JPH024250A - Negative photosensitive printing plate - Google Patents

Abstract

PURPOSE:To obtain the title printing plate having high sensitivity in a photosensitive layer, high developability and high durability for printing, and superior suitability for UV ink by incorporating methyl acrylate in combination with a photosensitive diazo resin as binder into the photosensitive layer. CONSTITUTION:A photosensitive layer on a base body contains a photosensitive diazo resin, a high molecular compd. contg. methyl acrylate as constitutional unit, and a silane coupling agent and/or a titan coupling agent. The content of the constitutional unit constituted of methyl acrylate is 5-40mol.%, pref. 10-30mol.%. A photosensitive planographic plate is obtd. by coating the surface of the base body with said photosensitive compsn. and drying. Thus, a negative photosensitive printing plate having superior developability, high durability for printing, and superior suitability for UV ink is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a negative-working photosensitive composition, and particularly to a negative-working photosensitive composition that has excellent chemical resistance, UV ink suitability, and developability in plate making and printing processes. Regarding the sex print version.

[Conventional technology]

Negative-working photosensitive lithographic printing plates generally have a photosensitive composition coated on a support such as an aluminum plate whose surface has been treated to make it hydrophilic, and when this is exposed to actinic light such as ultraviolet rays through a transparent negative, In the exposed area, polymerization or crosslinking occurs to form an insoluble and lipophilic film. On the other hand, by eluting the unexposed areas using a developer, the hydrophilic surface of the support is exposed. That is, an image area that repels water and receives ink and a non-image area that receives water and repel ink are obtained.

Examples of photosensitive substances in this case include diazo resins, typified by formaldehyde condensates of p-diazodiphenylamine, but they are not used alone, and are generally mixed with a polymer compound as a binder. It is used.

As a polymer compound used as a binder in combination with such a diazo resin, a polymer compound having a functional group such as a hydroxyl group, an amino group, a cyano group, or a urethane group in its molecule is effective. -43890
A polymer compound having a phenolic hydroxyl group, such as p-hydroxyphenyl (meth)acrylamide, in the polymer structure described in Japanese Patent Publication No. 52-7364 and Japanese Patent Publication No. 55-34929 Ta2-
Polymer compounds having a structural unit having an alcoholic hydroxyl group, such as a polymer compound containing an oxyalkyl (meth)acrylate monomer, a diazo compound, a 2-oxyalkyl (meth)acrylate monomer, and an acrylonitrile monomer, etc. Are known.

On the other hand, in order to obtain a large number of printed materials on a single printing plate, the image area and the support are strongly bonded, and in order to improve the chemical resistance against various chemicals used in the plate-making process and the printing process. Furthermore, JP-A-59-192250 discloses providing a non-photosensitive intermediate layer containing a silane coupling agent between the support and the photosensitive layer.

[Problem to be solved by the invention]

However, as mentioned above, when a printing plate is manufactured using a polymer compound having a phenolic hydroxyl group as a binder, it generally improves the resist strength peculiar to aromatic rings, that is, the stiffness resistance, and the printing plate. Although high ink affinity and resist strength against various printing processing chemicals can be achieved, there is a problem in that poor solubility in developing solutions tends to cause poor development.

On the other hand, when using a polymer compound having an alcoholic hydroxyl group, although the developability is generally good, it is easily scratched due to poor physical strength and is weak against impact force, especially for high-speed printing such as off-wheels. Problems include poor printing durability and erosion of the resist due to processing chemicals during printing.

On the other hand, when a non-photosensitive intermediate layer containing a silane coupling agent is provided between the support and the photosensitive layer as in JP-A-59-192250, there are drawbacks such as staining in non-image areas. be.

Therefore, the main object of the present invention is to provide a negative-working photosensitive printing plate that has high sensitivity in the photosensitive layer, excellent developability and stiffness resistance, good suitability for UV ink, and is free from stains in non-image areas. There is a particular thing.

[Means to solve the problem]

The above problem is solved by providing a negative photosensitive printing plate having a photosensitive layer on a support, in which the photosensitive layer contains (A) a photosensitive diazo resin, (B) a polymer compound having methyl acrylate as a structural unit, ( C) This problem can be solved by containing at least one coupling agent among a silane cuff pulling agent and a titanium coupling agent.

[Specific structure of the invention]

The present invention will be explained in more detail below.

