JPS62262050A - Diazo photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE:To improve a shelf life and the stability to processing chemicals to be used by incorporating a photosensitive diazo resin, lipophilic high-polymer compd. and silane coupling agent into a photosensitive layer. CONSTITUTION:This printing plate has the photosensitive layer consisting of the compsn. contg. the photosensitive diazo resin and lipophilic high-polymer compd. and further contg. the silane coupling agent on a base. The silane coupling agent is incorporated usually at 0.01-5wt%m more preferably 0.1-1.5wt% into the photosensitive compsn. The lipophilic high-polymer compd. is incorporated at usually 40-99wt%, more preferably 50-95wt% into the solid content of the photosensitive compsn. The photosensitive diazo resin is incorporated at usually 1-60wt%, more preferably 3-30wt% into said compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a diazo-sensitive lithographic printing plate, and more particularly, to storage stability and stability against processing chemicals used in the printing process, that is, chemical resistance. This invention relates to an improved diazo-sensitive lithographic printing plate.

[Prior art]

Planographic printing is a printing method that uses water and ink on a planographic printing plate, supplying ink to image areas and water to non-image areas. It is necessary that the image area and the support are firmly adhered. In addition, the image area must have good stability (chemical resistance) to various chemicals used in the plate-making process where the lithographic printing plate material is exposed and then subjected to development treatment to obtain the lithographic printing plate, as well as the various chemicals used in the printing process. It is. Furthermore, it is also required that no stains occur in non-image areas during the printing process.

As a means to meet the above requirements, conventionally, in lithographic printing plate materials having a photosensitive layer on a support, a non-photosensitive material containing a silane coupling agent between the support and the photosensitive layer has been used. A method is known (Japanese Unexamined Patent Publication No. 192250/1983) in which a neutral intermediate layer is provided adjacent to the support. When stored in a lithographic printing plate, there are drawbacks such as insufficient storage stability, such as stains occurring in non-image areas during the printing process and a significant decrease in rigidity and chemical resistance. Since additional equipment for providing the intermediate layer is required for manufacturing, it is not economically preferable.

[Purpose of the invention]

An object of the present invention is to solve the above-mentioned problems and provide a diazo-sensitive lithographic printing plate which has excellent storage stability and improved stability against processing chemicals used, that is, chemical resistance. .

[Structure of the invention]

The above-mentioned object of the present invention is to provide a diazo-sensitive lithographic printing plate having a photosensitive layer formed of a composition containing a photosensitive diazo resin and a lipophilic polymer compound and further containing a silane coupling agent on a support. achieved.

[Specific structure of the invention]

The present invention will be explained in detail below. In the present invention, the silane cuff pulling agent used as a component of the photosensitive layer refers to a compound in which at least two reactive groups and/or atoms are bonded to a tetravalent silicon atom directly or via a linking group. say.

Examples of reactive groups here include amino group, vinyl group, epoxyethyl group (CH, -CH-), epo\, 1-oxyethylene! (-CH-C11-), a mercapto group, an alkoxy group, an alkyl group, an acyloxy group, and an ammonium compound residue. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group and an ethoxy group. Examples of the alkyl group include those having 1 to 4 carbon atoms, such as a methyl group and an ethyl group. Examples of the acyloxyl group include alkylcarbonyloxy groups having 2 to 4 carbon atoms, such as an acetyloxy group and a butyryloxy group. Examples of ammonium compound residues include quaternary ammonium compound residues such as octadecyldimethylammonium chloride residues.

These groups may have a substituent, and examples of groups having a substituent include α-methylvinyl group, β-methoxyethoxy group, anilino group, bis(β-hydroxyethyl)
Examples include amino groups.

Examples of the atom bonded to the silicon atom directly or via a linking group include a halogen atom such as a chlorine atom.

Examples of the above-mentioned linking group include alkylene groups having 1 to 5 carbon atoms such as ethylene, propylene, trimethylene, and tetramethylene groups, and carbon atoms such as trimethyleneoxymethylene and ethyleneoxyethylene groups. 2 to 8 carbon atoms, such as an alkyleneoxyalkylene group or a trimethyleneaminoethylene group
an alkylene-oquinecarbonyl group having 2 to 5 carbon atoms, such as an alkyleneaminoalkylene group, an ethyleneoxycarbonyl group, or a trimethyleneoxycarbonyl group (however, 9 alkylene groups are bonded directly to the silicon atom); Examples include alkyleneaminoalkyleneaminophenylene groups having 9 to 15 carbon atoms such as trimethyleneaminoethyleneaminomethylenephenylene group (however, the alkylene group is directly bonded to the silicon atom). Further, the above-mentioned epoxyethyl group is bonded to a linking group and bonded to a silicon atom as an epoxycycloalkylalkyl group, such as a β-(3,4-epoxycyclohexylethyl group).

