JPH02189544A - Production of planographic printing plate - Google Patents

Abstract

PURPOSE:To form the detail printed matter which has no contaminations without having toxicity, smells, danger to fires, etc., by using a cocondensation compd. contg. an arom. compd. having at least one specific group and an arom. diazonium compd. as constituting units. CONSTITUTION:The cocondensation compd. contg. the arom. compd. having at least one group selected from a carboxyl group, hydroxyl group, sulfonic acid group, sulfonate group, sulfinic acid group, and sulfinate group, and the arom. diazonium compd. as the constituting units is used as a photosensitive component and the photosensitive planographic printing plate having a photosensitive layer contg. this component and a lipophilic high-molecular compd. on a base body is subjected to image exposing and is then developed by an aq. alkaline soln. which has >=pH 12 and contains substantially no org. solvent, by which the planographic printing plate is produced. The toxicity and the smells as well as the danger to fires and the remaining of diazo are obviated in this way and the printability is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing a lithographic printing plate, and particularly to a negative photosensitive lithographic printing plate.

(Prior art) Photosensitive printing plates are generally produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, and polymerizing or polymerizing the irradiated areas. It is cross-linked and insolubilized in a developing solution, and the non-irradiated areas are eluted into the developing solution, and each area is divided into an image area that repels water and accepts oil-based ink, and a non-image area that accepts water and repels oil-based ink. This can be obtained by making it an image part.

In this case, the photosensitive composition used is a diazo resin such as a condensate of p-diazodiphenylamine and formaldehyde, and the developer containing an organic solvent and an alkaline agent is widely used. .

However, organic solvents are generally toxic and odoriferous, and pose a danger to flames, and they also have BOD levels in waste liquids.
It has many disadvantages such as being subject to regulations, and costs are also high. Therefore, there is a need for a developing solution that does not contain organic solvents and does not have these problems. However, since conventional diazo resins generally do not have alkali solubility, they are difficult to use for photosensitive compositions containing them. After that, when developing with an alkaline developer, the developability, especially under under conditions, is not good, and the diazo resin remains in the form of a film on the surface of the support after development, resulting in so-called diazo residue. There are problems that lead to a decline in aptitude.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a lithographic printing plate produced by developing with an alkaline aqueous solution that does not substantially contain an organic solvent by using an alkali-soluble photosensitive composition.

(Means for solving the problem) The above purpose is to
By using as a photosensitive component a co-condensation compound containing an aromatic compound having at least one group selected from the group consisting of sulfonic acid groups, sulfinic acid groups, and sulfinic acid groups and an aromatic diazonium compound as a constituent unit. achieved.

That is, the gist of the present invention is to provide an aromatic compound having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group, and an aromatic diazonium compound. After imagewise exposure of a photosensitive lithographic printing plate having a photosensitive layer containing a co-condensed compound containing as a constituent unit and a lipophilic polymer compound on a support, an alkaline aqueous solution having a pH of 12 or higher and substantially free of organic solvents is applied. The present invention relates to a method for producing a lithographic printing plate, characterized in that the lithographic printing plate is produced by developing the plate.

To explain the present invention below, the co-condensation compound (hereinafter referred to as "diazo resin") used in the present invention includes, for example, an aromatic diazonium compound unit represented by the following formula I and the following general formula 2. Examples include cocondensates containing aromatic compound units having specific substituents.

In the formula, R, R, and R3 are each hydrogen, an alkyl group, or an alkoxy group, R4 and R1 are each hydrogen, an alkyl group, or a phenyl group, X is PF or BF, and Y is ~NH
--3- or -0-1Z has at least one group selected from the group consisting of carboxyl group, hydroxyl group, sulfonic acid group, sulfonic acid group, sulfinic acid group, and sulfinic acid group as a substituent, and represents a phenylene group or naphthylene group with or without a substituent.

Such a diazo resin can be obtained by co-condensing an aromatic diazo compound represented by the following formula (1) with an aromatic compound representing Z in the formula (1) (hereinafter simply referred to as a Z compound) with an active carbonyl compound. It will be done.

