JPH02195356A - Production of planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain good printing characteristics even if an org. solvent is not used by using a planographic printing plate formed by incorporating other specific components in addition to a diazo resin into a photosensitive layer and using an aq. alkaline soln. of PH >=12 at the time of development. CONSTITUTION:The photosensitive planographic printing plate having the photosensitive layer contg. a diazo compd., lipohilic high-polymer compd., nonionic surfactant, and/or fluorine surfactant on a base is developed by the aq. alkaline soln.which has PH >=12 and contains substantially no org. solvent after image exposing. The diazo compd. to be incorporated into the photosensitive compsn. of the planographic printing plate includes the diazo resin represented by the condensation product of an arom. diazonium compd. and, for example, an active carbonyl-contg. compd., more particularly formaldehyde, and the diazo resin soluble in an org. solvent is preferably adapted. The planographic printing plate having excellent developability and plate wear is obtd. in this way without using a developer contg. the org. solvent.

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 active light such as ultraviolet rays through a negative image, and polymerizing or crosslinking the irradiated areas. An image area that repels water and receives oil-based ink, and a non-image area that accepts water and repels oil-based ink. It can be obtained by

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

(Problems to be solved by the invention) However, organic solvents are generally toxic, have an odor, and have a risk of fire, and also have many disadvantages such as being subject to BOD regulations for waste liquid, and are expensive. There is a problem.

(Means for Solving the Problems) Therefore, as a result of intensive studies to solve these problems, the present inventors developed a lithographic printing plate containing a specific component in addition to the diazo resin in the photosensitive layer. and pH during development.
It was discovered that a printing plate having good printing properties could be obtained without using an organic solvent by using an aqueous alkali solution of 12 or more, and the present invention was achieved based on this finding.

That is, the gist of the present invention is to image a photosensitive lithographic printing plate having a photosensitive layer containing a diazo compound, a lipophilic polymer compound, and a nonionic surfactant and/or a fluorine surfactant on a support. The present invention relates to a method for producing a lithographic printing plate, characterized in that after exposure, the lithographic printing plate is produced by developing with an alkaline aqueous solution having a pH of 12 or higher and substantially free of organic solvents.

(Specific Structure of the Invention) The present invention will be described in detail below.The present invention relates to a method for producing a lithographic printing plate, and the diazo compound contained in the photosensitive composition of the lithographic printing plate includes: Conventionally known ones can be used as appropriate, but include diazo resins represented by condensates of aromatic diazonium salts and active carbonyl-containing compounds, particularly formaldehyde, among which diazo resins soluble in organic solvents are preferred.

Examples of the diazo resin include diazo resin inorganic salts, which are organic solvent-soluble reaction products of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, and hexafluorophosphate or tetrafluoroborate; The above condensate and sulfonic acids such as para-toluenesulfonic acid or its salts, phosphinic acids such as benzenephosphinic acid or its salts, hydroxyl group-containing compounds such as 2.4 as described in Japanese Patent No. 3,300.309 -dihydroxybenzophenone, 2-
Examples include organic solvent-soluble diazo resin organic acid salts which are reaction products such as hydroxy-4-methoxybenzophenone-5-sulfonic acid or its salts.

The following diazo resins also contain 1 in the photosensitive layer.
The content is desirably 70% by weight, particularly 3 to 60% by weight.

Other diazo resins that can be suitably used in the present invention include aromatic compounds having at least one organic group of at least one carboxyl group and at least one hydroxyl group; diazonium compounds;
Preferably, it is a (co)condensate containing an aromatic diazonium compound as a structural unit.

The above-mentioned aromatic compound having a carboxyl group and/or a hydroxyl group 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 with the same aromatic ring.

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

Furthermore, the above carboxyl group or hydroxyl group may be bonded directly to the aromatic ring or may be bonded via a joint.

In the above case, the number of carboxyl groups bonded to one aromatic ring is preferably 1 or 2, and the number of hydroxyl groups bonded to one aromatic ring is preferably 1 to 3. For example, an alkylene group having 1 to 4 carbon atoms can be mentioned.

