JPH04204449A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having high sensitivity and satisfactory ink receptivity and fit for UV ink by incorporating o- naphthoquinonediazidosulfonic ester and a copolymer resin having specified structural units and structural units each having a carboxyl group. CONSTITUTION:The o-naphthoquinonediazidosulfonic ester and a copolymer resin having structural units represented by formula I (where each of R1 and R2 is H or alkyl) and structural units each having a carboxyl group are incorporated to obtain a photosensitive compsn. having high sensitivity, superior ink receptivity and alkali resistance, not causing stain at the non-image area and having superior printing resistance even when UV ink is used.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a photosensitive composition suitable for use in a photosensitive lithographic printing plate, and more particularly, to a photosensitive composition suitable for use in a lithographic printing plate having UV ink suitability. The present invention relates to photosensitive compositions that can be used.

[Background of the Invention] A photosensitive lithographic printing plate has an ink-receptive photosensitive layer provided on a hydrophilic support. For example, in a positive photosensitive lithographic printing plate, an ink-receptive photosensitive layer is provided on a hydrophilic support. An ink-receptive photosensitive layer is formed which is solubilized by exposure to actinic rays. When the photosensitive layer of such a positive-working photosensitive lithographic printing plate is subjected to imagewise exposure and then developed, the photosensitive layer in the exposed areas is removed and the surface of the hydrophilic support is exposed, while the photosensitive layer in the unexposed areas is removed. remains on the support to form an ink-receiving layer.

In planographic printing, the difference in properties is utilized in that the exposed areas are hydrophilic and the unexposed areas are lipophilic.

In recent years, ultraviolet curable UV inks have been used as planographic printing inks, and there has been a demand for photosensitive planographic printing plates that are suitable for UV inks.

As a photosensitive composition for obtaining a photosensitive lithographic printing plate having UV ink suitability, a polymeric substance having an N-(sulfamoyl-substituted phenyl)carbamoyl group is used as a binder, or as described in JP-A No. 2-866. Are listed. However, the photosensitive composition has problems in that it does not have sufficient solubility in an aqueous alkaline developer, requires a long time for printing, and causes staining in non-image areas.

[Object of the Invention] Therefore, an object of the present invention is to provide a photosensitive composition having high sensitivity, good ink receptivity, and suitability for UV inks.

[Structure of the Invention] The above object is to (1) contain a copolymer resin having an o-naphthoquinonediazide sulfonic acid ester and a structural unit represented by the following general formula [I] and a structural unit having a carboxyl group. Characteristic planographic printing plate.

General formula [I] "Yu CH2-C'+- C=OH In the formula, R5 and R3 each represent a hydrogen atom or an alkyl group.

(2) A resin comprising a compound having a polyoxyalkylene structural unit and a condensate of a substituted phenol represented by the following general formula [I1] and an aldehyde, and/or an 0-naphthoquinonediazide sulfonic acid ester compound of the resin The photosensitive composition according to item (1) above, characterized in that it contains.

General formula [IIcoH In the formula, R1 and R4 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R5 represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms.

achieved by.

The present invention will be explained in detail below.

Examples of the 0-naphthoquinonediazide sulfonic acid ester used in the present invention include ester compounds of 0-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones.

Examples of the above phenols include phenol, 0-
Cresol, m-cresol, p-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Further, examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and the like.

Specific examples of polycondensation resins include phenol/formaldehyde resin, m-cresol/formaldehyde resin, m-, p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/formaldehyde resin.
Examples include acetone resin.

In the above 0-naphthoquinonediazide sulfonic acid ester, the condensation rate of 0-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol (reaction rate with respect to one OH group) is preferably 15 to 80%, more preferably 20%.
~45%.

Further, as the 0-naphthoquinonediazide sulfonic acid ester used in the present invention, there can be mentioned the 0-naphthoquinonediazide sulfonic acid ester described in JP-A-58-43451.