One aromatic diazo compound is represented by the following formula (2): In the formula, RISR2, R3, X and Y have the same meanings as in the formula (2). Examples of R+, Rz and R3 include hydrogen, alkyl groups such as methyl and ethyl groups, and alkoxy groups such as methoxy and ethoxy groups, with hydrogen or methoxy groups being preferred, and hydrogen being particularly preferred. Among the groups represented by Y, -NH- is preferred.

Specific examples of such aromatic diazo compounds used in the present invention include 4-diazo-4'-methoxydiphenylamine hexafluorophosphate, 4-diazo-4'-ethoxydiphenylamine hexafluorophosphate , 4-diazo-4'
-Proboxydiphenylamine/tetrafluoroborate, 4
-Diazo-3-methoxydiphenylamine/hexafluorophosphate, 4-diazo-3-methoxydiphenylamine/
Examples include tetrafluoroborate, 4-diazo-diphenylamine/hexafluorophosphate, and the like. Among these, preferred aromatic diazo compounds include 4-diazo 4'-methoxydiphenylamine salt, 4-diazo-4'-ethoxydiphenylamine salt, 4-diazo-3-methoxydiphenylamine salt, and 4-diazo-diphenylamine salt.

In addition, the other two compounds have at least one substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group, and have other substituents. A phenyl compound or a naphthyl compound with or without a sulfonic acid group, preferably a phenyl compound substituted with a sulfonic acid group or a sulfonic acid group.

Examples of other substituents in Z compound include amino group,
Examples include carboxyl groups and halogens such as chlorine.

Specific examples of such Z compounds include benzenesulfonic acid, sodium benzenesulfonate, disodium m-benzenedisulfonic acid, p-)toluenesulfonic acid, sodium p-toluenesulfonate, p-)toluenesulfinic acid, p-toluene. Sodium sulfinate, benzenesulfinic acid sorta, a, niline-2-sulfonic acid, 4-amino-m-1-
Luenesulfonic acid, 4-amino-m-)Sodium luenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 1-
Naphthalenesulfonic acid, 1-amino-2-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 7
-amino-1,3-naphthalenedisulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 4-amino-1
- Sodium naphthalenesulfonate, sodium 5-amino-1-aphthalenesulfonate, sodium 6-amino-1-naphthalenesulfonate, sodium 5-sulfoisophthalate, 2
-Sul# Benzoic acid, p-chlorobenzenesulfonic acid,
Benzoic acid, 0-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-methoxybenzoyl)benzoic acid,
4-(p-methylanilino)benzoic acid, 4-phenylsulfonylbenzoic acid, phenol, (o, m.

p) Cresol, xylenol, resorcinol, 2-methylresorcinol, (om,p)-methoxyphenol, m
-Ethoxyphenol, catechol, phloroglycin,
P-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcinol, biphenyl 4,4-diol, 1.2.4-benzenetriol, bisphenol A, 2.4-dihydroxybenzophenone, 2゜3.
4-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-propyl salicylic acid, 6-lauryl salicylic acid, 6
-styarylsalicylic acid, 4,6-dimethylsalicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid,
2,6-dimethyl-4-hydroxybenzoic acid, 2,4-
Dihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 2.6-dihydroxybenzoic acid, 2.6
-cyhydroxy-4-benzoic acid, 4-chloro-2゜6-
Dihydroxybenzoic acid, 4-methoxy-2゜6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2
, 4.5-) dihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(
p-)ruyl) gallic acid, protocatechoyl-gallic acid, 4,6-cyhydroxyphthalic acid, (2,4-dihydroxyphenyl)acetic acid, (2,6-dihydroxyphenyl)acetic acid, (3,4,5) -)dihydroxyphenyl)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)benzoic acid, etc. Among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, metachlorobenzoic acid,
Benzene sulfonic acid, sodium benzene sulfonate, p-
) luenesulfonic acid, sodium p-toluenesulfonate,
P-toluenesulfine M, p-) Sodium toluenesulfinate, benzenesulfinic acid, sodium 5-sulfoisophthalate, 2-sulfobenzoic acid, 4-amino-m-toluenesulfonic acid, 4-amino-m-toluenesulfonic acid Soda, 1-naphthalenesulfonic acid, 2-amino-1
, 5-naphthalenedisulfonic acid, sodium 5-amino-1-naphthalenesulfonic acid, and p-chlorobenzenesulfonic acid.