Specific examples of the above-mentioned aromatic compounds containing carboxyl groups and/or hydroxyl groups include 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, resorcin, 2-methylresorcin, (olm
, p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycine, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl 4,4'-diol, 1° 2.4-
Benzenetriol, bisphenol A12.4-dihydroxybenzophenone, 2.3°4-trihydroxybenzophenone, P-hydroxyacetophenone, 4.
4-dihydroxydiphenyl ether, 4.4'-dihydroxydiphenylamine, 4.4'-dihydroxydiphenylsulfidocumylphenol, (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-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
-trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, in-benzoyl gallic acid, m-(p-)ruyl) gallic acid, protocatechoyl gallic acid, 4.
6-cyhydroxyphthalic acid, (2,4-dihydroxyphenyl) vinegar 1 (2,6-dihydroxyphenyl) vinegar L (3,4,5-1-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. Particularly preferred are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid.

As the aromatic diazonium compound constituting 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 diphenylamine-4-diazonium salts are particularly preferred. .

Diphenylamine-4-diazonium salts are derived from 4-amino-diphenylamines, such as 4-amino-diphenylamine, 4-amino-3-methoxy-diphenylamine, 4-amino-diphenylamine, Amino-2-methoxy-diphenylamine, 4'-amino-2-methoxy-diphenylamine, 4'-amino-4-methoxy-diphenylamine,
4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine, 4-amino-3-
β-Hydroxy-ethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-
Examples include diphenylamine-2-carboxylic acid and 4-amino-diphenylamine-2'-carboxylic acid, with 3-methoxy-4-amino-diphenylamine and 4-amino-diphenylamine being particularly preferred.

The above-mentioned co-condensed diazo resin can be prepared by a known method, for example, Photographic Science and Engineering (Photo, 5ci-+ Eng, ) Vol. 17,
No. 33 (1973), U.S. Patent Box 2.063,631
No., No. 2.679.498 According to the methods described in each specification, diazonium salt,
It is obtained by polycondensing an aromatic compound having a carboxyl and/or hydroxyl group with an aldehyde such as paraformaldehyde, acetaldehyde, benzaldehyde or a ketone such as acetone or acetophenone.

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

The charging molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazo compound is 1:0, i-0,1:IS, preferably t:O, 5 to 0.2jl, and more. Preferably 1:1-0
．． 2:l. In this case, the molar ratio of the sum of aromatic compounds and aromatic diazo compounds having at least one of a carboxyl group and a hydroxyl group to aldehydes or ketones is usually 1:0.6 to 1.2, preferably 1: A co-condensed diazo resin can be obtained by charging 0.7 to 1.5 and reacting at a low temperature for a short time, for example, about 3 hours.

The counter anion of the diazo resin used in the present invention is
It contains an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent.

These 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-
Aliphatic and aromatic sulfonic acids such as methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5-sulfoisophthalate, 2.2', 4.4'-tetrahydroxybenzophenone, Hydroxyl group-containing aromatic compounds such as 1,2,3-1-lihydroxybenzophenone, 2,2',4-trihydroxybenzophenone, hexafluorophosphoric acid,
Halogenated Lewis acids such as tetrafluoroboric acid, Cf0
Examples include, but are not limited to, perhalogen acids such as 4.10°.Among these, particularly preferred are hexafluorophosphoric acid and 2-hydroxy-4-methoxybenzophenone-5-sulfone. It is an acid.

The above-mentioned co-condensed diazo resin 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, Molecular weight is about 400 to io, ooo
Although any number of particles can be used, it is preferably about 800 to 5,000.

The aforementioned diazo compound is preferably used together with a water-insoluble, alkali-soluble (or swellable) lipophilic polymer compound as a binder.

As this lipophilic polymer compound, the following (1) to (12)
Examples include copolymers whose structural units are monomers shown in ) 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)
Alkylamide or N-(4-hydroxyphenyl)methacrylamide, 0-m-1p-hydroxystyrene,
0-1m-1p-hydroxyphenyl acrylate or methacrylate, (2) acrylic esters and methacrylic esters with aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (3) acrylic acid , methacrylic acid, alpha, beta-unsaturated carboxylic acids such as maleic anhydride, (4) methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(5) Alkyl acrylates such as 2-chloroethyl, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, (substituted) alkyl methacrylates such as N-dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexyl Acrylamide, 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 acetate, vinyl benzoate, etc. (9) Styrene, α-methylstyrene, methylstyrene, chloromethyl Styrenes such as styrene, θ0)
Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc., 00 Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc., 021 N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine , acrylonitrile, methacrylate trile, etc.

