JPH032867A - Photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the planographic printing plate which can be developed by an alkaline developing soln. and has excellent printing performance by incorporating a diazo resin having at least one piece of specific repeating units into an intermediate layer or photosensitive layer. CONSTITUTION:This planographic printing plate has the photosensitive layer formed of a photopolymerizable compsn. consisting of a polymerizable compd. having an ethylenic unsatd. bond, a photopolymn. initiator and a high-molecular polymer which is soluble in alkaline water or swellable in alkaline water and allows film formation and, if necessary, the intermediate layer on a base having a hydrophilic surface. The diazo resin having at least one piece of the repeating units expressed by formula I is incorporated into the intermediate layer or the photosensitive layer in this case. In the formula, R1 denotes a hydrogen atom, alkyl group which may have a substituent, alkoxy group, etc.; R2 denotes a carboxyl group, etc.; R3 denotes a hydrogen atom, alkyl group, etc.; R4 denotes a hydrogen atom, etc.; X<-> denotes anion; Y denotes -NH-, etc. The planographic printing plate which can be developed by the aq. alkaline soln. and has the excellent printing performance is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate, and more particularly, the present invention relates to a photosensitive lithographic printing plate having improved adhesion to a support having a hydrophilic surface and a lithographic printing plate soluble in an alkaline aqueous solution. The present invention relates to a photosensitive lithographic printing plate provided with a photopolymerizable photosensitive layer.

[Prior art and problems to be solved] There have been many attempts to use a photopolymerizable composition as a photosensitive image forming layer of a photosensitive lithographic printing plate. Basic composition consisting of polymer, monomer and photopolymerization initiator, Japanese Patent Publication No. 49-3404
Compositions in which unsaturated double bonds are introduced into a polymer as a binder to improve curing efficiency as disclosed in Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 53-276
Compositions using novel photopolymerization initiators are known, such as those disclosed in Patent No. 05 and British Patent No. 1,388,492.

However, the photosensitive layer does not have sufficient adhesive strength with the aluminum support, so if it is used as is, the image may peel off or be scratched by rubbing with a brush during development, resulting in insufficient image strength. This tendency is particularly noticeable at low exposure times, resulting in lower sensitivity and other problems.

Many attempts have been made to improve this poor adhesion. For example, Japanese Patent Application Laid-Open No. 54-72104, U.S. Patent No. 3
An attempt was made to use a negative-acting diazo resin as an undercoat layer as disclosed in the specifications of JP-A No. 905815,
Attempts to add diazo resin to photosensitive compositions as disclosed in No. 1-38943, attempts to use various adhesive layers,
For example, there have been attempts to use polyester resin, polyurethane, or epoxy resin as an undercoat, and in order to increase the adhesive strength on the support side, anodization was carried out on an aluminum support described in Japanese Patent Publication No. 46-26521. Method of anodizing film with phosphoric acid, JP-A-49-8428, JP-A-49-12903, JP-A-50-13890
No. 3, and JP-A No. 49-93101, the aluminum has been subjected to sulfuric acid electrolysis and then subjected to etching treatment using phosphoric acid, polyphosphoric acid, or alkaline solution to enlarge the anodized bore diameter. A method using a support is known.

However, in these methods, when the lithographic printing plate is developed with a developer consisting of alkaline water, the performance as a lithographic printing plate is insufficient.For example, when using a negative-working diazo, alkaline development It has poor solubility in liquids, and as a result, the diazo resin and photosensitive layer remain as residual films in non-image areas, causing problems such as staining during printing.

Furthermore, even when various types of adhesive layers are used, it is impossible to balance the contradictory properties of ease of removal during development and adhesive strength when forming an image area. Furthermore, from the aluminum support side,
In the case of the method of increasing the adhesive strength, at the same time the adhesive strength with the photosensitive layer is increased, the aluminum support in the non-image area receives ink easily during printing, which causes problems such as easy staining. There was a point.

Therefore, the present invention uses a photopolymerizable photosensitive composition to provide a lithographic printing plate that can be developed with an alkaline developer and has excellent printing performance while maintaining the excellent performance of the photosensitive layer obtained thereby. The purpose is to provide a photosensitive lithographic printing plate.

[Means to solve the problem]

The present inventor has prepared a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymeric polymer that is soluble in alkaline water or swellable in alkaline water and capable of forming a film on a support having a hydrophilic surface. A photosensitive lithographic printing plate having a photosensitive layer formed from a photopolymerizable composition and, if necessary, an intermediate layer: A diazo resin having at least one specific repeating unit is used in the intermediate layer or the photosensitive layer. It has been discovered that the above object can be achieved by incorporating it into the layer, and the present invention has been achieved based on this knowledge.