The photosensitive diazo resin according to the present invention can be prepared by a known method, for example, Photographic Science &
Vol. 33 (1973L U.S. Pat. No. 2,063.63)
According to the methods described in the specifications of No. 1 and No. 2,679,498, in sulfuric acid, phosphoric acid, or hydrochloric acid,
It can be obtained by polycondensing the diazonium salt represented by Z compound and aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

In addition, the aromatic diazo compound represented by the above-mentioned formula (■) and Z
The molar ratio of the compound to be charged is 1:0.1 to 0°1:1, preferably O,S:t to 1:0.2, more preferably ]:1.
~1:0.2. In this case, the molar ratio of the sum of the aromatic diazo compounds and Z compounds represented by general 2 and the aldehydes or ketones is usually 0.6 to 1.5:t.
A diazo resin can be obtained by charging the mixture at a ratio of 4:1, preferably 0.7 to 1°, and reacting at a low temperature for a short period of time, for example, about 3 hours.

The counter anion of the diazo resin used in the present invention is
Hexafluorophosphoric acid and tetrafluoroboric acid.

Specific examples of the diazo resin in the present invention include benzenesulfonic acid 4-diazo-4'-methoxydiphenylamine/sun hexafluoride l salt-#lumaldehyde resin, benzenesulfonic acid sodium 4-diazo-4'-methoxydiphenylamine・Hexafluorophosphate-formaldehyde resin, P-toluenesulfonic acid-4-diazo-4'-methoxydiphenylamine ・Hexafluorophosphate-formaldehyde resin, benzenesulfonic acid sodium 4-diazo-3-methoxydiphenylamine・Hexafluorophosphate-
Formaldehyde resin, m-benzenedisulfonic acid disodium 4-diazo-4'-methoxydiphenylamine,
Hexafluorophosphate-formaldehyde resin, 4-amino-m-)luenesulfonic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehy YHJ'fx, 1-/naphthalenesulfonic acid- 4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 1-amino-2-naphthalenesulfonic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin,
5-amino-1-naphthalenesulfonic acid soda 4-diazo-diphenylamine/hexafluorophosphate-formaldehyde resin, 4-amino-m-1 luenesulfonic acid sorter 4-diazo-4'-methoxydiphenylamine/
Tetrafluoroborate-formaldehyde resin, 2-sulfobenzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, p-toluenesulfonic acid sodium 4-diazo-4'-methoxy Diphenylamine/hexafluorophosphate-formaldehyde resin, sodium benzenesulfonate 4-diazo-diphenylamine/hexafluorophosphate-formaldehyde resin, p-)luenesulfinic acid-4-diazo 4'methoxydiphenylamine/hexafluoride Phosphate-formaldehyde resin, p-toluenesulfinic acid sodium 4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, benzenesulfinic acid sodium 4-diazo-4'-methoxydiphenylamine/
Hexafluorophosphate - formaldehyde resin salicylic acid -
4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, 4-methylsalicylic acid-4-diazodiphenylamine/tetrafluoroborate-formaldehyde resin, p-hydroxybenzoic acid-4-diazodiphenylamine/phosphorus hexafluoride acid salt-formaldehyde resin,
2.4-dihydroxybenzoic acid-4-diazodiphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate-formaldehyde resin, gallic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, fluoro Glucine carboxylic acid-4-
Diazodiphenylamine/tetrafluoroborate-a7taldehyde resin, (2,4=dihydroxyphenyl)acetic acid-4-(N-ethyl-N-hydroxyethyl)-aminobenzenediazonium/hexafluorophosphoric acid Salt - Benzaldehyde resin, 4-(o-hydroxybenzoyl)benzoic acid-4-diazodiphenylamine hexafluorophosphate -
Formaldehyde resin, 4-(p-hydroxyphenoxy)benzoic acid-4-diazophenylamine/hexafluorophosphate-formaldehyde resin, 4-(p-hydroxyanilino)benzoic acid-4-diazodiphenylamine/hexafluoride Phosphate-formaldehyde resin, 4-(p-hydroxyphenylsulfonyl)benzoic acid-4-diazodiphenylamine, hexafluorophosphate-formaldehyde resin, p-cresol-4-diazodiphenylamine.
Tetrafluoroborate-formaldehyde resin, resorcin-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin-2-methylresorcin-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, p-methoxy Phenol-4-diazodiphenylamine/2-hydroxy-4-methoxybenzophenone-5-sulfonate-acetaldehyde resin, pyrogallol-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, phloroglycine-4-diazodiphenylamine/ Tetrafluoroborate-acetone resin, 4,4'-dihydroxydiphenyl ether-4-