More specifically, Jay Kosar (J, Kosar)
Author: “Light Sensitive Systems”
t-9ensistive Systems”) 3rd
pp. 39-352 (1985), John Wiley & Sons, Inc.
Yaduburi Ninis Day Forest (111,s
, De Forest) “Photoresist” (“
Photoresist'') Volume 50 (1975),
1,2-naphthoquinone diand-4- described in McGrav-Hill (McGrav-Hi II) etc.
Sulfonic acid phenyl ester, 1.2-naphthoquinone cyacito-5-sulfonic acid phenyl ester, 1.2-naphthoquinone cyacito-4-sulfonic acid cyclohexyl ester, 1.2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1 - (1,2-naphthoquinone diacid-5-sulfonyloxy)-3,5-dimethylpyrazole, 1,2-naphthoquinone diacid-4-
Sulfonic acid-4'-hydroxydiphenyl-4'-azo β-naphthol ester, 2'-(1,2-naphthoquinonediazide-4-sulfonyloxy)=1-hydroxy-anthraquinone, 1,2-naphthoquinone cyasito-4 -sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-4-sulfonic acid-2,3゜4-trihydroxybenzophenone ester, 2 moles of 1゜2-naphthoquinonediazide-4-sulfonic acid chloride and 4.4'-dihydroxy-1,1'
- condensate of 1 mole of diphenylsulfone, condensate of 1 mole of 1,2-naphdoquinone diazito-4-sulfonic acid chloride and 1 mole of purbrogalin, 1,2-naphthoquinone siato-5-sulfonic acid-4'-hydro quindiphenyl
4'-azo-β-naphthol ester, 2'-(1
, 2-naphthoquinonediazide-5-sulfonyloxy)
-1-Hydroxy-anthraquinone, 1.2=naphthoquinone cyasito-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1.2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester , 1.2-naphthoquinonediazide-
A condensate of 2 moles of 5-sulfonic acid chloride and 1 mole of 4,4'-dihydroquine-1,1'-diphenylsulfone,
〇- such as a condensate of 1 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of purprogalan
Naphthoquinonediazide sulfonic acid ester can be cited as an example.

Also, Special Publication No. 37-1953, No. 37-3827,
No. 37-13109, No. 40-26126, No. 40
-3801, 45-5604, 45-2734
No. 5, No. 51-13013, JP-A-48-96575
4g-[I3g02 and 48-63803] may also be mentioned.

Among the above 0-naphthoquinonediazide sulfonic acid esters, 1,2-naphthoquinonediazide sulfonylcrocyto and pyrogallol/acetone condensation resin or 2,3.4-)
O- obtained by reacting rehydroquine benzophenone
Particularly preferred are naphthoquinonediazide sulfonic acid esters.

As the 0-naphthoquinonediazide sulfonic acid ester used in the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination.

The proportion of 0-naphthoquinonediazide sulfonic acid ester used in the present invention in the photosensitive composition is 5 to 60%.
% by weight is preferred, particularly preferably 10-50% by weight
It is.

Next, a copolymer resin having a structural unit represented by the general formula [I] and a structural unit having a carboxyl group (hereinafter referred to as the binder resin of the present invention) will be described.

In general formula [I], R1 and R2 are t7/L.

The kill group is preferably a lower alkyl group, such as a methyl group or an ethyl group.

Preferred examples of R and R2 are a hydrogen atom and a methyl group.

Specific examples of the structural unit represented by general formula [I] are shown below.

Margin below -al-b 云CH2CH+ *CL C
H sho c=o c=.

-cI-d CHi　　　　　　　　　　　CH.

-1- CH2-CH juice -+ C
I(2-CH square c=o
c=.

(CH, -CH← Published CH2-CH
←c=o c=.

(CH2-CH← (Cfl>-CH
Soup c=o c=.

The structural unit having a blank carboxyl group is not particularly limited as long as it has a carboxyl group. Examples include structural units having the following structure.

Specific examples of the monomer include acrylic acids such as acrylic acid and methacrylic acid, and unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride.

The binder resin of the present invention has a structural unit represented by the general formula [I] and a structural unit having a carboxyl group, but in addition to the above structural units, one or more other monomers may be added. may have a structural unit derived from a copolymer component (hereinafter referred to as a copolymer component structural unit).

Monomers that lead to these copolymer component structural units include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; styrene, α
- Styrenes such as methylstyrene, p-methylstyrene, and p-chlorostyrene; methyl diacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate;
Esters of α-methylene aliphatic monocarboxylic acids such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide anilides such as acryloanilide, p-chloroacryloanilide, m-nitroacryloanilide, and m-methoxyacryloanilide.