That is, the present invention provides a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer that is soluble in alkaline water or swellable in alkaline water and capable of forming a film on a support having a hydrophilic surface. In a photosensitive lithographic printing plate having a photosensitive layer formed from a photopolymerizable composition consisting of a polymer and, if necessary, an intermediate layer, a diazo resin having at least one repeating unit represented by the following general formula (I) is used. It relates to a photosensitive lithographic printing plate characterized in that it is contained in its intermediate layer or photosensitive layer.

In formula C, R represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a hydroxy group, a carboxy ester group, or a carboxyl group, and R7 represents a carboxyl group or at least one Represents a group having a carboxyl group, R1 represents a hydrogen atom, an alkyl group or an alkoxy group, R4 represents a hydrogen atom, an alkyl group or an alkoxy group, X'' represents an anion, and Y represents -NH-
--0- or -3-. ] Hereinafter, the present invention will be explained in detail.

The polymerizable compound having an ethylenically unsaturated bond in the photopolymerizable composition of the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure, and is a monomer prepolymer, i.e. 2 mer, trimer and other oligomers, mixtures thereof, and copolymers thereof. Examples thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid,
These include maleic acid.

Salts of unsaturated carboxylic acids include alkali metal salts of the aforementioned acids, such as sodium and potassium salts.

Specific examples of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic esters, such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. acrylate,
Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol triacrylate , sorbitol hexaacrylate,
Examples include polyester acrylate oligomers.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triester glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, and pentaerythritol dimethacrylate. Erythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis-[p(3-methacryloxy-2-hydroxypropoquine) phenylcdimethylmethane, bisCI)
-(methacryloxyethoxy)phenyldimethylmethane and the like. As itaconate ester,
ethylene glycol shiitaconate, propylene glycol diitaconate), 1,3-butanediol shiitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, pentaerythritol shiitaconate, sorbitol tetratrataconate etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate, and the like. Isocrotonic acid esters include ethylene glycol diisocronate, pentaerythritol diincrotonate, sorbitol tetraisocrotonate, and the like.

Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and norbitol tetramaleate. Furthermore, mixtures of the aforementioned esters may also be mentioned.

Specific examples of amides of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1.6-hexamethylenebis-methacrylamide. , diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide, and the like.

As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule described in Japanese Patent Publication No. 48-4 Nia 03 can be added to a polyisocyanate compound having the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group represented by It) is added.

CH2=C(R)COOCH, CH(R')OH(I
I) (However, R and R' represent a water atom or a methyl group.) As the photopolymerization initiator used in the present invention, the photopolymerization initiator disclosed in US Pat. No. 2,367.660 is used. Nar polyketaldonyl compounds, U.S. Pat. No. 2,367.6
61 and 2,367,670, U.S. Pat. No. 2,448,8
28, α-hydrocarbon-substituted aromatic acyloin compounds disclosed in U.S. Pat. No. 2,722,512, U.S. Pat. No. 3,046,127 No. 2.951.75
Polynuclear quinone compounds disclosed in US Pat. No. 8, doryarylimidazole dimer/p-aminophenyl ketone combinations disclosed in US Pat. No. 3,549,367, US Pat. benzothiazole compounds disclosed in US Pat. No. 4,239.850/trihalomethyl-5-)! J azine compounds, acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751,259, and oxadiazole compounds disclosed in U.S. Pat. No. 4,212,970. The amount used is in the range of about 0.5% to about 15% by weight, preferably 2 to 10% by weight, based on the total weight of the photopolymerizable composition. Or, as a polymer that can swell and form a film, Japanese Patent Publication No. 1987-
Benzyl (as described in No. 44615)
meth)acrylate/(meth)acrylic acid/addition-polymerizable vinyl monomer copolymer as required; methacrylic acid/methyl methacrylate or ester as described in Japanese Patent Publication No. 54-34327; Alkyl methacrylate copolymer; Other Japanese Patent Publication No. 8-12577
No., Special Publication No. 54-25957, Japanese Patent Publication No. 54-9272
(meth)acrylic acid copolymer as described in each specification of No. 3; allyl (meth)acrylate/(meth) as described in JP-A No. 59-53836;
Acrylic acid/other addition-polymerizable vinyl monomer copolymer as required, pentaerythritol triacrylate was added by half-esterification to the maleic anhydride copolymer described in JP-A-59-71048. -C○OH in polymers such as vinyl methacrylate/methacrylic acid/other addition-polymerizable vinyl monomer copolymers as required.

-PO3H2, -3OiH, -5OzNHz, -3O2
Examples include acidic vinyl copolymers having an NHCO group and an acid value of 50 to 200.

In particular, benzyl (meth)acrylate/(meth)acrylic acid/addition-polymerizable vinyl monomer copolymer and allyl (meth)acrylate/
(Meth)acrylic acid/other addition-polymerizable vinyl monomer copolymers as required are suitable.