Diazophenylamine/hexafluorophosphate-acetaldehyde resin, p-hydroxyethylphenol-4-diazodiphenylamine/hexafluorophosphate-benzaldehyde resin, 2,4-dihydroxybenzophenone-4
- Diazodiphenylamine/hexafluorophosphate - formaldehyde resin, 4,4'-dihydroxydiphenylamine -4-diazodiphenylamine/hexafluorophosphate - formaldehyde resin, 4-anilinobenzoic acid-4-
Among these, preferred are diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, p-phenoxybenzoic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, etc. is benzenesulfonic acid-4-diazo-4
'-Methoxyphenolamine hexafluorophosphate-Formaldehyde resin, Sodium benzenesulfonic acid 4-
Diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde I fat, p-chlorobenzenesulfonic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 1-naphthalene Sulfonic acid-4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, 4-amino-m-toluenesulfonic acid sodium 4-
Diazo-4'-methoxydiphenylamine/tetrafluoroborate-formaldehyde resin, p-toluenesulfonic acid-4-diazo-4'-methoxydiphenylamine
Hexafluorophosphate-formaldehyde resin, p-toluenesulfonic acid sodium 4-diazo-4'-methoxydiphenylamine/hexafluorophosphate-formaldehyde resin, p-toluenesulfinic acid-4-diazo-4'-methoxy diphenylamine/hexafluorophosphate-formaldehyde resin, resorcinol-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, 2-methylresorcin-4-diazophenylamine/hexafluorophosphate-formaldehyde resin, Pyrogallol-4-
Diazodiphenylamine/hexafluorophosphate - formaldehyde resin, 2,4-dihydroxybenzophenone -
4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, salicylic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin, p
-Hydroxybenzoic acid-4-diazodiphenylamine・
Hexafluorophosphate-formaldehyde resin, 2. 4-
') Hydroxybenzoic acid-4-diazodiphenylamine/2-hydroxy-4-methoxybenzophenone-5-
sulfonate-formaldehyde resin, and 4-(p
-Hydroxyanilino)benzoic acid-4-diazodiphenylamine/hexafluorophosphate-formaldehyde resin.

The diazo resin of the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions, but in order to effectively serve the purpose of the present invention, Those with a molecular weight of about 400 to 10,000 can be used, but preferably about 800 to 5,000.
A value of 0 is appropriate.

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

As this lipophilic polymer compound, the following (1) to 02)
Examples include copolymers whose structural units are the monomers shown below and which usually have a molecular weight of 20,000 to 200,000.

(1) Acrylamides, methacrylamides, acrylic esters, and methacrylic esters having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)
Acrylamide or N-(4-hydroxyphenyl)methacrylamide, 〇-m-1p-hydroxystyrene,
0-1m-1P-hydroxyethyl acrylate or methacrylate, (2) acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid, α,β-unsaturated carboxylic acids such as methacrylic acid, maleic anhydride, itaconic acid, (4)
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-acrylate
(Substituted) alkyl acrylates such as chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, hydroxybutyl methacrylate, glycidyl methacrylate, (Substituted) alkyl methacrylates such as N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (9) Styrene, α-methylstyrene, methylstyrene, chloro Styrenes such as methylstyrene, vinyl ketones such as 0ω methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) olefins such as ethylene, propylene, imbutylene, butadiene, isoprene, Q7J N-vinyl Furthermore, monomers that can be copolymerized with the above monomers may be copolymerized, such as pyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, and methacrylateril. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, it contains the monomers listed in (1) and (2) above. A copolymer having a hydroxyl group is preferable,
More preferred are copolymers having aromatic hydroxyl groups.