The silane coupling agent used in the present invention includes:
Furthermore, disilanzane compounds such as hexaalkyldisilanzane are also contained.

Next, specific examples of silane coupling agents that can be used in the present invention will be shown.

Flame ball stopper (1) fjl z = C1l S i (QC
)I i) 5(2) CH2= C1l S i
(OCR2CII□0CHi)z(3) CIl□
-CIISi (OCOCIh) 3(4) CII
z=CCOO(CHz)tsi(OClh)tC1lyu(5) CIl□-CIlSi (OCzlls)
x(OCI+3)i) ・HCJ (7) Cll z ” Cll5 i C1z(8
) C) It-CCOO(CHz)sSi(OCHt
CHtOCHs)s■ CI.

(9) MHz(CHt)tNH(CHt)*5i(
OCRs)s(10)NHt(CHt)tNH(CHt
)zsi(OCRs)iCHt1 (11)NOx(CHz)sSi(OCtHs)s(1
2) NHzCHxSi(OCxHs)z(13) N
Ht(CHi)zsi(OCtHs)s(14) N
Ht (CHz), 5i (OCH,) x (15) (H
OCHtCHt)tN(CHt)ssi(OCll(s
)s(19)CHsSi(OCHzClh)s(20)
CHsSi(OCRs)s (21) (CHs)zsiα (22) CHiSiCIs (23) (CHl3) zsicjg(24)
α(Cllz)ssi(OCRs)3(25) (J
(CHz)ssi(OCH2hCHl (26) 03(Cilz)3si(OCHs)tCH
l (27) HS (CIlz) zsi (OCHs)
tC+, Hzt N”(CHz)ist(OCHt
)i■ α- (29) (Clls) 5siNH3i(CHi)
Among the above-mentioned silane coupling agents, preferred in the present invention are those in which 2 to 3 alkoxy groups are directly bonded to a silicon atom and a vinyl group is further bonded to a silicon atom via a linking group.

In the present invention, the amount of the silane coupling agent in the photosensitive composition constituting the photosensitive layer is usually 0.01 to 5% by weight, particularly 0.1 to 1.5% by weight! ! It is preferable to contain it in a proportion of % by weight.

Examples of the photosensitive diazo resin used as a component of the photosensitive layer in the present invention include those manufactured by Photographic Science and Engineering (Photo).

Sci, Eng,) Volume 17, Page 33 (1973)
, U.S. Patent Nos. 2,063,631 and 2,679.
No. 498, specifications of No. 3,050,502, JP-A-5
A diazo resin obtained by condensing a diazo compound whose manufacturing method is described in Publication No. 9-78340 and an active carbonyl compound, such as formaldehyde, acetaldehyde, or benzaldehyde, in an acidic medium such as sulfuric acid, phosphoric acid, or hydrochloric acid. , a diazo resin obtained by condensing a diazo compound and a diphenyl ether derivative, the manufacturing method of which is described in Japanese Patent Publication No. 49-4001, and others.

Considering the sensitivity, storage stability, and film strength of the finally obtained photosensitive layer, in the present invention, the following general formula (1) is used.
Use a photosensitive diazo resin represented by, especially a photosensitive diazo resin containing a resin in which n in the general formula (1) is 5 or more in a proportion of 20 mol% or more, particularly preferably 20 to 60 mol%. is preferred.

Gosho style (1) In the formula, R1, R2 and R1 are each the same or different,
represents a hydrogen atom, an alkyl group or an alkoxy group, R represents a hydrogen atom, an alkyl group or a phenyl group, X represents a pair 7 anion, n represents a number from 1 to 200, and R
Examples of the alkyl group and alkoxy group of lo, R2 and R1 include an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms, and examples of the alkyl group of R include 1 to 5 carbon atoms. 5 alkyl groups can be mentioned.

Such a photosensitive diazo resin can be prepared by a known method, for example, Photo, Sci, Eng., Vol. 17, No. 3.
3 pages (1973), U.S. Patent No. 2,063,631;
It can be obtained by polycondensing a diazonium salt with aldehydes such as paraformaldehyde, acetaldehyde, and benzaldehyde in sulfuric acid, phosphoric acid, or hydrochloric acid according to the method described in each specification of No. 2,679,498.