Vinyl acetate, vinyl propionate, vinyl benzoate,
Vinyl esters such as vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride; vinylidene chloride: vinylidene cyanite, 1-methyl-1-methoxyethylene, 1.1
- Ethylene derivatives such as dimethoxyethylene, 1,2-cymethine ethylene, 1-dimethoxycarbonylethylene, 1-methyl-1-ditroethylene; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N -N-vinyl compounds such as vinylpyrrolidone and N-vinylpyrrolidone; and other vinyl monomers. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above-mentioned monomers, esters of aliphatic monocarboxylic acids and nitriles are preferred because they exhibit excellent performance for the purpose of the present invention.

These structural units may be bound in the binder resin of the present invention in either a block or random manner.

Typical binder resins of the present invention are illustrated below. In addition, in the following, Mw is weight average molecular weight, M
n is the number average molecular weight, s, (1°m and n are the mol% of the respective structural units.

The following margins (CH2-CH)-r-one child CL-C), -one child CL-
CHh.

11 l C”OCOOC2H5C0OH H (a-2) CH,CH3 −+ CH2−CH)−t−(−force2 C′h−+C
H2C) Ql 1
1C=OCOOC2H5C0OH H m: n: g-35+50:15 + 1
1-(CF+2-C←"-→CH,-C←"-yunC
H2) 0 sho ``-Yun CH2-CH soup.

1 1
I IC=OC00CH,C0
OHCN H Mw-3,3X10' Mw/Mn-5,2rn
', n: Q: k-20:30:10:30C=
OC00CH3C0OHCN H Mw= 3.0X10' Mw/Mn= 4.2
m:n: 9:k=20:30:10:30il (CH2-CH←, (C)!2-C light "HCO2C"
HCO2CH square.

C"OC00C2H40HC0OHCNH m: n: Q: k=30:10:20:40 (
CH2-C Wanting→CH, -C←, t(, L-C←"→C
H2-CH square.

l) I
IC=OC=OC0OHCN m:n: Q: k-30:30:20:20C=O
C=OCOOCH3CN C0OH(d-2
) CH3CHi C=OC=OC00C, H5CN C0OH
I Mw-2, 2X10' Mw/Mn= 5.9m
'n:il:k:5-10:10:10:
40:30 The binder resin of the present invention is capable of deriving a structural unit having an ethylenically unsaturated monomer and a carboxyl group that can be cleaved to derive a structural unit represented by the general formula [I]. The ethylenically unsaturated monomers that can be prepared and, if necessary, the other monomers mentioned above, are co-produced with or without a polymerization initiator and with or without a solvent. It can be obtained by polymerization.

At this time, the molecular weight and the molar ratio of each structural unit can be set over a wide range by varying the charging molar ratio of each carmer and the polymerization conditions.

However, in order to effectively serve the purpose of the present invention, the weight average molecular weight must be set to 5. OX 103~2,0×10
It is appropriate to set it as 5. OX 103~50×
104 is preferred. Further, the molar content of the structural unit represented by the general formula [I] and the structural unit having a carboxyl group is preferably at least 10 mol%. More preferably, it is 10 to 40 mol%.

The content of the binder resin of the present invention in the photosensitive composition is preferably 30 to 95% by weight, more preferably 5% by weight.
It is 0 to 80% by weight.

Moreover, the above molecular weight was measured by GPC (gel permeation chromatography method).

In the present invention, various known compounds having a polyoxyalkylene structural unit can be used, but surfactants having at least one of the following structural units [I[[] and [IV] can be particularly preferably used. .

Structural unit [III] (CH2C820 sho.

Structural unit [IV] CH3 Published CH2CHO*-4 (In each formula, n represents an integer of 2 to 5000.) Especially, in each of structural units [In] and [IV], n is 2
A compound in which n is an integer within the range of 5,000 and has a boiling point of 240°C or higher is preferable, and more preferably n is 2 to 5.
The compound is an integer within the range of 000 and has a boiling point of 280°C or higher, and most preferably n is 3 to I00.
is a compound that is an integer within the range of .

Examples of such compounds include: -Polyethylene glycol CFIO+CH2CH2@,H) -Polyoxyethylene alkyl ether -Polyokine ethylene alkylphenyl ether -Polyoxyethylene polystyrylphenyl ether -Polyoxyethylene-polyoxypropylene glycolFor example, - Polyoxyethylene-polyoxybrobylene alkyl ether, including random polymers.