The copolymer preferably contains an α,β-unsaturated carboxylic acid listed in (3), and the copolymer preferably has an acid value of 10 to 100.

The preferred molecular weight of the above copolymer is 30,000 to 130,000.

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

The lipophilic polymer compound used in the present invention is usually 40 to 990 to 99% by weight or 50 to 99% by weight in the solid content of the photosensitive composition.
Contains 95% by weight. Further, the photosensitive diazo resin used in the present invention is usually 1 to 60% by weight, preferably 3 to 3% by weight.
Contains 0% by weight.

A dye can further be used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, one that changes color tone by reacting with free radicals or acids can be preferably used.

Here, "the color tone changes" includes both a change from colorless to a colored tone, and a change from a color to colorless or a different colored tone. Preferred dyes are those that change color tone by forming salts with acids.

For example, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue #603 [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 auramine, 4-p-diethylaminophenylimino naphthoquinone, triphenylmethane, diphenylmethane represented by cyano-p-diethylaminophenyl acetanilide, etc. type, oxazine type, xanthine type,
Iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes are examples of color-changing agents that change color from colored to colorless or to a different colored tone.

On the other hand, examples of color changing agents that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, 0-chloroaniline, I, 2゜3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis -dimethylaminodiphenylamine,
1.2-Dianilinoethylene, p,p',p"-tris-dimethylaminotriphenylmethane, p,p'-bis-dimethylaminodiphenylmethylimine, p.

p', p'-) riamino-〇-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-
Examples include primary or secondary arylamine dyes typified by anilinonaphthylmethane and p,p'p"-triaminotriphenylmethane.

Particularly preferably triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylamine dyes, particularly Victoria Pure Blue B OH.

The above-mentioned dye is usually contained preferably in an amount of about 0.5 to about 10% by weight, more preferably in an amount of about 1 to 5% by weight in the photosensitive composition.

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

For example, alkyl ethers (
(e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka Corporation)), plasticizers for imparting flexibility and abrasion resistance to coating films. agents (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), fat-sensitizing agents for improving the fat-sensitivity of image areas (for example, JP-A-55-527) Half esters of the styrene-maleic anhydride copolymers described above with alcohol, etc.), 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.)], development accelerators (e.g., higher alcohols, acid anhydrides, etc.), and the like. The amount of these additives added varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

When such a photosensitive composition is applied to the production of a photosensitive lithographic printing plate, it is coated on a suitable support.

The support used in the photosensitive lithographic printing plate is as follows:
Paper, plastic (e.g. polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate , plastic films such as polyethylene, polypropylene, polycarbonate polyvinyl acetal, etc., paper or plastic films laminated or vapor-deposited with metals such as those mentioned above, steel plates plated with aluminum or chrome, etc. Among these, in particular, Aluminum and aluminum-coated composite supports are preferred.

Further, the surface of the aluminum material is preferably roughened for the purpose of increasing water retention and improving adhesion with the photosensitive layer.

Examples of surface roughening methods include generally known methods such as brush polishing, ball polishing, electrolytic etching, chemical etching, liquid honing, and sandblasting, and combinations thereof, and preferably brush polishing, electrolytic etching, and chemical etching. Mention may be made of target etching and liquid honing, among which roughening methods involving the use of electrolytic etching are particularly preferred. The electrolytic bath used in electrolytic etching is an aqueous solution containing an acid, an alkali, or a salt thereof, or an aqueous solution containing an organic solvent. Liquid is preferred. Further, the roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary. It is desirable that the aluminum plate thus obtained is subjected to anodizing treatment, and particularly preferred is a method of treatment in a bath containing sulfuric acid or phosphoric acid. Further, if necessary, a sealing treatment using an alkali silicate or hot water, and a surface treatment such as immersion in a water-soluble polymer compound or an aqueous potassium fluorozirconate solution can be performed.