In normal cases, the molar ratio of diazonium salt and aldehyde is t:o, 6 to 1:2, preferably 1:0.7 to
A highly sensitive photosensitive diazo resin can be obtained by charging at a ratio of t:t, S and reacting at a low temperature for a short time, for example, at a temperature of 10'C or less for about 3 hours.

The counter anion of the diazo resin described above includes an anion that forms a stable salt with the diazo resin and solubilizes the resin in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenyl phosphoric acid, and sulfonic acids, typical examples being methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzene sulfonic acid, etc. Sulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2
Aliphatic and aromatic sulfonic acids such as -hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroquinonesulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5-sulfoisophthalate, 2,2°, 4.4°
-Tetrahydroxybenzophenone, 1,2.3-)
Hydroxyl group-containing aromatic compounds such as trihydroxybenzophenone, 2,2', 4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, α04.10. Examples include perhalogen acids such as, but are not limited to.

Particularly preferred among these is hexafluorophosphoric acid.

In the present invention, the lipophilic polymer compound used as a component of the photosensitive layer includes polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane, polyvinychloride and its copolymer, polyvinyl butyral resin, polyvinyl formal resin, shellac, Epoxy resin, phenolic resin, acrylic resin,
Others can be mentioned.

More preferred are copolymers having a molecular weight of usually 20,000 to 200,000, which are obtained from the seven polymers shown in (1) to (12) below.

(1) Monomers having aromatic water groups, such as N-(4
-hydroxyphenyl)acrylamide or N-(4
-Hydroxyphenyl) methacrylamide, 0-1m-
1p-hydroxystyrene, 0-1m-1p-hydroxyphenyl-acrylate or monomethacrylate (2) Monomers with aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate (3) Acrylic acid, methacrylic acid, α, β-unsaturated carboxylic acids such as 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, 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-methylo-4-reacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, Acrylamides or methacrylamides such as N-hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acryl 7mide, N-ethyl-N-phenylacrylamide (7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (9) Styrene, α-methylstyrene, Styrenes such as methylstyrene and chloromethylstyrene (10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone (11) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene (12) ) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylaterile, etc. Furthermore, copolymers obtained by copolymerizing monomers that can be copolymerized with the above monomers may also be used.

It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and further modified with, for example, glycidyl methacrylate, glycidyl acrylate, and the like.

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

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

In the present invention, the lipophilic polymer compound is usually 40 to 99% by weight, preferably 50 to 99% by weight in the solid content of the photosensitive composition.
The content is 95% by weight. The photosensitive diazo resin is usually contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

In the present invention, the photosensitive composition for forming the photosensitive layer may contain a color change agent (pigment) that changes color tone by reacting with free radicals or acids. The color change agent is used for the purpose of obtaining a visible image by exposure (exposed visible image) or a visible image after development.

As such a color change agent, any color change agent can be used as long as it reacts with free radicals or acids to change color tone. Here, "change in tone" includes both a change from colorless to a colored tone and a change from colored to colorless or a different colored tone. Preferred color changing agents are those that change color tone by forming a salt with an acid.

Examples of such color changing agents include Victoria Pure Blue Rot (manufactured by Hodogaya Chemical Co., Ltd.) and Oil Blue 1603.
(manufactured by Orient Chemical Industry Co., Ltd.), Patent Pure Blue (
(Manufactured by Sumitomo Chemical Co., Ltd.), Crystal Bioleft, Brilliant Green, Ethyl Bioleft, Methyl Bioleft, Methyl Green, Erythrosin B2 Basic Tsuksin, Malachite Green, Oil Red, m-Cresol Purple, Rhodamine B1 Auramine, 4-p −
Diethylaminophenylimino naphthoquinone, cyano
Discoloration of triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine spinning wheel, or anthraquinone-based pigments represented by p-diethylaminophenylacetanilide, etc., 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-)riphenylguanidine, naphthylamine, diaminodipheni)remethane, 9. 9'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, ρ°, p
”-tris-dimethylaminotriphenylmethane, p,
p'-bis-dimethylaminodiphenylmethylimine,
Primary or Examples include secondary arylamine dyes.

Particularly preferably, triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, and Victoria Pure Blue 808 is particularly preferred.