・Ethylene oxide derivative of alkylphenol formalin condensate ・Polyoxyethylene polyhydric alcohol fatty acid partial ester C) 120 (CH2C1 (20). OCRC10 (CI
(2CI(20) Rabbit CR Cf(O(Ct(2cHzo), f( CI(0(C)12(:H2O) IIH 臂CHO(CH2C)I20).H C)1,0(CI(2C)120 ), polyoxyethylene alkylamine in H.polyoxyethylene fatty acid ester (for example, RCOO(CH2CH20)nH), and the like.

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 sorbitate tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, These include polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphene and ether formaldehyde condensate, oxyethylene oxypropylene block copolymer, tetraethylene glycol, polyethylene glyfur, and the like.

The proportion of the nonionic surfactant in the photosensitive composition is preferably 0.05 to 10% by weight, more preferably 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 the present invention, a resin consisting of a condensate of a substituted phenol and an aldehyde represented by the following general formula [II] and/or an 0-naphthoquinonediazide sulfonic acid ester compound of the resin is mainly used in printing ink for images. It is used as a fat-sensitizing agent that has the function of increasing ink adhesion with.

General Formula [I1] In the formula, R3 and R4 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R5 represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms.

In the general formula [■], R1 and R4 each include a hydrogen atom and an alkyl group (containing 1 to 3 carbon atoms).Alkyl groups having 1 to 2 carbon atoms are particularly useful.

) or a halogen atom (fluorine, chlorine, bromine, and iodine, particularly chlorine and bromine are preferred), and R5 is an alkyl group having 2 or more carbon atoms (preferably an alkyl group having 15 or less carbon atoms, and 3 to 3 carbon atoms). 8 alkyl groups are particularly useful) or cycloalkyl groups (preferably cycloalkyl groups containing 3 to 15 carbon atoms, and cycloalkyl groups containing 3 to 8 carbon atoms are particularly useful). .

Examples of the substituted phenols include isopropylphenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-tert-butylphenol, isopropylcresol, tert- butyl cresol, t
ert-amyl cresol, hexyl cresol, te
These include rt-octyl cresol and cyclohexyl cresol, among which tert-octyl cresol and tert-butyl cresol are particularly preferred.

Further, the above aldehydes can be condensed with substituted phenols to produce resins, and include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, allurolein, crotonaldehyde, and furfural, among which formaldehyde is preferred. and benzaldehyde.

The resin made of the condensate of substituted phenols and aldehydes in the present invention is usually synthesized by polycondensing the substituted phenol represented by general formula [I1] and aldehydes in the presence of an acidic catalyst. .

Acidic catalysts used include hydrochloric acid, oxalic acid, sulfuric acid,
An inorganic acid or an organic acid such as phosphoric acid is used, and the blending ratio of substituted phenol and aldehyde is 0.7 to 1.0 mole per mole of substituted phenol. Alcohols, acetone, water, tetrahydrofuran, etc. are used as the reaction solvent, and after reaction at a predetermined temperature (-5 to 120°C) for a predetermined time (3 to 48 hours), the product is heated under reduced pressure, washed with water, and dehydrated. Alternatively, water may be precipitated to obtain a condensed resin as a reactant.

In the present invention, this condensation resin is used as it is or as an 0-naphthoquinonediazide sulfonic acid ester compound of the resin.

The ester compound is prepared by dissolving the condensation resin in a suitable solvent such as dioxane.

- Naphthoquinone diazide sulfonic acid chloride is added, heated and stirred, and then an alkali such as an alkali carbonate is added dropwise to the equivalence point to cause esterification.

In the ester compound, the condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to the hydroxyl group of the phenol (reaction rate % with respect to one hydroxyl group) is 5 to 80.
%, more preferably 20 to 70%, still more preferably 30 to 60%.

The condensation rate is a value obtained by determining the content of sulfur atoms in the sulfonyl group by elemental analysis.

The photosensitive composition of the present invention can contain a known alkali-soluble resin. Examples of alkali-soluble resins include novolak resins, such as phenol-formaldehyde resins, cresol-formaldehyde resins, phenol-modified xylene resins, and polyhydroquinestyrene, but such alkali-soluble polymer compounds account for 40% of the total composition by weight. % or less.