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with, for example, glycidyl methacrylate, glycidyl acrylate-1.

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

It is particularly preferable that the copolymer contains an α,β-unsaturated carboxylic acid listed in (3), and the preferable acid value of the copolymer is 10 to 100.

The preferred molecular weight of the lipophilic polymer compound is 40,000 to 150,000.

Further, the lipophilic polymer compound may be used in combination with polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novola resin, or natural resin, if necessary.

This type of alkali-soluble polymer is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight.

Further, particularly preferred as the lipophilic polymer compound as a binder is a polymer having methyl acrylate as a structural unit. In this case, it is more preferable to
It is the following copolymer.

That is, in the molecular structure, (a) a structural unit having an alcoholic hydroxyl group and/or
or 1 to 50 mol% of a structural unit having a phenolic hydroxyl group, (c) the following soft formula I, -C11□-C-...1N (wherein R1 represents a hydrogen atom or an alkyl group); 5 to 40 mol% of the represented structural unit, (C) 5 to 40 mol% of units formed from methyl acrylate, (d) following - soft formula ■, -CI! -C-...■0OR3 (In the formula, Rz represents a hydrogen atom, a methyl group, or an ethyl group, and R3 represents an alkyl group or an alkyl-substituted aryl group having 2 to 12 carbon atoms.) It is a copolymer containing 25 to 60 mol% of units and 2 to 30 mol% of structural units having (e) carboxyl groups, and has a weight average molecular weight of 50,000 to 200,000.

Specific examples of the monomer forming the structural unit having an alcoholic hydroxyl group include (meth)acrylic esters (hereinafter the same) as the compound shown in the following general formula (1) as described in Japanese Patent Publication No. 527364. Acrylic and methacrylic compounds are collectively referred to as (meth)acrylic, etc.) and acrylamides.

In the formula, R4 is a hydrogen atom or a methyl group, RS is a hydrogen atom,
Methyl group, ethyl group or chloromethyl group, and n is 1
Indicates an integer of -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, N
- and droxyethyl (meth)acrylamide. Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming a structural unit having a phenolic hydroxyl group include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-(meth)acrylamide, N-(4-hydroxyphenyl)-(meth)acrylamide, Monomers of (meth)acrylamides such as hydroxynaphthyl)-(meth)acrylamide 20-1m- or p-hydroxyphenyl (meth)acrylate monomers: o-
Examples include m- or p-hydroxystyrene monomers. Preferably, 0-lm- or p-hydroxyphenyl (meth)acrylate monomer N-(4-hydroxyphenyl)-(meth)acrylamide monomer,
More preferably N-(4-hydroxyphenyl)-(
meth)acrylamide monomer.

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

Examples of monomers having a cyano group in the side chain that form the structural unit represented by -soft formula (II) include acrylonitrile, methacrylaterile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, 0- Examples include 1m-1p-cyanostyrene. Preferred are acrylonitrile and methacrylatetrile. The proportion of the structural unit having a cyano group in the side chain contained in the molecule of the polymer compound is selected from the range of 5 to 40 mol%, preferably 15 to 35 mol%.

The unit formed from methyl acrylate is 5 to 40 mol%, preferably 10 to 30 mol% in the polymer compound.
selected from the range.

Examples of monomers having a carboxy ester group in the side chain that form the structural unit represented by the soft formula (-) include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate,
amyl methacrylate, hexyl acrylate, tortyl acrylate, 2-chloroethyl acrylate, 2-
Examples include hydroxyethyl acrylate, glycidyl acrylate, and the like. The unit formed from the monomer accounts for 25 to 60 mol%, preferably 3% by mole in the polymer compound.
It is selected from the range of 5 to 60 mol%.

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

In addition, the seven degrees listed above are specific examples of each structural degree.
It is not limited to units formed from.

As a method for synthesizing a lipophilic polymer compound as a binder in a photosensitive composition, a generally known radical polymerization method or the like is used to synthesize an initiator (0,1- 4.0 mol%) by a solution polymerization method.

In the present invention, various known nonionic surfactants can be used as the nonionic surfactant contained in the photosensitive layer of the photosensitive lithographic printing plate together with the diazo compound and the lipophilic polymer compound.