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

In the present invention, various additives can be further added to the photosensitive composition for forming the photosensitive layer.

Examples of additives include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, and nonionic surfactants (e.g., Pluronic T, -64 (Asahi Denka) to improve coating properties. (manufactured by Co., Ltd.)], stabilizers for imparting flexibility and abrasion resistance to the coating film (e.g., butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic or methacrylic acid)
, an oil-sensitizing agent for improving the oil-sensitivity of the image area (for example, hafestelization T of a styrene-maleic anhydride copolymer with alcohol described in JP-A No. 55-527)
he), 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.)] etc. can be mentioned. The amount of these additives added varies depending on the composition and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content of the photosensitive composition.

In order to provide a photosensitive layer on a support using such a photosensitive composition, the above-mentioned photosensitive diazo resin, lipophilic polymer compound, silane coupling agent, and various additives added as necessary are required. A photosensitive composition coating solution is prepared by dissolving a predetermined amount of each in an appropriate solvent (such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water, or a mixture thereof). may be prepared, coated on a support, and dried. The concentration of the photosensitive composition in the coating solution during coating is preferably in the range of 1 to 50% by weight, and in this case, the coating amount of the photosensitive composition is approximately 0.2 to 1% by weight.
It may be about 0 g/m.

In the present invention, as the support, for example, silver, plastic, metal, etc. can be used. Examples of metals include aluminum, magnesium, zinc, chromium,
Mention may be made of iron, nickel, and alloys of these metals, among others.

It is desirable that at least the surface of the support is made of these materials.

That is, the back side of the support is combined with other base materials, such as paper, plastic, or other metal base materials bonded to the back side of a thin metal plate, or paper or plastic on one or both sides. It may be a metal plated or plated, a metal foil pasted together, or a metal plate plated with another metal.

Furthermore, the surface of the support is preferably roughened.

Various conventionally known methods can be used to roughen the surface of the metal support, including mechanical methods such as ball polishing and brush polishing, and acid or alkali methods. '8? Examples include chemical methods such as etching with &, and electrochemical methods such as electrolytic etching.

Preferred supports in the present invention include aluminum supports, and aluminum supports with roughened surfaces are more preferred, particularly those whose roughened surfaces have been anodized and hydrophilized. preferable.

Aluminum plate used as a support in the present invention (
To roughen the surface of aluminum (including laminates of other metals, paper, plastic, etc.), the same applies below), for example, brush polishing, ball polishing, honing, chemical polishing after degreasing the surface. Polishing method, electrolytic etching method, or a combination of two or more of these polishing methods can be applied. The anodizing treatment is performed, for example, in a single 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 in a mixed aqueous solution of two or more of these acids, and preferably in a GEA aqueous solution. This is done by passing an electric current through the aluminum plate as an anode.

The amount of anodic oxide coating is preferably 5 to 60 .mu./dya", more preferably 5 to 30 .mu./dya".

Examples of hydrophilic treatment include hot water sealing treatment and sodium silicate treatment, but sodium silicate treatment is preferred because it provides good adhesion and storage stability. The object to be treated is placed in a sodium metasilicate solution with a concentration of 0.1 to 5% at a temperature of 50°C to 95°C for 10 seconds.
This is done by soaking for 5 minutes. Preferably, it is then treated by immersion in water at 60°C to 100°C for 10 seconds to 5 minutes.

The photosensitive layer formed on the support is subjected to conventional methods to produce a lithographic printing plate. That is, a negative relief image is formed on the original image by exposing the photosensitive layer to light through a transparent original image such as a line image or halftone image, 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.

The developer used in the development of the diazo-sensitive lithographic printing plate according to the present invention may be any known developer, but the following are preferred.

That is, a developer suitable for developing the diazo-sensitive lithographic printing plate according to the present invention contains a specific organic solvent, an alkaline agent, and water as essential components.

Here, the specific organic solvent is one that can dissolve or swell the non-exposed area (non-image area) of the photosensitive layer made of the above-mentioned photosensitive composition when it is contained in the developer, and that can be used at room temperature ( An organic solvent having a solubility in water of 10% by weight or less at 20°C) is not particularly limited as long as it has the above-mentioned characteristics.Therefore, the organic solvent used is not limited. Examples include carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone , ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol sundyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methyl amyl alcohol, n-amyl alcohol, methyl amyl alcohol; such as xylene alkyltta aromatic hydrocarbons; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. One or more of these organic solvents may be used, and among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is approximately 1 to 20% by weight, particularly 2 to 10% by weight.
More preferable results can be obtained when the amount is fiffi%.