In addition to the materials described above, the photosensitive composition of the present invention can contain other additives as necessary. Plasticizers include various low-molecular compounds such as phthalate esters, triphenyl phosphates, maleate esters, and coating properties improvers include surfactants such as fluorine surfactants and ethyl cellulose polyalkylene ether. Examples include nonionic activators and the like, as well as printout materials for forming visible images upon exposure to light. The printout material consists of a compound that generates acid or free radicals when exposed to light, and an organic dye that changes its color tone by interacting with it. 0-Naphthoquinonediazide-4-sulfonic acid halide described in Publication No. 50-38209, JP-A-5
Trihalomethyl-2-pyrone and trihalomethyl-triazine described in Publication No. 3-36223, JP-A-5
Ester compounds of 0-naphthoquinonediazide-4-sulfonic acid chloride and phenols or anilines having an electron-withdrawing substituent, which are described in Japanese Patent Application Laid-Open No. 55-77742, Examples include halomethyl-vinyl-oxadiazole compounds and diazonium salts.

Among these, halomethyl-vinyl-oxadiazole compounds are preferred, and in particular, as described in JP-A-138539, an oxygen-containing heterocyclic group such as a benzofuryl group is attached to the 5-position via a vinyl group. More preferred are 2-halomethyl-1,3,4-oxadiazole compounds having the following.

In addition, as the dye mentioned above, for example, Victoria Pure Blue BOH [Oudugaya Chemical Co., Ltd., Oil Blue #6
03 [Orient Chemical], Patent Pure Blue [
Made by Sumitomo Mikuni Chemical], crystal violet, brilliant green, ethyl violet, methyl green,
Erythrosin B1 basic tsuksin, malachite green, oil red, m-cresol purple, rhodamine B1 auramine, 4-p-ethylaminophenylimino naphthoquinone, triphenylmethane type represented by cyano-p-diethylaminophenyl acetanilide, etc., diphenylmethane Examples include dyes of the oxazine type, xanthine type, iminonaphthoquinone type, azomethine type, and anthraquinone type. Among these, triphenylmethane dyes are preferred.

Further, a sensitizer for improving sensitivity can also be added to the photosensitive composition of the present invention. As the sensitizer, gallic acid derivatives described in JP-A No. 57-118237, 5-membered cyclic acid anhydrides such as those described in JP-A-52-80022, such as phthalic anhydride; , tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, pyrometic acid, itaconic acid, etc., and JP-A-Sho.

Examples include 6-membered cyclic acid anhydrides such as those described in No. 58-119!12, such as glutaric anhydride and its derivatives. Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

A positive-working photosensitive lithographic printing plate can be formed by dissolving the photosensitive composition of the present invention in a solvent that dissolves each of the above-mentioned components, and applying and drying the solution on the surface of a suitable support. Examples of solvents that can be used 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.

Examples of the support on which the photosensitive layer using the photosensitive composition of the present invention is provided include metal plates such as aluminum, zinc, copper, and steel, and metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, and the like. Examples include metal plates, paper, plastic films, paper coated with resin, paper covered with metal foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, aluminum plates are preferred.

When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing.

The various methods described above can be used alone or in combination depending on the composition of the aluminum material. Preferred is electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining treatment, if necessary, desmut treatment is performed with an aqueous alkali or acid solution, neutralized, and washed with water.

The anodic oxidation 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 electrolytic solution. The amount of anodic oxide film formed is 1 to 50s+g/d
rrr is appropriate, preferably 10 to 40 mg/
d rrr. The amount of anodized film can be determined by, for example, applying an aluminum plate to a phosphoric acid chromic acid solution (85% phosphoric acid solution: 35%
m1 chromium oxide (Vl) (produced by dissolving 20 g in 1 g of water) to dissolve the oxide film, and is determined by measuring the change in weight of the plate before and after the film is dissolved.

Specific examples of the sealing treatment include hot water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, in general, when contact baking a film original onto a photosensitive lithographic printing plate, the printing frame is vacuumed, or the vacuum adhesion is improved. Can be applied to printing plates. Methods for improving vacuum adhesion include mechanically creating unevenness on the surface of the photosensitive layer, scattering solid powder on the surface of the photosensitive layer,
A method of providing a matte layer on the surface of a photosensitive layer as described in JP-A-50-125805, and JP-A-50-125805.
Examples include a method of heat-sealing a solid powder onto the surface of a photosensitive layer as described in Japanese Patent No. 5-12974.

A positive-working photosensitive lithographic printing plate to which the photosensitive composition of the present invention is applied can be used in the same manner as conventionally used. For example, an ultra-high pressure mercury lamp is passed through a transparent film,
The support is exposed to light using a light source such as a metal halide lamp, a xenon lamp, or a tungsten lamp, and then developed with an alkaline developer, leaving only the unexposed portion on the surface of the support to form a positive relief image.