As an example, polyethylene glycol (110-1-Cfl*C1110+r H”), polyoxyethylene alkyl ether (RO(CIlIC1
1! 0) 1% 11) ・Polyoxyethylene alkylphenyl ether ・Polyoxyethylene polystyrylphenyl ether (including block polymers and random polymers) ・Polyoxyethylene-polyoxypropylene alkyl ether ・Alkylphenol formalin condensate Ethylene oxide derivatives, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene polyhydric alcohol fatty acid partial ester, e.g. CHg0(CHzCHzO)1%0CRC)10 (C
H o CH, 0), 10 CRC) 10 (CHtCIlf
fiO), 11CHO(C1l, C11□0)lIH Cllo(C1(ICH,0), 11 CHzO(CHzCHtO)11 ・Polyoxyethylene fatty acid ester (e.g. RCOO(CIltCfbO)-H) ・Polyoxyethylene alkylamine, etc. can be given.

Specific examples of the above-mentioned compounds include the following. That is, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,
Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, poly Oxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene These include glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensed IFl, t-oxyethylene oxypropylene block copolymer, tetraethylene glycol, polyethylene glycol, and the like.

The proportion of the nonionic surfactant in the photosensitive composition is preferably selected from the range of 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight based on the total composition. .

Further, in the present invention, the above-mentioned nonionic surfactants may be used alone or in combination of two or more.

In addition, the fluorine-based surfactant used in the present invention is one in which the hydrogen atoms bonded to the carbon atoms of the hydrophobic group of the surfactant are partially or completely replaced with fluorine atoms, such as those shown below. Anion type, cation type, nonion type,
Both amphoteric type and polymer type can be used, but
Nonionic fluorosurfactants are preferred.

l) Anionic fluorosurfactant hydrophilic group Toshichi C00M, -0303M, -5O
J.

0P (OH) x, etc., for example, Rf
COOM% RfSOJ(R')xctl□C00
M, RfBNR' Ctf140SOJ, RfSO3M
, RfCtltOC-Hz-SOsM, etc.

(In the formula, Rf and Rf' each represent a fluorinated carbon group (having 2 to 20 carbon atoms) in which some or all of the hydrogen atoms of the alkyl group are replaced with elementary atoms, and B is GO, So! , R′ represents a hydrogen atom or a lower alkyl group, and M represents a hydrogen atom, an alkali metal, or an alkaline earth metal.)2) Cationic fluorine-based surfactant R′ RfBNHCJJ R”Xo (in the formula, R# represents a hydrogen atom or a lower alkyl group, X represents silver halide, HX represents an acid, Rf
, B and R' have the same meanings as Rf, B and R' in the anionic fluorosurfactant, respectively.

3) Amphoteric fluorine-based surfactants such as RfBNH(CzHa)N (R' )zc, )lz
, cOo.

RfBNHC-fb-Ne (R' LCj!.

(In the formula, Rf, B and R' are respectively synonymous with Rf, B and R' in the anionic surfactant.

4) Nonionic fluorosurfactant A hydrophilic group containing 10H, -3)I, -0-, etc. For example, RfOH9RfSH1Rf-A-(C
++)LO), R, etc.

(In the formula, A is 1 + CI Yamazu O, NR, - + CHg + r
-0-0(CHt+t-C0NRt, 5Ox
−−CO,+, and −SOgN(Rs)CIh
A group selected from the group consisting of COg-, where m is 0 to 2
an integer of 0, l represents an integer of 0 to 5, Rb5Rq and R8 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or -(-C)IzC)bO+rR,
R,,R.

and R6 may each be the same or different.

X represents an integer of 1 to 20, and R9 represents an alkyl group having 1 to 6 carbon atoms.
Examples include 00CHtRf compounds.

Preferred specific examples of the nonionic fluorosurfactant are illustrated below.

[Exemplary compounds] (1) CF s (CF ri ?・(C11zCH
zO) +. ■(2) CFs (CFg)tsOtN
(CJs) (CHgCHzO)+aH(3) CFs
(Ch)tsOJ(Czlls)C11zCOO(CH
zCIlzO)t. 11(4) Ch(Ch)?・
(CF low), ・C0N (Cfls) (CI□CII□O
)+J(5) CF3(CFri?5O1N(C,lC
! I(4(OC3H&)sOH The amount of the fluorosurfactant used in the present invention in the photosensitive composition is 0.05
~10ffi amount% is preferable, more preferably 0.1~
It is 5% by weight.