These high molecular weight polymers can be used alone or as a mixture of two or more types. The molecular weight of the high molecular weight polymer is
Although the value can vary widely depending on the type of polymer, it is generally 5,000 to 100,000, preferably 10,000 to 500,000. The amount of the polymer used is 10% to 90%, preferably 30 to 8%, based on the total photopolymerizable composition.
It is 5%.

The diazo resin used in the present invention has at least one repeating unit represented by the following general formula N).

In the above formula, R6 represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy ester group, or a carboxyl group which may have a substituent, preferably a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. Alkyl group, carbon number 1-3
represents an alkoxy group or a hydroxy group.

R2 represents a carboxyl group or a group having at least 1' carboxyl group, preferably a carboxyl group or a group having 15 or less carbon atoms and having at least one carboxyl group.

R1 represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms.

R represents a hydrogen atom, an alkyl group or an alkoxy group,
Preferably it represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms.

X- represents an anion, preferably an anion of an inorganic or organic acid with a pKa of 4 or less, specifically a hydrohalic acid, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, Sulfuric acid, nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid, inorganic iso- and polyacids such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters, arsonic acids, phosphines acids, fluorocarboxylic acids such as trifluoroacetic acid, amidosulfonic acids, selenic acid, hydrofluoroboric acid, hexafluorophosphoric acid, perhydrochloric acid, as well as aliphatic and aromatic sulfonic acids,
For example, fluoroalkanesulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-
3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, cyamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4
-Butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-thalolopennesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, p-acetylbenzene Sulfonic acid, 5-nitro-〇-
Toluenesulfonic acid, 2-nitrobenzenesulfonic acid,
3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid acid,
2-Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid , dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, tributylnaphthalenesulfonic acid, 1-naphthol-
5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro-naphthalene-3,6-disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid , 1.2-naphthoquinone-2-diazido-4-sulfonic acid, 1.2-naphthoquinone-2-diazido-5-sulfonic acid and anion of 1.2-naphthoquinone-■-diazido-4-sulfonic acid, or anion of these Contains a mixture of anions. Particularly preferred among these anions are hexafluorophosphoric acid,
methanesulfonic acid, dodecylbenzenesulfonic acid or 2
-Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid anion.

Y represents -NH--0-1 or -5-, preferably -
Indicates NH-.

As a method for synthesizing the diazo resin used in the present invention, for example, 4
- A diazo monomer having a diazodiphenylamine skeleton, a 4-diazodiphenyl ether skeleton, or a 4-diazodiphenyl sulfide skeleton and an aldehyde having a carboxyl group or an acetal thereof, each preferably in a molar ratio of 1
:10-1:0.05, more preferably 1:2-1:
A method of condensation in an acidic medium at a ratio of 0.2 is exemplified. When performing the condensation reaction, a carboxyl group such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 1so-butyraldehyde, benzaldehyde, acetone, methyl ethyl ketone, or acetophenone is used to adjust the carboxylic acid value and molecular weight of the diazo resin produced. Active carbonyl compounds or their acetals which do not have a

The active carbonyl compound is most preferably formaldehyde, and its charging ratio is a molar ratio to the diazo monomer, preferably 1:0 to 1:5, more preferably;
Ma1: 0.1 to 1:1. -; When using an aldehyde having a carboxyl group and an active carbonyl compound not having a carboxyl group, first, the diazo monomer and the aldehyde having a carboxyl group are condensed in an acidic medium, and then more If the postcondensation is carried out using a highly reactive active carbonyl compound having no carboxyl group, such as formaldehyde, a diazo resin with a higher molecular weight can be obtained.

