -Formation IA include acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-
Examples include methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-p-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 the above-mentioned -Formation IIA includes:
Examples include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, and the like. The unit formed from the monomer preferably accounts for 25 to 60 mol% in the polymer compound.
, more preferably from the range of 35 to 60 mol %.

Further, the above-mentioned preferred polymer compound may contain, for example, 2 to 30 mol % of a structural unit having a carboxyl group in its molecular structure.

Monomers forming the structural unit having a carboxyl group include methacrylic acid, acrylic acid, maleic anhydride, maleic acid, and the like. The monomer is selected from the range of 2 to 30 mol%, preferably 5 to 15 mol% in the polymer compound.

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, the alkali-soluble/swellable polymer compound is
In the solid content of the photosensitive composition and in the solid content constituting the photosensitive layer on the support, preferably 40 to 99% by weight,
More preferably, it is contained in an amount of 50 to 95% by weight. Further, in the present invention, the photosensitive diazo resin is preferably contained in an amount of usually 1 to 60% by weight, more preferably 3 to 30% by weight.

Next, the nonionic surfactant contained in the photosensitive composition of the present invention and that the photosensitive lithographic printing plate of the present invention has will be explained.

Any nonionic surfactant can be used in the present invention.

Particularly preferably, polyoxyethylene alkylphenyl ethers and polyethylene glycols can be used. Preferred examples of polyoxyethylene alkylphenyl ethers include polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and others.

However, the nonionic surfactants that can be used in the present invention are not limited to those mentioned above, and various kinds can be used as desired.

In particular, as a diazo resin, the above general formula [! When using the co-condensed diazo resin represented by ], the effects of the present invention can be exhibited with almost any nonionic surfactant.

- Formation (When using a diazo resin other than the co-condensed diazo resin represented by 13, it is particularly effective to use the above-mentioned preferred nonionic surfactants.

Nonionic surfactants that can be preferably used in the present invention are listed below. However, as a matter of course, the present invention is not limited to the following examples.

That is, preferred nonionic surfactants include sorbitan fatty acid ester glycerin fatty acid ester decaglycerin fatty acid ester and other polyglycerin fatty acid esters propylene glycol/pentaerythritol fatty acid ester polyoxyethylene sorbitan fatty acid ester polyoxyethylene sorbitol fatty acid ester polyoxyethylene glycerin Fatty acid ester polyethylene glycol fatty acid ester polyoxyethylene alkyl ether (1
) Polyoxyethylene alkyl ether (2) Polyoxyethylene phytosterol, phytosterol polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative polyoxyethylene alkylamine, fatty acid amide Mention may be made of polyoxyethylene alkylphenyl formaldehyde condensates, single chain length polyoxyethylene alkyl ether polyethylene glycols.

As mentioned above, among these, polyoxyethylene alkyl phenyl ethers and polyoxyethylene, in the present invention, the content of nonionic surfactants in the photosensitive composition or the photosensitive layer of the photosensitive lithographic printing plate is preferably The amount is preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the alkali-soluble/swellable compound.

The photosensitive composition of the present invention or the photosensitive layer of the photosensitive lithographic printing plate of the present invention may contain an acid and/or an acid anhydride.

When using an acid, it can be arbitrarily selected from any organic acid or anhydrous acid. The organic acid is preferably a monocarboxylic acid or a polycarboxylic acid having at least one carboxyl group. Malic acid, tartaric acid, and polyacrylic acid (commercially available under the trade name Jurimer, etc.) can be preferably used. In addition, organic acids (citric acid, citric acid, benzenesulfonic acid, naphthalenesulfonic acid,
-methoxy-2-hydroxybenzophenone-5-sulfonic acid, etc.) can also be used. As an inorganic acid,
Phosphoric acid, phosphorous acid, etc. can be used. These acids can also function as stabilizers.

When using an acid anhydride, the type of acid anhydride is arbitrary, such as acetic anhydride, propionic anhydride, benzoic anhydride, etc.
Examples include those derived from aliphatic/aromatic monocarboxylic acids, and those derived from aliphatic/aromatic dicarboxylic acids such as succinic anhydride, maleic anhydride, gluguric anhydride, and phthalic anhydride.

The photosensitive material composition of the present invention or the photosensitive lithographic printing plate of the present invention may contain a dye, particularly a dye that changes color from color 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 B OH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue 9603 (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 B, peisysofucsin, malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-dimethylaminophenylimino naphthoquine, cyano-p-diethylaminophenyl acetanilide, etc. Examples of pigments that change color from colored to colorless or to a different color include triphenylmethane, diphenylmethane, oxazine, xanthine, iminonaphthoquinone, azomethine, and anthraquinone pigments.

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 preferably contained in the photosensitive composition or the photosensitive layer in an amount of usually about 0.5 to about 10% by weight, more preferably about 1 to 5% by weight.

In the present invention, various additives can be further added.