To provide the above photosensitive composition on a support, predetermined amounts of a photosensitive diazo resin, a lipophilic polymer compound, and optionally various additives are mixed with a suitable solvent (methyl cellosolve,
Prepare a coating solution of the photosensitive composition by dissolving it in ethyl cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof, apply this onto a support, and dry it. do it. The concentration of the photosensitive composition at the time of coating is preferably in the range of 1 to 50% by weight. In this case, the coating amount of the photosensitive composition may be approximately 0.2 to 10 g/rrl.

A conventional method is applied to coat the photosensitive material on the support. That is, by exposing a transparent original image having a line image, a halftone image, etc. to light, and then developing it with an aqueous developer, a negative relief image can be obtained with respect to the original image. Examples of active light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The alkaline aqueous solution according to the present invention is substantially free of organic solvents.

"Substantially no organic solvent" means that the organic solvent is not contained in such an amount as to impair the above-mentioned sanitary and safety effects, and - 1% by weight or less in the developer composition for boat fishing. If so, there is no problem.

In the present invention, the preferred organic solvent content is 0.5% by weight.
The following is a more preferable embodiment in which it is not contained at all. The alkaline agent used in the developer according to the present invention is preferably potassium silicate, lithium silicate, sodium silicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Sodium triphosphate, sodium diphosphate, potassium triphosphate, potassium diphosphate, sodium carbonate,
Examples include potassium carbonate. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, or sodium silicate is most preferable because it has good development gradation.
O! ) / CM) =0.5~1゜5 (here (
SiO□] and (M) indicate the molar concentration of SiO□ and the molar concentration of total alkali metal, respectively. ), and 5iO
A developer containing 0.8 to 8% by weight of z is preferably used. Of this alkali silicate composition, especially in terms of molar ratio (
SiO□]/(M]=0.5 to 0.75, and S
A developer solution with in. of 0.8 to 4% is preferably used because it is easy to neutralize the developer waste solution due to its low concentration.
．． The molar ratio is more than 75 and up to 1.3, and SiO□
A developer containing 1 to 8% by weight is preferably used because it has a high buffering power and a high processing ability. The pH (25°C) of the developer according to the present invention is 12 or more, preferably 12
．． 5 to I4. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite can be added to the 2H developer.

The preferred content of sulfite in the developer composition is:
The amount is 0.05 to 4% by weight, more preferably 0.1 to 1% by weight.

In addition, anionic surfactants and amphoteric surfactants such as those described in JP-A-50-51324 and JP-A-59-75255 and JP-A-60 are also added to the developer.
By containing at least one of the nonionic surfactants as described in Japanese Patent Application Laid-Open No. 55-95946 and Japanese Patent Application Laid-open No. 56-1
As described in Japanese Patent No. 42528, by incorporating a polymer electrolyte, the wettability to the photosensitive composition can be improved and the gradation can be further improved, and thus it is preferably used. The amount of surfactant added is not particularly limited, but O
, OO3-3 weight% is preferred, and a concentration of 0.006-1% by weight is particularly preferred. Further, it is preferable that the alkali silicate contains at least 20 mol% of potassium as the alkali metal in all the alkali metals, since the generation of insoluble matter in the developer is small, and more preferably 90 mol% or more of potassium. , most preferably when the potassium content is 100 mol %.

Furthermore, the developer used in the present invention can contain an antifoaming agent. Suitable antifoaming agents include organosilane compounds.

Various conventionally known methods can be used to develop the photosensitive lithographic printing plate according to the present invention which has been imagewise exposed with the developer as described above. Specifically, a method of immersing an image-exposed photosensitive lithographic printing plate according to the present invention in a developer;
A method of ejecting a developer from a number of nozzles onto the photosensitive layer of the photosensitive lithographic printing plate according to the present invention, and wiping the photosensitive layer of the photosensitive lithographic printing plate according to the present invention with a sponge moistened with the developer. method, and a method of applying a developer to the surface of the photosensitive layer of the photosensitive lithographic printing plate according to the present invention with a roller. Further, after applying a developer to the photosensitive layer of the photosensitive lithographic printing plate according to the present invention in this manner, the surface of the photosensitive layer may be lightly rubbed with a brush or the like. The developing conditions can be appropriately selected depending on the developing method. - To give an example, for example, in a development method by immersion, about 10
A method of immersing the film in a developer solution at ~40°C for about 10 to 80 seconds is selected.