Examples of alkaline developers include sodium hydroxide,
Examples include aqueous solutions of alkali metal salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate.

The concentration of alkali metal salt is 0. , l-10% by weight is preferred.

In addition, an anionic surfactant may be added to the developer as necessary.
Amphoteric surfactants and organic solvents such as alcohols can be added.

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 [Synthesis of exemplary binder resin (a-1)] Synthesis method of N-(p-aminosulfonylphenyl)acrylamide 300 g of p-aminohenzenesulfonamide, 2 g of hydroquinone monomethyl ether, 3 p of acetone, and 160 g of pyridine. The mixture was mixed and cooled from the outside using a cryogen, and when the internal temperature had dropped to -10°C, 170 g of acrylic acid chloride was added dropwise with stirring. Reaction temperature: 0℃
Adjust the dropping speed so that it is 0 to 3℃ after finishing dropping.
The mixture was stirred for 2 hours.

Next, after stirring at 25°C for 2 hours, the reaction solution was concentrated to 1/3, poured into dilute hydrochloric acid (pH approximately 1.0), and the resulting precipitate was suction-filtered to form a white solid. I got it.

This white solid was dissolved in warm methanol 12, and 1 p of a 5% aqueous sodium carbonate solution was added thereto, followed by stirring at 40° C. for 30 minutes.

This dark red solution was then poured into 4 ρ of 5% hydrochloric acid to form a precipitate, which was filtered with suction and dried to give a white solid. This was recrystallized from a mixed solvent of ethanol and water to obtain 300 g of N-(p-aminosulfonylphenyl)acrylamide.

The obtained N-(p-aminosulfonylphenyl)acrylamide 181.3g, methyl methacrylate 37.
7 g, acrylic acid 13.6 g and α,α'-azobisisobutyronitrile 325 g were dissolved in 500 ml of N,N-dimethylformamide, and the mixture was purged with nitrogen gas.
Heated at 80°C for 5 hours to obtain a polymer solution.

The polymer solution was poured into 59 5% hydrochloric acid, the white precipitate formed was filtered and dried, and the exemplified binder resin (a-
230g of 1) was obtained.

Similarly, exemplary binder resins (' b -1), (c
-1) and (d-1) were synthesized.

[Synthesis of oil sensitizing agent [, I]] Novolac resin (M w-1300) which is a polycondensate of p-tert-butylphenol and benzaldehyde
Dissolve 20 g in 240 ml of dioxane, 0-naphthoquinone diazido 5-sulfonyl chloride t+,
After dissolving 3 g of potassium carbonate, a potassium carbonate aqueous solution of 3.5 g dissolved in 23 ml of water was added dropwise, and the mixture was heated at 40 to 50°C.
The condensation reaction was carried out for minutes. After the reaction, the reaction solution was diluted with diluted hydrochloric acid (water 5
The precipitated resin was collected by filtration and dried.

In this way, p = tert-butylphenol.
28 g of an 0-naphthoquinonediazide sulfonic acid ester compound of penzalphehyde resin was obtained. As a result of analysis, the condensation rate of OH groups was 50%.

After degreasing an aluminum plate with a thickness of 024 in a 5% sodium hydroxide aqueous solution, it was heated in a 0.3 molar nitric acid aqueous solution at a temperature of 30°C and a current density of 50A/d'rrr.
An electrolytic etching process was performed for a processing time of 30 seconds. Next, a desmut treatment was performed with a 5% aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. When the amount of anodic oxide film was measured using the method described above,
It was 20 g/drrr. Next, it was immersed in a hot aqueous solution at 90°C for pore sealing treatment.

The aluminum support thus obtained was coated with photosensitive liquid (I), photosensitive liquid (■), photosensitive liquid (■), photosensitive liquid (■), photosensitive liquid (V), photosensitive liquid (comparison) having the following compositions. were applied using a rotary coater, dried at 100°C for 4 minutes, and had a film thickness of 24 Mg/drr? Photosensitive lithographic printing plate sample N of
α1-6 were obtained.