In addition, alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka Corporation)), and coatings to improve coating properties may also be used. Plasticizers (e.g. butylphthalyl, polyethylene glycol, tributyl citrate,
diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid), oil sensitivity of image area For example, a sensitizer for improving the sensitizing agent (for example, a half-esterified product of a styrene-maleic anhydride copolymer with alcohol described in JP-A-55-527), and the like. The amount of these additives added varies depending on the object and purpose of use, but is generally preferably 0.01 to 30% of the total solid content.
Weight%.

In order to obtain the photosensitive lithographic printing plate of the present invention, for example, predetermined amounts of a diazo resin, an alkali-soluble/swellable compound, a cellulose compound, and, if necessary, various additives are mixed in a suitable solvent (methyl cellosolve, ethyl A coating solution of the photosensitive composition is prepared by dissolving the photosensitive composition in (cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof, etc.), and this is coated on a support and dried. It can be obtained as a printed version. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition is preferably about 0.2 to 10 g/d.

In the photosensitive lithographic printed matter of the present invention, as a support,
Various types can be used. 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. To eliminate this problem,
Conventionally, various proposals have been made.

For example, a method in which the surface of an aluminum plate is grained and then treated with a silicate (U.S. Pat. No. 2,714°066), a method in which it is treated with an organic acid salt (U.S. Pat.
066), a method of treatment with phosphonic acids and their m8 forms (US Pat. No. 3,220.832), a method of treatment with potassium hexafluorozirconate (US Pat. No. 2, US Pat.
, 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 ball 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 5-6
0 ■/dpo is preferable, more preferably 5 to 30 ■/d
d rd.

When carrying out sealing treatment in carrying out the present invention, preferably a sodium silicate aqueous solution with a concentration of 0.1 to 3% is added 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 method can be used to develop the image-exposed photosensitive lithographic printing plate (hereinafter sometimes referred to as "RPS plate"), and for example, various conventionally known methods can be used.

Specifically, the methods include immersing the image-exposed PS plate in a developer, spraying the developer from multiple nozzles onto the photosensitive layer of the PS plate, and exposing 28 plates using a sponge moistened with the developer. Various methods can be used, such as wiping the layer or applying a developer to the surface of the photosensitive layer of the 28 plate with a roller. Further, after applying the developer to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer can be lightly rubbed with a brush or the like.

Any developer can be used to develop the photosensitive composition of the present invention and/or the photosensitive lithographic printing plate of the present invention using the photosensitive composition, as long as it can develop the photosensitive composition.

Preferably, a developer containing a specific organic solvent, an alkaline agent, and water as essential 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 1°C.
0% by weight or less of organic solvent is preferred. Such organic solvents only need to have the characteristics described above, and are not limited to the following, examples of which include ethyl acetate, propyl acetate, etc. , butyl acetate, amyl acetate, benzyl acetate,
Carboxylic acid esters such as ethylene glycol motuptylacetate, butyl acetate, butyl levulinate; Ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; ethylene glycol monobutyl ether, ethylene glycol benzyl ether, petylene glycol monophenyl ether , benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, monochlorobenzene, etc. There is. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ethylene glycol monophenylniter and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developer is preferably approximately 1 to 20% by weight, particularly 2% by weight.
More favorable results are obtained when the amount is ~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, dibasic or tribasic sodium/or ammonium phosphate; , sodium metasilicate 5, an inorganic alkali agent such as sodium carbonate or ammonium, (B) mono-, di- or trimethylamine, mono.

Examples include organic amine compounds such as di- or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triethanolamine, mono-, di- or tri-isopropanolamine, ethyleneimine, and ethylenediamine.

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-soluble 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 F% by weight.

If such a developer is brought into contact with the photosensitive composition after development and exposure, or is rubbed with the developer, after 10 to 60 seconds at room temperature to 40°C, the exposed areas of the photosensitive composition layer will be affected. The photosensitive composition in the unexposed areas is completely removed without causing any adverse effects, for example, a photosensitive lithographic printing plate is obtained.

The developing conditions can be appropriately selected depending on the developing method. - To give an example, for example, in a developing method by immersion, a method of immersing in a developer at about 10 to 40° C. for about 10 to 80 seconds can be used. [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 description of Examples, the polymer compound and diazo resin used in each Example will be explained.

＼ Addition of Al - 130 g of acetone and 130 g of methanol under a nitrogen stream
Dissolve 7.97 g of p-hydroxyphenylmethacrylamide, 25.5 g of ethyl acrylate, 5.3 g of acrylonitrile, 5.3 g of methacrylic acid, and 1.23 g of azobisisobutyronitrile in a mixed solvent of This mixture was refluxed at 60° C. for 6 hours while stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the polymer compound.

This was filtered and vacuum-dried at 50°C overnight.

The obtained polymer compound was dissolved in tetrahydrofuran,
When the molecular weight was measured by gel permeation chromatography (GPC: polystyrene standard), the weight average molecular weight was 45.000.

130g of acetone and 130g of methanol under nitrogen flow
in a mixed solvent of hydroxyethyl methacrylate) 11
．． 05g of ethyl acrylate, 25g of ethyl acrylate, 5.3g of acrylonitrile, 5.6g of methacrylic acid, and 1.23g 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 filtered and vacuum-dried at 50°C overnight.