On the other hand, alkaline agents contained as essential components in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium dibasic or tertiary phosphate, or Inorganic alkaline agents such as ammonium salts, sodium metasilicate, sodium carbonate, ammonia, etc. (B) Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triethanolamine, mono , di- or triisopropanolamine, ethyleneimine, ethylenediamine, and other organic amine compounds.

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

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

Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water.

As such a solubilizing agent, in order to achieve the desired effects of the present invention, it is preferable to use alcohols and ketones that are more water soluble and have lower molecular weight than the aqueous solvent used. Also anion・
Activators, amphoteric activators, etc. can also be used. Examples of such low-molecular alcohols and ketones include methanol, ethanol, propatool, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol,
-Methoxy-4-methylbutanol, N-methylpyrrolidone, etc. can be preferably used. Further, examples of the activator include sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, and sodium N-butylnaphthalenesulfonate.
-Methyl-N-pentadecylaminoacetic acid sodium salt, lauryl sulfate sodium salt, etc. are preferred. There are no particular restrictions on the amount of solubilizers such as alcohols and ketones used, but generally about 3
The content is preferably 0% by weight or less.

After the diazo-sensitive lithographic printing plate of the present invention has been imagewise exposed, it can be brought into contact with the above-mentioned developer at a temperature of about room temperature to 40°C, or by further rubbing, for 10 to 60 seconds. In this method, the unexposed areas of the photosensitive layer can be completely removed without adversely affecting the exposed areas of the photosensitive layer, and excellent developability can be obtained. In addition, the printing plate obtained in this way has good developability over time (storage stability).
It also has excellent rigidity resistance, does not cause any deterioration in finish, and is free from pollution and occupational health problems.

Examples of producing lipophilic polymer compounds, photosensitive diazo resins, and supports used in the practice of the present invention are shown below.

Synthesis of 1-character high hesonic compound a N-(4-hydroxyphenyl) methacrylamide 10
．． 0 g, 25 g of acrylonitrile, 60 g of ethyl acrylate, 5 g of methacrylic acid and 1.642 g of azobisisobutyronitrile in 1.0 g of acetone and methanol.
The mixture was dissolved in 112 mff1 of a 7-volume medium, and after purging with nitrogen, it was heated at a temperature of 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 lipophilic polymer compound a.
I got it.

The molecular weight of this lipophilic polymer compound a was determined by gel permeation chromatography (hereinafter abbreviated as rGPcl).
The weight average molecular weight was 8,50,000 as measured by .

The relationship between the group and the group 50.0 g of 2-hydroxyethyl methacrylate.

Acrylonitrile 20g, methyl methacrylate 25g
A mixture of 5 g of methacrylic acid and 1.2 g of hendiyl peroxide was added to 300 g of ethylene glycol monomethyl ether heated to 100° C. over a period of 2 hours. After the dropwise addition was completed, 30 g of ethylene glycol monomethyl ether and 0.3 g of hendiyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, the mixture was diluted with methanol and poured into water 51 with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 90 g of a lipophilic polymer compound.

When the molecular weight of this lipophilic polymer compound was measured by GPC, the weight average molecular weight was 65,000.

p-diazodiphenylamine sulfate 14.5 g (5
0 mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise to this solution. At this time, the reaction temperature is 1
The temperature was made not to exceed 0°C. After that, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 50 lsl of ethanol under water cooling, and the resulting precipitate was filtered off. After washing with ethanol,
100 wj of this sediment! Dissolve in pure water, and in this liquid,
A cold IJI-aqueous solution containing 6.8 g of zinc chloride was added. The resulting precipitate was filtered and washed with ethanol.
This was dissolved in 150+11 pure water.

In this solution, 8 g of ammonium hexafluorophosphate was dissolved in a cold solution. mrq-aqueous solution was added. The resulting precipitate was collected by filtration, washed with water, and then dried at a temperature of 30° C. for one day and night to obtain photosensitive diazo resin a.

When the molecular weight of this photosensitive diazo fat a was measured by GPC, it was found that it contained about 50 mol% of hexamer or more.