Further, in the present invention, the above-mentioned fluorosurfactants may be used alone or in combination of two or more.

Furthermore, in the present invention, both the above-mentioned nonionic surfactant and fluorine-based surfactant may be used, or only one of them may be used.

When a nonionic surfactant and a fluorosurfactant are used together, the amount of both surfactants in the photosensitive composition is preferably 0.05 to 10% by weight in total of both surfactants, More preferably, it is 0.1 to 5% by weight. Further, there is no particular restriction on the ratio of both surfactants.

A dye can further be used in the photosensitive layer of the photosensitive lithographic printing plate in 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 BO)i (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 B, Pesic Tsuksin, Malachite Green, 1st Ruretsudo, m-Glesol Barbre, Rhodamine B, Auramine, 4-p-diethylaminophenyl imino naphthoquinone, Discoloration in which triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based pigments, such as cyano-p-diethylaminophenylacetanilide, change from colored to colorless or a different colored tone. Examples of agents include:

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, 1,2°3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis -dimethylaminodiphenylamine, l,2-dianilinoethylene, p, p', p'-)
Lis-dimethylaminotriphenylmethane, p, p'
-bis-dimethylaminodiphenylmethylimine, p,
pp'-triamino-0-methyltriphenylmethane,
Examples include primary or secondary arylamine dyes represented by p,p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane and p,p',p''-triaminotriphenylmethane.

Particularly preferably triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, especially Victoria Pure Blue BOH.

The above-mentioned dye is usually included in the photosensitive composition from about 0.5 to about 10!
% by weight is preferred, more preferably about 1-5% by weight.

Various additives can be further added to the photosensitive layer of the photosensitive lithographic printing plate of the present invention. For example, as a coating property improver, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants (e.g. Bluronic L-64 (manufactured by Jimika Co., Ltd.)), etc. can be used to improve coating properties. Butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, phosphoric acid as plasticizers to impart flexibility and wear resistance. Trioctyl, tetrahydrofurfuryl oleate, oligomers or polymers of acrylic acid or methacrylic acid, etc. may be mentioned. Examples of the oil-sensitizing agent for improving the oil-sensitivity of the image area include those described in JP-A-55-527. Examples of the stabilizer include a half ester of styrene-maleic anhydride copolymer with alcohol, etc.
Polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (
acrylic acid, methacrylic acid, citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, etc.)
etc. The amount of these additives added varies depending on the purpose of use, but -a is 0 to the total solid content.
．． 01 to 30% by weight.

A photosensitive lithographic printing plate is obtained by applying the above photosensitive composition onto the surface of a support and drying it.

Examples of the coating solvent include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, cyclohexanone, trichloroethylene, and methyl ethyl ketone.

These solvents may be used alone or in combination of two or more.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, curtain coating, etc. can be used. The coating amount is preferably 0.2 to 10 g/m'' in terms of solid content.

It is preferable to use an aluminum plate as the support of the photosensitive lithographic printing plate of the present invention, which is electrolytically roughened in an electrolytic solution containing acetic acid or nitric acid as a main component, or hydrochloric acid or an electrolytic solution containing hydrochloric acid as a main component. The material is grained and preferably further subjected to anodizing treatment and, if necessary, surface treatment such as sealing treatment.

Electrolytic surface roughening is performed by immersing an aluminum plate in a bath containing 0.1 to 0.5 mol/β, preferably 0.2 to 0.4 mol/l of nitric acid or hydrochloric acid, and heating at 20 to 50°C.
1 Preferably a temperature of 25 to 40°C, a current density of 20 to 20
It is preferable to perform electrolytic etching at OA/da'' for about 10 seconds to 3 minutes. After this graining treatment, if necessary, a desmut treatment is performed with an aqueous alkali or acid solution to neutralize it, followed by washing with water.

The anodizing treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolyte. The amount of anodic oxide film formed was 1 to 50 mg/
dm” is appropriate, preferably 10 to 40 μ/dIl
! It is. Here, the amount of anodic oxide film is determined by, for example, replacing aluminum solution with phosphoric acid chromic acid solution (35ml of 85% phosphoric acid aqueous solution).
It can be determined by dipping the oxide film into a solution (produced by dissolving 11 and 20 g of chromium oxide (Vl) in 1β of water) to dissolve the oxide film, and measuring the weight change before and after dissolving the plate skin W4.