Specific examples of the diazo monomer include 4-diazodiphenylamine, 4'-hydroxy-4-diazodiphenylamine, 4'-methoxy4-diazodiphenylamine, and 4'-ethoxy-4-diazodiphenylamine.
4/, -propoxy-4-diazodiphenylamine, 4'-i propoxy-4-diazodiphenylamine,
4'~Methyl-4-diazodiphenylamine, 4'ethyl-4-diazodiphenylamine 4/-n-propyl-4-diazodiphenylamine, 4'-1-propyl-
4-diazodiphenylamine, 4'-n-butyl-4-
Diazodiphenylamine, 4'-hydroxymethyl-4
-diazodiphenylamine, 4'-β-hydroxyethyl-4-diazodiphenylamine, 4'-γ-hydroxypropyl-4-diazodiphenylamine, 4'-methoxymethyl-4-diazodiphenylamine, 4'-ethoxymethyl-4-diazo diphenylamine, 4'-β-
Methoxyethyl-4-diazodiphenylamine, 4'-
β-ethoxyethyl-4-diazodiphenylamine, 4
'-Carbomethoxy-4-diazodiphenylamine, 4
'-Carboethoxy-4-diazodiphenylamine, 4
'-Carboxy-4-diazodiphenylamine, 4-diazo-3-methoxy-diphenylamine, 4-diazo-
2-methoxydiphenylamine, 2'methoxy-4-diazodiphenylamine, 3-methyl-4-diazodiphenylamine, 3-ethyl-4-diazodiphenylamine, 3'-methyl-4-diazodiphenylamine, 3-ethoxy-4- Diazodiphenylamine, 3-hexyloxy-4-diazodiphenylamine, 3-β-hydroxyethoxy-4-diazodiphenylamine, 2-methoxy-5'-methyl-4-diazodiphenylamine, 4-diazo-3-methoxy-6-methyl diphenylamine, 3
．． 3'-dimethyl-4-diazodiphenylamine, 3
'-〇-butoxy 4-diazodiphenylamine, 3.
4'-dimethoxy-4-diazodiphenylamine, 2'
- Ruboxy-4-diazodiphenylamine, 4-diazodiphenyl ether, 4'-methoxy-4-diazodiphenyl ether, 4'-dimethoxy-4-diazodiphenyl ether, 4'-diazodiphenyl ether, 3.3'-dimethyl-4-diazodiphenyl ether, 4-diazodiphenyl sulfide, 4
'-Methyl-4-diazodiphenyl sulfide, 4'-
Examples include methyl-2,5-dimethoxy-4-diazodiphenyl sulfide.

Preferably, the aldehyde or acetal thereof having a carboxyl group includes an aldehyde having a structure represented by the following general formula (III) or an acetal thereof.

OOH R3 (II
[)HO [wherein R, may have a single bond or a substituent 2
It represents an organic group having a valence of 1 to 14 carbon atoms (for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, etc.). R
Examples of the group substituted with , include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom,
It includes a hydroxy group, a substituted or unsubstituted amino group, a carboxy ester group, a carboxyl group, and the like. ] Specific examples of these carboxyl group-containing aldehydes or their acecules include glyoxylic acid, malonaldehydic acid, succinic aldehydic acid, 2-methylsuccinaldehydic acid, 2-methoxysuccinaldehydic acid, 2-hydroxysuccinic acid, and Cinaldehydic acid, 2-chlorosuccinaldehydic acid, 2-aminosuccinic aldehydic acid, glutaraldehydic acid, 2-methylglutaraldehydic acid, 2-methoxyglutaraldehydic acid, 2-hydroxyglutaraldehydic acid, 2-chloroglutaraldehyde Acid, adipinaldehydic acid, pimelinaldehydic acid, sperinaldehydic acid, azelaic aldehydic acid, sebacinaldehydic acid, 2-formylmethylsuccinic acid, 2
- formyl ethyl succinic acid, formyl methyl malonic acid,
Formyl phthalmalonic acid, N- (2-formyl-2-
hydroxyethyl)glycine, N-(2-formyl-2
-hydroxyvinyl)glycine, 4,6-thioxohexanoic acid, 6-oxo-2,4-hexadinic acid, 3-
Formylcyclohexanecarboxylic acid, 4-formylphenylacetic acid, malealdehydic acid, fumaraldehydic acid, dibromomamalaldehydic acid, glucuronic acid, galactronic acid, mannuronic acid, idronic acid, guluronic acid, phthalaldehydic acid, 3,4-dimethoxyphthalaldehyde acid,
Isophthalaldehydic acid, terephthalaldehydic acid, 3
-Formyl-4-methoxybenzoic acid, 4-formylphthalic acid, 5-formylisophthalic acid, 4-formylmethylphthalic acid, 4-formyletherphthalic acid, 4-formylethoxyphthalic acid, 5-formylethoxyisophthalic acid, 4 -carboxymethylphthalic acid, 3-formyl-1-
Examples include naphthoic acid, 6-formyl-1-naphthoic acid, and acetals thereof.

When synthesizing the diazo resin used in the present invention: Specific examples of the acidic medium used include strong acids such as superacid, phosphoric acid, methanesulfonic acid, or sulfuric acid. These are used in concentrations of at least 30% by weight, preferably from 70 to 100% by weight.

Generally the remainder is water, but partially or completely organic solvents,
For example, it may consist of methanol, acetic acid, N-methylpyrrolidone, etc. Good results are e.g. 85-93%
- phosphoric acid, 80% - sulfuric acid or 90% - methanesulfonic acid or mixtures of these acids.

The temperature during condensation is about 0 to 70°C, preferably about 5 to 50°C.
It is ℃.