Photosensitive liquid (1) Trihydroxybenzophenone and naphthoquinone-(1,,2)-diazide-(2)-5-
Ester compound with sulfonic acid chloride 3.0g The above-mentioned binder resin (a-1) 7.0g Liposensitizing agent [
I]]o,tegg2-trichloromethyl5-[β-(2-benzofuryl)vinyl]-1,3,4-oxadiazole 0.126g surfactant (Emarken 906 manufactured by Kao ■) O,1g methyl cellosolve 100ml Photosensitive liquid (I
I) -ester compound of trihydroxybenzophenone and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride
3.0g of the above-mentioned binder resin (b-1)
7. Og liposensitized north side I 1
0.168g 2-Trichloromethyl-5-[β-(2-benzofuryl)vinyl]-1,3,4-oxadiazole (1,128g surfactant (Emulken 906 manufactured by Kao ■) 0.1g Methyl cellosolve 100 ml Photosensitive liquid (II
I) Ester compound of trihydroxybenzophenone and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride 3.0g The aforementioned binder resin (c-1) 7.0g Liposensitizing agent [
I] 0.1.68g 2-Trichloromethyl-5-[β = (2-benzofuryl)vinyl]-1,3,4-oxadiazole 0.126g Surfactant (Emulken 906 manufactured by Kao ■) OAg methyl cellosolve 100ml Photosensitive liquid (IV) Ester compound of trihydroxybenzophenone and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride 3.0g The above-mentioned binder resin (d-1) 7.0g Sensitized Agent [
I] ]0. lHg2-Trichloromethyl 5-[β-(2-benzofuryl)vinyl]-1,3,4-oxadiazole 0.126g Surfactant (Emulken 906 manufactured by Kao ■) O, 1g Methyl cellosolve 100ml Photosensitive liquid (V) Ester compound of trihydroxybenzophenone and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride 3.0g The above-mentioned binder resin (a 1) 7.0g 2-trichloromethyl-5-[β- (2-benzofuryl)vinyl] ~ 1.3.4-oxadiazole O, 126g surfactant (Emulken 906 manufactured by Kao ■) 0. Lg methyl cellosolve 100 ml photosensitive solution (
Comparison) Ester compound of trihydroxybenzophenone and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride 3.0 g Comparative binder resin (polymer compound b described in JP-A-2-866) ) 7.0 g 2-trichloromethyl-5-[β-(2-benzofuryl)vinyl]-1,3,4-oxadiazole 0.126 g Methyl cellosolve 100 ml Pass the obtained photosensitive lithographic printing plate through an original film. Exposure for 30 seconds from a distance of 60 cm using a 3kV ultra-high pressure mercury lamp, then P
Using a 7-fold dilution of a positive developer for S plates "5DP-1" (manufactured by Konica Corporation), development was performed at 25° C. for 45 seconds, and stains in non-image areas were observed.

Further, the lithographic printing plate sample obtained under the above exposure and development conditions was printed with UV ink under the following conditions.

[Printing conditions using UV ink] Printing machine: Hamada Star CD I-900 Printing ink: Toyo Flush Dry 〇L-Beni Ap (manufactured by Toyo Ink Co., Ltd.) Reducer: Toyo Flash Dry Reducer. p(
(Manufactured by Toyo Ink Co., Ltd.) Plate: Toyo Furani Dry Plate ``No''-
Cleaner paper (manufactured by Toyo Ink Co., Ltd.), high-quality paper Printing speed: 7000 sheets/hour Continue printing until poor inkling appears in the solid areas of the image area of this print, or until ink is inked in the non-image areas. The number of printed sheets was counted at the time when the condition appeared.

The results are shown in Table 1.

The following margin table 1 [Effects of the invention] The photosensitive composition of the present invention has high sensitivity, excellent ink receptivity and alkali resistance, and does not cause staining in non-image areas.
Furthermore, it has excellent printing durability even when UV ink is used.

Claims (2)

[Claims] (1) A lithographic printing plate characterized by containing o-naphthoquinonediazide sulfonic acid ester and a copolymer resin having a structural unit represented by the following general formula [I] and a structural unit having a carboxyl group. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent a hydrogen atom or an alkyl group. (2) A resin comprising a compound having a polyoxyalkylene structural unit and a condensate of a substituted phenol and an aldehyde represented by the following general formula [II], and/or an o-naphthoquinonediazide sulfonic acid ester compound of the resin. The photosensitive composition according to claim 1, further comprising: General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, R_3 and R_4 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R_5 represents an alkyl group or cycloalkyl group having 2 or more carbon atoms.