Pore sealing treatments include boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, and the like. In addition, water-soluble polymer compounds,
Subbing treatment can also be performed using an aqueous solution of a metal salt such as fluorinated zirconate.

The photosensitive lithographic printing plate thus obtained can be used by a known method. Typically, a negative film is brought into close contact with a photosensitive printing plate, exposed to light using an ultra-high pressure mercury lamp, metal halide lamp, etc., and developed using various known developers to obtain a printing plate. The lithographic printing plate produced in this way can be used in sheet-fed and off-wheel printing presses.

That is, by exposing to light through a transparent original having line images, halftone images, etc., and then developing with an aqueous developer,
A negative relief image is obtained for the original image. Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, and the like.

The developer used in the development of the photosensitive lithographic printing plate in the present invention is an alkaline aqueous solution containing substantially no organic solvent.

The phrase "substantially does not contain" an organic solvent means that it does not contain it in an amount that impairs the above-mentioned sanitary and safety effects, and generally contains less than 1% by weight of an organic solvent in the developer composition. If there is, there is no problem.

In the present invention, the preferred organic solvent content is 0.5% by weight.
The alkaline agents used in the developer according to the present invention are preferably calcium silicate, lithium silicate, sodium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, Examples include sodium triphosphate, sodium diphosphate, potassium triphosphate, potassium diphosphate, sodium carbonate, potassium carbonate, and the like. 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.
ng ) / [M ) = 0.5 to 1.5, where (Sing) and (M) indicate the molarity of 5ift and the molarity of total alkali metals, respectively, and 5i
A developer containing 0.8 to 8% by weight of nt is preferably used. Among this alkali silicate composition, a developer having a molar ratio of (Sins)/(M) -0.5 to 0.75 and 0.8 to 4% by weight of 5108 is particularly difficult to develop due to its low concentration. It is preferably used because it is easy to neutralize the waste liquid. On the other hand, a developer with a molar ratio of more than 0.75 and up to 1.3 and a Sin content of 1 to 8% by weight has a high buffering power and has a high processing capacity. It is preferably used because of its high value.

The pH (25°C) of the developer according to the present invention is 12 or more, preferably 12.5 to 14. In addition, the developer contains, for example, sodium sulfite, potassium sulfite,
Water-soluble sulfites such as lithium sulfite and magnesium sulfite can be added.

The preferred content of sulfite in the developer composition is 0.
．． 05-4% by weight, more preferably 0.1-1% by weight
It is.

In addition, an anionic surfactant and an amphoteric surfactant as described in JP-A-50-51324, and an amphoteric surfactant as described in JP-A-59-75255 and JP-A-59-75255,
By containing at least one of the nonionic surfactants as described in JP-A-55-95946 and JP-A-55-95946,
As described in Japanese Patent No. 142528, the inclusion of a polymer electrolyte can improve the wettability of the photosensitive composition and further improve the gradation, and is therefore preferably used. There is no particular limit to the amount of surfactant added, but
0.0 O3 to 3% by weight is preferable, especially 0.006 to 3% by weight.
A concentration of 1% by weight is 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, methods include immersing an image-exposed printing plate in a developer, squirting the developer from a number of nozzles onto the photosensitive layer of the printing plate, and using a sponge moistened with the developer to remove the printing plate. Examples include a method of wiping the photosensitive layer of the PS plate, and a method of applying a developer to the surface of the photosensitive layer of the PS plate using a roller. Further, after applying the developer to the photosensitive layer of the PS plate in this manner, the surface of the photosensitive layer may be lightly rubbed with a brush or the like.Development conditions can be appropriately selected depending on the development method described above. - 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 is selected.

〔Example〕

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.

(Manufacture of Aluminum Plate-1) An aluminum plate with a thickness of 0.24 m was electrolytically polished in a 17 g/42 hydrochloric acid bath at a bath temperature of 25°C and 50 A/cm2 for 25 seconds to give a maximum roughness of 4 μm. I got a grained board.

The grained board was placed in a 40% by weight phosphoric acid bath at a bath temperature of 35°C.
Anodizing treatment was performed for 20 seconds at 3.2 A/c.

Next, the anodized aluminum plate was immersed in a 1% by weight sodium metasilicate solution at 90°C for 30 seconds to seal the holes.