The weight average molecular weight of the diazo resin used in the present invention is approximately 5.
00 to 100,000, preferably about i,
The range is from o o o to 10.000. When this diazo resin is contained in the photosensitive layer, the content is 0.1 to 30
% by weight, preferably from 1 to 10% by weight.

In addition to the diazo resin of the present invention, if necessary, Japanese Patent Publication No. 47-1
167, JP-A-50-118802, JP-A-52-7364, and JP-A-59-22283.
A diazo resin as described in specifications such as Publication No. 4 may be used in combination in an amount of 50% by weight or less based on the diazo resin of the present invention.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive layer, such as hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, etc. 4'
-Thiobis(3-methyl-6-t-butylphenol), 2.2'methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. are useful, and in some cases, coloring of the photosensitive layer For this purpose, dyes or pigments, pH indicators, etc. can be added as print-out agents.

Furthermore, as a stabilizer for the diazo resin, malic acid, phosphorous acid, tartaric acid, citric acid, phosphoric acid, dipicolinic acid, polynuclear aromatic sulfonic acid and its salts, sulfosalicylic acid, etc. can be added as necessary. . Further, a wax agent can be added to prevent the polymerization inhibiting effect due to the influence of acid residue in the air. The wax used is solid at room temperature, but dissolves in the coating solution and precipitates on the surface during the coating and drying process. Examples include higher fatty acids such as stearic acid and behenic acid, higher fatty acid amides such as stearic acid amide and behenic acid amide, and other higher alcohols.

A photopolymerizable composition comprising a polymerizable compound having ethylenically unsaturated condensation, a photopolymerization initiator, and an alkaline water-soluble or highly swellable and film-formable polymer,
For example, dissolved in a suitable solvent such as 2-methoxyethanol, 2-methoxyethyl acetate, cyclohexane, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene dichloride, propylene glycol monomethyl ether, methyl lactate, etc. alone or in a mixed solvent of an appropriate combination of these solvents. On the support: It is divided into two parts, and the amount of coverage after drying is about 0. ig/m'' ~ approx. 10g/
The range of m' is suitable, preferably 0.5g to 5g.
g/m'.

In the present invention, the thickness of the intermediate layer provided as necessary can be changed arbitrarily, but it must be a thickness that allows a uniform bond-forming reaction to occur with the upper photosensitive layer when exposed to light. Usually about 1 to 100 mg/m' in dry solid form
A coating ratio of 5 to 40 mg/m'' is particularly good.

Furthermore, in addition to the diazo resin, diazo stabilizers, sensitizers,
Various additives such as antihalation agents, polymeric binders, and surfactants may also be blended.The ratio of the diazo resin to the intermediate layer is 30% to 100% by weight, preferably,
6d-100 weight 96.

The intermediate layer is formed by dissolving the diazo resin and the compound used in the present invention in a solvent, coating it on a support, and drying it. In addition, as a method other than coating, it can also be obtained by dipping the support in a solution containing components for the intermediate layer and drying.

The support having a hydrophilic surface used in the present invention is
A dimensionally stable plate-like material is desirable. Such dimensionally stable plate-like materials include those used as supports for previously unprinted materials, and can be suitably used in the present invention.

Such supports include paper, paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), plates of metals such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, triacetate, etc. cellulose acetate, cellulose propionate,
Films of plastics such as cellulose acetate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above are included. Among these supports, aluminum plates are preferred because they are extremely dimensionally stable, inexpensive, and have particularly good adhesion to the photopolymerizable composition of the present invention. In addition, the special public official
Also preferred are composite sheets in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in Japanese Patent No. 18327.

Further, in the case of a metal 1 support, particularly an aluminum support, it is preferable that the support be subjected to surface treatment such as graining treatment or anodizing treatment.

Further: To increase the hydrophilicity of the surface; Sodium silicate,
It is preferable to perform immersion treatment in an aqueous solution of potassium fluorozirconate, phosphate, or the like. U.S. Patent No. 2,71
As described in Japanese Patent Publication No. 4,066: After graining, the treated aluminum plate was immersed in an aqueous sodium silicate solution, and the aluminum plate was anodized as described in Japanese Patent Publication No. 475125. After the treatment, those treated by immersion in an aqueous solution of an alkali metal silicate are also suitably used.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-5
8602 and JP-A-52-30503; a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodizing treatment and sodium silicate treatment as disclosed in these publications is also useful.

Furthermore, those which are sequentially subjected to brush graining, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after these treatments, it is also suitable to apply an undercoat with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, or the like.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. This is done for the purpose of improving.

On the intermediate layer and photosensitive layer provided on the support, in order to completely prevent the polymerization inhibiting effect caused by oxygen in the air, a material with oxygen barrier properties such as polyvinyl alcohol, acidic cellulose, etc. is used. A protective layer made of polyamide 7 may also be provided. A method of applying such a protective layer is described, for example, in U.S. Pat. No. 3,458,311,
It is described in detail in each specification of No. 49729.