An aluminum plate of +i'1 thickness 0, 21* of aluminum plate a was degreased by immersing it in 8 liquids of 3% hydroxide-sodium water, washed with water, and then soaked in 4 liquids of hydrochloric acid.
at a temperature of 2% in an aqueous solution with a concentration of 1% and a concentration of boric acid of 1%.
Electrolytic etching was performed at 5°C for 5 minutes at 3 A/dad', and after washing with water, anodization was performed at 30°C for 2 minutes at 1.5 A/d' in a 40% sulfuric acid aqueous solution, washed with water, and 1% Immerse in sodium metasilicate water solution for 37 seconds at a temperature of 85°C, and then soak in water (pl + 8.5°C) at a temperature of 90°C.
) for 25 seconds, washed with water, and dried to obtain aluminum plate a.

Aluminum Plate 1 An aluminum plate with a thickness of 0.24 mm was attached to a rotating drum, which was rotated at a circumferential speed of 12 m/min. The mixture was sprayed using a centrifugal sprayer. After washing with water,
25 parts of 2000 mesh alumina abrasive and 75 parts of water (
A mixture with volume ratio) 1 was sprayed in the same manner as above. After washing with water, it was immersed in a 1% sodium hydroxide aqueous solution at a temperature of 50°C for 9 seconds, then anodized in the same way as aluminum plate a, treated with sodium silicate, washed with water, and dried to obtain an aluminum plate. Ta.

An aluminum 4C plate with a thickness of 0.3fi was ball polished for 15 minutes using an alundum abrasive with a grain size of 1000 mesh, and after washing with water, the concentration of sodium hydroxide was 2% and the concentration of sodium gluconate was 0.5. Temperature 60℃ using % aqueous solution
After chemical etching for 2 minutes and washing with water, it was anodized in the same manner as aluminum plate A, treated with sodium silicate, washed with water, and dried to obtain aluminum plate C.

Aluminum d An aluminum plate prepared in the same manner as aluminum plate a was further prepared in Example 1 of JP-A-59-192250.
The silane coupling agent NHz (Clh
,) JR (CHz) Ji (OCH*) 2 of 0.
It was immersed in a 2% aqueous solution at a temperature of 25°C for 0 seconds to form a film.
O,10*/cla" (D An intermediate layer was provided to obtain an aluminum plate d.

〔Example〕

Sensitivity group i-1 10 g of a lipophilic polymer compound of the type shown in Table 1, a silane coupling agent of the type and amount shown in Table 1, and the following substance were mixed with methyl cellosolve. 1flOmm
! A coating solution for forming a photosensitive layer was prepared using each of the five types of photosensitive compositions A to E.

Photosensitive diazo resin a Ig “Victoria Pure Blue BOHJ [Manufactured by Hodogaya Chemical ■] 0.2 g Jurimer AC-1OL [Polyacrylic acid manufactured by Niki Pure Chemical ■] 0.6 g
1 The coating solution obtained as described above was coated on each of the aluminum plates a to d using a whirler according to what is shown in Table 2, in an amount that gave a dry weight of 1.5 g/m. The photosensitive layer was coated and then dried at a temperature of 85° C. for 3 minutes to form a photosensitive layer, thereby obtaining a total of 10 types of diazo-sensitive lithographic printing plates. These are designated as samples 1 to 10.

After storing each of Samples 1 to 10 for 7 days at a temperature of 40°C and a relative humidity of 80%, they were exposed to light for 30 seconds from a distance of 60 values using an ultra-high pressure mercury lamp with a power consumption of 3KH, and the composition shown below was 4 in developer A at a temperature of 25°C.
By dipping for 5 seconds and developing, a lithographic printing plate is prepared, which is mounted on a printing machine, and a printing test is performed to observe the presence or absence of contamination, and the chemical resistance and stiffness resistance are simultaneously tested. For this purpose, use Ultra Plate Cleaner (ABC Chemical Co., Ltd.) every 2000 sheets.
Printing was continued while washing the plate using a printing press (manufactured by Co., Ltd.), and the number of prints until the image area became defective and the printed matter became incomplete was determined as the stiffness resistance.

Benzyl alcohol 360 g Sodium sulfite 36 g Triethanolamine 240 g Perex NBL
(Sodium t-butylnaphthalene sulfonate manufactured by Kao Atlas Co., Ltd.) 360 g Water 12
f Table 2

Claims (1)

[Claims] (1) In a diazo-sensitive lithographic printing plate having a photosensitive layer on a support, the photosensitive layer comprises a) a photosensitive diazo resin, b)
A diazo-sensitive lithographic printing plate comprising a composition containing a lipophilic polymer compound and c) a silane coupling agent.