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

(Synthesis of diazo compound-1) 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 l
It was added so as not to exceed OoC. Thereafter, stirring was continued for 2 hours under water cooling.

This reaction mixture was heated under ice cooling at 500 mj! was added dropwise to ethanol, and the resulting precipitate was filtered. After washing with ethanol,
100mj of this sediment! Dissolve in pure water and add 6 to this solution.
．． A cold concentrated aqueous solution of 8 g of zinc chloride was added. The resulting precipitate was filtered and washed with ethanol.
It was dissolved in 0mf 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 on 30'C11 day and night to obtain diazo compound-1.

When the molecular weight of this diazo compound-1 was measured by GPC, it was found that it contained about 50 mol% of pentamers or more.

(Synthesis of diazo compound-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 paraformaldehyde (0,0
9 mol) was added slowly. 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 mixture was poured into 12 ethanol under water cooling,
The resulting precipitate was filtered. After washing with ethanol, this precipitate was washed with 200mj! Dissolve in pure water and add 10.5% to this solution.
A cold concentrated aqueous solution of 1 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and washed with 300 m
j! was dissolved in pure water. To this liquid was added a cold concentrated aqueous solution in which 13.7 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was filtered, washed with water, and then dried at 30°C for 1 day and night to obtain diazo compound-2.

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

(Synthesis of lipophilic polymer compound-1) N-(4-hydroxyphenyl) methacrylamide 10
．． 0 g, acrylonitrile 25 g 1 ethyl acrylate 60 g 1 methacrylic acid 5 g and azobisisobutyronitrile 2.0 g in acetone-methanol 1:1 mixed solution 1
The solution was dissolved in 20mff1, and after purging 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 GPC, the weight average molecular weight was 63,000.

Examples = 1 to 6, 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, 85
It was dried at ℃ for 3 minutes to obtain a photosensitive planographic printing plate.

(Photosensitive liquid composition) Lipophilic polymer compound - 15.0 g Diazo compound Listed in Table 1 Jurimer AC-1OL 0.3 g (manufactured by Nippon Pure Chemical) Victoria Pure Blue B OHO, 2 g (manufactured by Hodogaya Chemical) Interface Activator Listed in Table-1 PP-3
121° 0.05 g Methyl cellosolve 10ml 1” PP-3121 *l) Surfactant Rheodol 5p-o io: Sorbitan monooleate [manufactured by Kao ■] Rheodol MO
-60: Glycerol monooleate [manufactured by Kao ■] Fluorine-1
: CPs(CFs)v ・(CIICHgO) I(IH
Fluorine-2: CFs (CFs) tsOzN (Cills) (C)
After exposing the obtained photosensitive lithographic printing plate to a 3 kW ultra-high pressure mercury lamp from a distance of 100 cI for 30 seconds, developer-1 shown below was diluted with water to a predetermined magnification and incubated at 25°C for 45 seconds. Development was carried out under the following conditions.

In addition, for those developed at a dilution rate of 4 times, a printing durability test was conducted using a general ink (Toyo Ultra King Beni) on high-quality paper using a GTO printing machine manufactured by Heidelberg.

The above results are shown in Table-2.

(Developer - 1) JIS Silicate League No. 3 (manufactured by Jimika Kogyo ■) Sodium hydroxide (industrial use) Sodium sulfite water 210g 150g 7g 2500mf Table 2 $2) Examples 1 to 4 that exceeded the developability standard ．． Comparative Examples 1 and 2 show that the photosensitive lithographic printing plate according to the present invention exhibits excellent developability when developed using the developer according to the present invention, and a lithographic printing plate with excellent stiffness resistance can be obtained. I understand.

(Effects of the Invention) As explained above, the method for producing a lithographic printing plate of the present invention has the effect of providing a lithographic printing plate with excellent developability and printing durability without using a developer containing an organic solvent. It is something to play.

Claims (1)

[Scope of Claims] A photosensitive lithographic plate having a photosensitive layer on a support containing (1) a diazo compound, (2) a lipophilic polymer compound, and (3) a nonionic surfactant and/or a fluorine surfactant. 1. A method for producing a lithographic printing plate, which comprises developing the printing plate with an alkaline aqueous solution substantially free of organic solvents having a pH of 12 or more after image exposure.