The photosensitive lithographic printing plate of the present invention is processed using a metallization lamp,
A lithographic printing plate is prepared by imagewise exposure using a light source rich in ultraviolet light such as a high-pressure mercury lamp, processing with a developer to remove unexposed areas of the photosensitive layer, and finally coating with a gum solution.

Examples of the developer for the photosensitive lithographic printing plate of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, sodium diphosphate, ammonium triphosphate, and diphosphate. Aqueous solutions of inorganic alkaline agents such as ammonium acid, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentration is 0.1 to 10% by weight,
It is preferably added in an amount of 0.5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as necessary. Preferred organic solvents include benzyl alcohol, 2-phenoxyethanol, 2-butoxyethanol, and n-propyl alcohol. In addition,
It is also preferred to add diazo solubility promoters, for example sulfites, methylresorcinol, pyrazolone compounds, amine compounds such as phenylenediamine. Additionally, U.S. Patent No. 3
, 475.171 and 3,615,480. Furthermore, Japanese Patent Application Publication No. 50-26601, Japanese Patent Publication No. 56-3946
4 and No. 56-42860 are also excellent as developers for printing plates using the photopolymerizable composition of the present invention.

〔Effect of the invention〕

The photosensitive lithographic printing plate of the present invention has high sensitivity, can be developed with an alkaline aqueous solution, and has excellent printing performance. Furthermore, it can be developed using a conventional positive PS plate developer (silicate aqueous solution) and can be developed using the same processing system.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples.

Note that "%" indicates weight % unless otherwise specified.

(Synthesis example) An example of synthesis of the diazo resin used in the present invention will be explained.

However, the scope of the present invention is not limited by these synthesis examples.

Synthesis Example 1 29.3 g of 4-diazodiphenylamine hydrogen sulfate
(0,10Omof) was dissolved in 85% phosphoric acid 70 mA. This includes glyoxylic acid monohydrate (9?%)
Add 4.74 g (0,0500 moj'),
The mixture was stirred at 0°C for 20 hours. Next, 1.58 g (0,050 g) of paraformaldehyde (95%) was added to the reaction mixture.
Omof) was added and stirred for an additional 20 hours at 40°C.

After that, the reaction solution was mixed with isopropyl alcohol 80++
+j7 with stirring to precipitate a yellow precipitate. By filtering this yellow precipitate and washing with isopropyl alcohol, 4-diazodiphenylamine-
A dihydrogen phosphate salt of a glyoxylic acid/formaldehyde condensate was obtained.

This condensate was dissolved in 400+1 of water, and 41.8 g of sodium n-dodecylbenzenesulfonate (0
, 12Omof) water 600mj! The solution was added with stirring. The produced yellow precipitate was collected by filtration and dried to give 4-
Diazodiphenylamine-glyoxylic acid/formaldehyde condensate n-dodecylbenzenesulfonate 44
(diazo resin (a) of the present invention).

The carboxylic acid value of the obtained diazo resin was 0.98 meq/
It was g. Further, the weight average molecular weight of the obtained diazo resin was measured using GPC (polystyrene standard) after coupling with -phenyl-3-methyl-5-pyrazolone, and found to be 1,950.

Synthesis Example 2 32.3 g (0, L OOmof) of 4'-methoxy-4-diazodiphenylamine hydrogen sulfate was dissolved in 85% phosphoric acid TOm1. This was supplemented with glyoxylic acid l-hydrate (97% > 6.64 g (0,070Omof)
was added and stirred at 40°C for 20 hours. Next: 3.96 g (0,090 g) of acetaldehyde is added to this reaction mixture.
Omof) was added and stirred for an additional 20 hours at 40°C. After that, the reaction solution was mixed with isopropyl alcohol 800+
nj! was added to the solution while stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain the dihydrogen phosphate salt of 4'-methoxy-4-diazodiphenylamine-glyoxylic acid/acetaldehyde condensate.

This condensate was dissolved in 400 ml of water, and a solution of 39.6 g (0.120 oz.) of sodium 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate in 600 ml of water was added with stirring.

The produced yellow precipitate is collected by filtration and dried to obtain 2-methoxy-4-hydroxy-5-benzoylbenzenesulfone of 4-diazodiphenylamine-glyoxylic acid/acetaldehyde condensate! 39 g of salt was obtained (diazo resin (b) of the present invention).

The carboxylic acid value of the obtained diazo resin was 1.10 meq/
It was g. Further, after coupling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using 2GPC (polystyrene standard) and found to be 1,730.