〔Example〕

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Production of Aluminum Plate-1 An aluminum plate with a thickness of 0.24 mm was weighed at 17 g/1.
2 at 50A/cta'' in a hydrochloric acid bath at a bath temperature of 25°C.
Electrolytic polishing was performed for 5 seconds to obtain a grained plate with a maximum roughness of 4 μm. The grained board was placed in a 40% by weight phosphoric acid bath at a bath temperature of 3.
Anodic oxidation treatment was performed at 5°C and 3.2A/cm2 for 20 seconds. Next, the anodized aluminum plate is
The pores were sealed by immersion in a 1% sodium metasilicate solution at 90'C for 30 seconds.

Thereafter, it was washed with water and dried to obtain an aluminum plate-1.

Synthesis of diazo resin-1 Sodium benzenesulfonate 4.5 g (0,025 mol)
, and 24.3 g (0,075 mol) of 4-diazo-4'-methoxydiphenylamine sulfate were dissolved in 90 g of concentrated sulfuric acid under water cooling. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) were slowly added. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was poured into 11 ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was
It was dissolved in 0 ml of pure water, and to this solution was added a cold concentrated aqueous solution in which 10.5 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and dissolved in 300 ml of pure water. A cold concentrated aqueous solution containing 13.7 g of ammonium bexafluorophosphate was added to this solution. The resulting precipitate was filtered, washed with water, and then dried at 30°C for one day and night to obtain diazo resin 1.

When the molecular weight of this diazo resin 1 was measured by GPC (gel permeation chromatography), the weight average molecular weight was about 2,300.

Synthesis of Diazo Resin-2 3.5 g (0,025 mol) of p-hydroxybenzoic acid and 22.0 g (0,025 mol) of 4-diazodiphenylamine sulfate
, 025 mol) was dissolved in 90 g of concentrated sulfuric acid under water cooling.

After this reaction, 2.7 g of roseformaldehyde (0,0
9 mol) was added slowly. At this time, the reaction temperature was 1O
It was added so as not to exceed oC. Thereafter, stirring was continued for 2 hours under water cooling.

This reaction mixture was poured into if ethanol under water cooling,
The resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 200 mf of pure water, and 10.5 g was added to this solution.
A cold concentrated aqueous solution of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and then filtered at 300mf.
was dissolved in pure water.

A cold concentrated aqueous solution containing 13.7 g of ammonium hexafluorophosphate was added to this solution. The resulting precipitate was filtered, washed with water, and then dried at 30°C for 1 day and night to obtain diazo resin-2.

When the molecular weight of this diazo resin-2 was measured by GPC, it was found to be about 2000 in weight average molecular weight.

Synthesis of Diazo Resin-3 Diazo Resin-3 was prepared in the same manner as in the synthesis of Diazo Resin-1, except that 3.9 g (0,025 mol) of p-toluenesulfinic acid was used for the sodium benzenesulfonic acid in Diazo Resin-1. I got it. When the molecular weight was measured by GPC,
The weight average molecular weight was approximately 2,500.

Synthesis of diazo resin-4 4-diazo-4'-methoxydiphenylamine sulfate of diazo resin-1 was converted into 4-diazodiphenylamine sulfate 2.
Diazo resin-4 was obtained in the same manner as in the synthesis of diazo resin 1, except that the amount was changed to 2.0 g (0,075 mol). G
When the molecular weight was measured by PC, the weight average molecular weight was about 2450.

Synthesis of diazo resin-5 P-diazodiphenylamine sulfate 14.5 g (50
mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. To this reaction solution, 1.5 g (50 mmol) of rose formaldehyde was slowly added dropwise. At this time, the reaction temperature is 1
It was added 2 times so as not to exceed 0°C. After that, 2
Stirring was continued under water cooling for an hour.