When the molecular weight was similarly measured by GPC, the weight average molecular weight was 43,000.

Diazo 11″(1) Mu4 p-diazodiphenylamine sulfate 145 g (0,
5 mol) was dissolved in 400 g of concentrated sulfuric acid under water cooling. 10.5 g (0.35 mol) of paraformaldehyde were slowly added to this solution. At this time, the reaction temperature was 10
The temperature was added so as not to exceed ℃. Thereafter, stirring was continued for 2 hours under water cooling. This reaction solution was mixed with 0.5N under water cooling.
was added dropwise to ethanol, and the resulting precipitate was filtered out. After washing the precipitate with ethanol, dissolve the precipitate in 11 pure water,
To this solution was added an aqueous solution containing 68 g of zinc chloride. The resulting precipitate was filtered and washed with ethanol.

Next, the obtained precipitate was dissolved in 1.51% pure water and 80%
An aqueous solution containing g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and dried at 25°C for 3 days to obtain diazo resin (1).
I got it.

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 was slowly added 2.7 g (90 mmol) of rose formaldehyde. At this time, the reaction temperature is 1
It was added so that the temperature did not exceed 0°C. After stirring the reaction solution for 2 hours, it was added dropwise to 11 ethanol, and the resulting precipitate was filtered out and washed with ethanol. The precipitate was dissolved in 200 ml of pure water, and an aqueous solution containing 10.5 g of zinc chloride was added. After filtering the resulting precipitate and washing with ethanol,
It was dissolved in 300ml of pure water. this? 8 liquid, 13.7
An aqueous solution containing g of ammonium hexafluorophosphate was added. The resulting precipitate was filtered, washed with water and ethanol, and dried at 25°C for - days to obtain a diazo resin (2
) was obtained.

Next, an example will be described.

Example 1 An aluminum plate was degreased with a 3% aqueous sodium hydroxide solution, electrolytically etched in a 2% hydrochloric acid bath at 25°C and at a current density of 3A/dm, washed with water, and then etched in a 30% sulfuric acid bath. , anodized for 2 minutes at 30°C and 1.5 A/dm2.Next, with a 1% aqueous sodium metasilicate solution,
The pores were sealed at 85° C. for 30 seconds, washed with water, and dried to obtain an aluminum plate for a lithographic printing plate. On this aluminum plate,
A photosensitive liquid with the following composition has a film weight of 1.7g after drying.
/rrf to obtain photosensitive lithographic printing plate sample No. 1=13 and comparative sample 1.

Composition of Photosensitive Liquid A negative transparent original image was placed on each lithographic printing plate sample prepared as described above, and exposed for 30 seconds from a distance of 60 cm using a 2 kW metal halide lamp.

Next, it was immersed in a developer having the following composition at 25°C for 40 seconds,
It was developed by rubbing it lightly with absorbent cotton. Also under similar conditions 20
The test was also carried out in the case of immersion in a developer for a second.

Developer Composition Each sample after development was printed using a Heidelberg GTO printing machine and the stains on the paper surface were observed, and the results were as shown in Table A.

Next, samples Nos. 1 to 13 before exposure and development, and comparative sample 1 were stored for 5 days at a temperature of 55°C and a humidity of 20% R11 for forced deterioration, and then exposed and developed in the same manner. I printed it and observed the stains on the paper. The results are shown in the table below.

Furthermore, when the coated surface of each sample before storage was observed with the naked eye, the Marangoni pattern was clearly visible on the coated surface of Comparative Sample 1, but the Marangoni pattern was mostly visible in Samples Nos. 1 to 13 according to the present invention. The coated surface was uniform.

In addition, when carried out using diazo resin (2) instead of diazo resin (1), when carried out using polymer compound 2 instead of polymer compound 1, and when carried out by replacing both of them. I also did this, and the same results were obtained.

Example 2 A photosensitive solution having the following composition was applied onto a grained board that had been anodized and grained in the same manner as in Example 1, until the coating weight after drying was 1.7.
mg/d+w! It was applied so that

The obtained lithographic printing plate samples Nos. 14 to 26 and Comparative Sample 2 were exposed and developed in the same manner as in Example 1 using the same developer as in Example 1, and the evaluation results are shown in Table-C.

In addition, as in Example 1, each sample was heated at a temperature of 55°C.
The table shows the results when stored for 7 days at a humidity of 20% R11.

In addition, when carried out using diazo resin (2) instead of diazo resin (1), when carried out using polymer compound 2 instead of polymer compound 1, and when carried out by replacing both of them. [Effects of the Invention] As described above, the photosensitive composition and lithographic printing plate of the present invention have extremely good developability, especially developability after long-term storage, and It has the effect that coating unevenness due to the Marangoni phenomenon does not occur.

Patent issuer Junjin Konica Co., Ltd. Same Mitsubishi Kasei Corporation

Claims (1)

[Scope of Claims] 1. A photosensitive composition containing a diazo resin, an alkali-soluble/swellable polymer compound, and a nonionic surfactant. 2. A photosensitive lithographic printing plate having a diazo resin, an alkali-soluble/swellable polymer compound, and a nonionic surfactant on a support.