Synthesis Example 3 29.3 g of 4-diazodiphenylamine hydrogen sulfate (0
, 70ml of 96% sulfuric acid! This was dissolved. To this was added 16.5 g of terephthalaldehydic acid (0,110
The mixture was stirred at 5° C. for 3 hours. Next, the reaction solution was poured into isopropyl alcohol at 800 mA with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain hydrogen sulfate of 4-diazodiphenylamine-terephthalaldehyde acid condensate.

Add this condensate to 200mj of water! and MEK 500mf, and a solution of 41.8 g (0.120 mof) of sodium n-dodecylbenzenesulfonate in 600 mof of water was added thereto with stirring. After stirring for a while, the mixture was allowed to stand and was separated into two layers.

The upper layer was poured into 2 fl of water with stirring, and the yellow precipitate produced was collected by filtration and dried to obtain diphenylamine-
46 g of n-dodecylbenzenesulfonate of terephthalaldehyde acid condensate was obtained (diazo resin of the present invention (C
)).

The carboxylic acid value of the obtained diazo resin was 0.89 meq/
The weight average molecular weight of the resulting diazo resin was measured using GPC (polystyrene standard) after coupling with 1-phenyl-3-methyl-5-pyrazolone, and found to be 1,450.

Synthesis Example 4 32.3 g of 4-diazo-3-methoxydiphenylamine hydrogen sulfate (0,100 moβ) was dissolved in 96% sulfuric acid 100
Dissolved in ml. This is combined with rose formaldehyde (95
%) 3.16g (0,100mof) was added, 5
Stirred at ℃ for 2 hours. Next, 7.50 g of terephthalaldehyde acid (0,0500 moj
of the mixture was added, and the mixture was further stirred at 5° C. for 2 hours. Thereafter, the reaction solution was poured into 800 ml of isopropyl alcohol with stirring to precipitate a yellow precipitate. This yellow precipitate was filtered and washed with isopropyl alcohol to obtain the hydrogen sulfate of 4-diazo-3-methoxydiphenylamine-formaldehyde/terephthalaldehyde acid condensate.

Add this condensate to 400 mj of water! 22.1 g of potassium hexafluorophosphate (0,1'20
A 600ml solution of water was added with stirring.

The produced yellow precipitate was collected by filtration and dried to give 4-diazo-3
-Methoxydiphenylamine-formaldehyde/terephthalaldehyde acid condensate hexafluorophosphate 2
8 g was obtained (diazo resin (d) of the present invention).

The carboxylic acid value of the obtained diazo resin was 0.54 meq/
It was g. Further, after coupling the obtained diazo resin with 1-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene PA$) and found to be 2,300.

Synthesis Example 5 37.4 g (0,100 m
of) was dissolved in 70 mj2 of 96% sulfuric acid. This includes glitaraldehyde acid (4-formylbutanoic acid) 4.64
g (0,0400 moj') was added and stirred at 5°C for 2 hours. Next, rose formaldehyde (95% > 1.90 g (0,0600 mol)) was added to the reaction mixture and stirred for an additional 2 hours at 5°C.Then, the reaction solution was poured into 1.51' of ice water with stirring. Then, 260 g of 50% zinc chloride aqueous solution was added to precipitate a yellow precipitate.The yellow precipitate was filtered and 4'-methyl-2,5
-Dimethoxy-4-diazodiphenyl sulfide-glutaraldehyde acid/formaldehyde condensate zinc chloride double salt was obtained.

This condensate was mixed with 800 mji of water! 22.1 g (0,120 mol) of potassium hexafluorophosphate was dissolved in
) was added to a 600% water solution with stirring.

The formed yellow precipitate was collected by filtration and dried to give 4'-methyl-
50 g of hexafluorophosphate of 2,5-dimethoxy-4-diazodiphenyl sulfide-glutaraldehyde acid/formaldehyde condensate was obtained (diazo resin (e) of the present invention).

The carboxylic acid value of the obtained diazo resin was 0.77 meq/
It was g. Further, after coupling the obtained diazo resin with (1)-phenyl-3-methyl-5-pyrazolone, the weight average molecular weight was measured using GPC (polystyrene standard) and found to be 2,130.

Example 1 The surface of an aluminum plate having a thickness of 0.30 mm was grained using a nylon brush and 400 ml of Bumiston water lily solution, and then thoroughly washed with water.

After etching by immersing in IJum (10% hydroxide) at 70°C for 60 seconds, washing with running water, neutralizing with 20% (N Oy) and washing with water. Electrolytic surface roughening treatment was performed using a sinusoidal alternating waveform current in a 1% nitric acid aqueous solution at an anode current of 160 corons/dm. When the surface roughness was measured, it was found to be 0.6μ.
(Ra display). followed by 30% H2SO,
After being immersed in an aqueous solution and desmutted for 2 minutes at 55°C, the current density was 2A/dm2 in a 20% H2SO+aqueous solution.
Anodic oxidation treatment was performed for 2 minutes to obtain a thickness of 2.7 g/m'. The obtained aluminum support was immersed in a 2.5% aqueous solution of sodium silicate at 70° C. for 1 minute, washed with water, and dried.