This reaction mixture was added dropwise to 500a+f of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol,
This precipitate was dissolved in 100 mf of pure water, and 6.
A cold concentrated aqueous solution of 8 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and then washed with 150
n/! was dissolved in pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for 11 days to obtain diazo resin-5.

When the molecular weight of this diazo resin-5 was measured by GPC, it was found that it contained about 50 mol% of pentamers or more.

Synthesis of polymer compound-1 N-(4-hydroxyphenyl) methacrylamide 53
g1 Acrylonitrile 16g, methyl methacrylate 30
g1 Acetone-ethanol 1:1 mixed solution of 8 g of ethyl acrylate, 2 g of methacrylic acid, and 3.3 g of azobisisobutyronitrile, 220 nj! After dissolving the mixture in the solution and purging it with nitrogen, it was heated at 60°C for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 90 g of polymer compound 1.

When the molecular weight of this lipophilic polymer compound 1 was measured by gel vermini-silane chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was 290,000.

Synthesis of polymer compound-2 21g of acrylonitrile, 22g of methyl methacrylate
All procedures were carried out in accordance with the synthesis of polymer compound-1, except that ethyl acrylate was changed to 6 g.

The weight average molecular weight was 32,000.

Synthesis of polymer compound-3 N-(4-hydroxyphenyl) methacrylamide)''1
0.0g, acrylonitrile 25g1 ethyl acrylate 60g, methacrylic M5g and abbisisobutyronitrile 2.0g in acetone-methanol 1:1 mixed solution 120mj! After dissolving the mixture in a nitrogen atmosphere, the mixture was heated at 60°C for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the white precipitate that had stopped was collected by filtration and dried to obtain 90 g of polymer compound-3.

When the molecular weight of this polymer compound-3 was measured by GPC, the weight average molecular weight was 63,000.

Examples 1 to 7 Comparative Examples 1 to 2 After applying a photosensitive liquid having the following composition to the aluminum plate-1 obtained as described above using a whirler,
It was dried at °C for 3 minutes to obtain a photosensitive planographic printing plate.

(Photosensitive liquid composition) High molecular compound Diazo resin described in Table-1 Jurimer AC-
10L 0.3g (manufactured by Nippon Pure Chemical) Victoria Pure Blue B OH0.2g (manufactured by Hodogaya Chemical) PP-3121” 0.05g Methyl cellosolve 70mff1”PP-3
121 The obtained photosensitive lithographic printing plate was heated to 3 to 1 using an ultra-high pressure mercury lamp.
After exposure for 30 seconds from a distance of 0.00 cm, development was performed at 25°C for 45 seconds using developer-1 or developer-2 shown below.

In addition, each photosensitive lithographic printing plate was left under conditions of 55° C. for 3 days to undergo forced deterioration, and then exposed and developed under the same conditions as above.

Furthermore, among these, printing was performed using the one developed with developer-1.

(Developer-1) (Developer-2) water 1tJI! .

From the above Examples 1 to 7 and Comparative Examples 1 to 2, it can be seen that the method for producing a lithographic printing plate of the present invention improves problems such as toxicity, odor, danger to flame, etc., and provides excellent printed matter without stains. I understand that.

(Effects of the Invention) As explained in detail above, the present invention provides an extremely excellent method for producing lithographic printing plates that provides clean, detailed printed matter without problems such as toxic odors and flame hazards. It will be done.

Applicant Mitsubishi Kasei Corporation Haka 1 person Agent: Patent attorney Haseyo - 1 other expert Continued Supplementary Masakichi Heisei 1 & 1, 81st zS day Display of incidents teenager

Claims (1)

[Claims] A cocondensation compound containing an aromatic diazonium compound as a structural unit and an aromatic compound having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a sulfonic acid group, a sulfonic acid group, a sulfinic acid group, and a sulfinic acid group. , and a photosensitive layer containing a lipophilic polymer compound,
After image exposure of the photosensitive lithographic printing plate on the support, pH
A lithographic printing plate is produced by developing with 12 or more alkaline aqueous solutions substantially free of organic solvents.
A method of manufacturing a lithographic printing plate.