Next, the following diazo resin solution was applied onto an aluminum support using a spin coater so that the weight after drying was 20 rag/m', dried at 80°C for 1 minute, and an intermediate coating was applied. formed a layer.

Next, the following photopolymerizable composition (I).

Photopolymerizable composition (I) 0 poly (allyl methacrylate/5.0
g methacrylic acid) copolymerization molar ratio 70/300 pentaerythritol tetra 1.5 g acrylate 0 combination of the following photoinitiators 0.3 g 10.3
g Rofin dimer/Michler's ketone op-methoxyphenol 0.01g
0 oil blue #603 0.15g
oF-177 (manufactured by Dainippon Ink @, 0.05g)
Fluorine surfactant) 100 g of ethylene glycol methyl ether 50 g of methanol 50 g of methyl ethyl ketone 2.
It was coated at 0 g/m' and dried at 80°C for 2 minutes to form a photosensitive layer.

Finally, polyvinyl alcohol for wearing overcoats (
Saponification degree 86.5-89.0mof%, polymerization degree 1ooo
A 3% by weight aqueous solution of the following) was coated on the surface of the photosensitive layer using a rotary coater to give a dry weight of 1.5 g/m' to produce a photosensitive lithographic printing plate: A2. .

Comparative Example 1 A photosensitive lithographic printing plate CB2 was produced in the same manner as in Example 1, except that the photopolymerizable composition (I) and an overcoat layer were directly provided on the aluminum support without providing the diazo intermediate layer.

A grayscale tablet manufactured by Fuji Photo Film @ and a halftone negative film were placed on top of these photosensitive planographic printing plates (A) and CB), and a printer FT manufactured by Nuark Co., Ltd. (USA) was placed.
It was exposed to light for 50 counts using a 26V2UPNS (light source: 2kw metal halide lamp), immersed in the following developer at 25°C for 1 minute, rubbed lightly with absorbent cotton, and washed with water.

(Developer) 0 Isopropylnaphthalene 5 g Sodium sulfonate 0 Pure water
1000 g Obtained lithographic printing plate [A]
and 2B] using a Heidelberg ff1KOR-D printing machine, and the results are shown in Table 1.

Table 0: 0.3 g of photopolymerization initiator The lithographic printing plate of the present invention has high sensitivity and excellent adhesion, so it has excellent scratch resistance and printing durability.

Example 2 On the aluminum support used in Example 1: The photopolymerizable composition (2) on the lower two sides was added in the same manner as in Example 1, with a dry weight of 2
．． It was coated and dried to give a coating weight of 0 g/m', thereby forming a photosensitive lithographic printing plate [C].

0 Behenic acid amide 0.2g 0 Malic acid 0.05
go Diazo resin Q) of the present invention (Synthesis Example 2) 0
．． 3go F 177 (Dainippon Ink, K,
) 0.05go ethylene glycol monomethyl ether too gO methyl ethyl ketone
50 go methanol
50 g Comparative Examples 2-3 Example 2 was repeated, except that a photopolymerizable composition not containing the diazo resin (b) of the present invention was applied to prepare a photosensitive lithographic printing plate CDE. Obtained. Example 2 was repeated except that n-dodecylbenzenesulfonic acid, a condensation product of p-diazodiphenylamine and formaldehyde, was used in place of the diazo resin (b) of the present invention to obtain a photosensitive lithographic printing plate CE]. .

These photosensitive planographic printing plates [C″: to [E] were prepared in Example 1.
Exposure, development, and printing were performed in the same manner as above.

The performance of these lithographic printing plates is shown in Table 2 below.

Claims (1)

[Scope of Claims] A polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer polymer that is soluble in alkaline water or swellable in alkaline water and capable of forming a film are placed on a support having a hydrophilic surface. In a photosensitive lithographic printing plate having a photosensitive layer formed from a photopolymerizable composition and an intermediate layer if necessary, a diazo resin having at least one repeating unit represented by the following general formula (I) is used. A photosensitive lithographic printing plate, characterized in that it is contained in the intermediate layer or photosensitive layer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 represents a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group, a hydroxy group, a carboxyester group, or a carboxyl group, and R_2 represents a carboxyl group or a group having at least one carboxyl group, R_3 represents a hydrogen atom, an alkyl group, or an alkoxy group, R_4 represents a hydrogen atom, an alkyl group, or an alkoxy group, and X^- represents an anion. , and Y represents -NH-, -O- or -S-. ]