In the present invention, in addition to the photosensitive diazo resin, a polymer compound having methyl acrylate as a structural unit is included as a binder.

In this case, it is preferable to use the following copolymer instead of a polymer compound having only methyl acrylate as a structural unit.

That is, in the molecular structure, (a structural unit having an alcoholic hydroxyl group and/or
or 1 to 50 mol % of a structural unit having a phenolic hydroxyl group, (b) 5 to 40 mol % of a structural unit represented by the following formula 11% formula (wherein R1 represents a hydrogen atom or an alkyl group) %, (5 to 40 mol% of units formed from C1 methyl acrylate, (dl below - formula ■, 1011□-C- .........■ C0OR' (in the formula, R2 is hydrogen atom, methyl group or ethyl group, R3 represents an alkyl group having 2 to 12 carbon atoms or an alkyl-substituted aryl group); and (e) a carboxyl group. It is a copolymer containing 2 to 30 mol% of structural units having the same structure, and having a weight average molecular weight of 50,000 to 200,000.

Specific examples of the hexamer forming the structural unit having an alcoholic hydroxyl group include compounds shown in the following formula (I[[) as described in Japanese Patent Publication No. 52-7364 (Meta) Examples include acrylic esters and acrylamides.

In the formula, R4 is a hydrogen atom or a methyl group, R5 is a hydrogen atom,
Methyl group, ethyl group or chloromethyl group, and n is 1
Indicates an integer between ~10.

Examples of (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and examples of acrylamides include N -Methylol (meth)acrylamide, N
-Hydroxyethyl (meth)acrylamide and the like. Preferably it is 2-hydroxyethyl (meth)acrylate.

In addition, examples of monomers forming a structural unit having a phenolic hydroxyl group include N-(4-hydroxyphenyl)-(meth)acrylamide, N-(2-hydroxyphenyl)-(meth)acrylamide, N-(4-hydroxyphenyl)-(meth)acrylamide, Monomers of (meth)acrylamides such as (hydroxynaphthyl)-(meth)acrylamide: o-, m- indicate p-hydroxyphenyl (meth)acrylate monomer m: 〇-
Examples include m- or halo-hydroxystyrene monomers. Preferably, o-, m- or p-hydroxyphenyl (meth)acrylate monomer N-(4-hydroxyphenyl)-(meth)acrylamide monomer, more preferably N-(4-hydroxyphenyl)-
(meth)acrylamide monomer.

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

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

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

Examples of the monomer having a carboxy ester group in the side chain and forming the structural unit represented by the formula (2) include ethyl acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, amyl acrylate,
amyl methacrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-
Examples include hydroxyacrylate, glycidyl acrylate, and the like. The units formed from the monomer account for 25 to 60 mol%, preferably 35 to 6 mol%, in the polymer compound.
It is selected from the range of 0 mol%.

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

Note that each of the above structural units is not limited to units formed from the monomers listed as specific examples.

As a method for synthesizing the polymer compound as a binder in the composition of the present invention, a generally known radical polymerization method or the like is used, for example, using an initiator (0.1 to 4.0 It is easily synthesized by solution polymerization method using (mol%).

The molecular weight of the polymer compound is 50,000 to 200,000, preferably 8,000 to 200,000, and preferably 8,000 to 200,000. A range of 150,000 to 150,000 is used.

The content of the polymer compound in the photosensitive composition is preferably 30 to 99% by weight, particularly preferably 40 to 97% by weight, based on the total composition.

The photosensitive layer in the present invention contains at least one type of coupling agent among a silane coupling agent and a chikan coupling agent.

The coupling agent is particularly preferably a silane coupling agent, which 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. Examples of reactive groups here include amine groups, alkoxy groups, alkyl groups, acyloxy groups, and ammonium compound residues.

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 an acetyloxy group,
Examples include alkylcarbonyloxy groups having 2 to 4 carbon atoms such as butyryloxy. 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
alkyleneaminoalkylene groups, alkyleneoxycarbonyl groups with 2 to 5 carbon atoms such as ethyleneoxycarbonyl groups, trimethyleneoxycarbonyl groups (however, the alkylene group is directly bonded to the silicon atom), trimethylene Examples include alkyleneaminoalkyleneaminophenylene groups having 9 to 15 carbon atoms such as aminoethyleneaminomethylenephenylene group (provided that 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, a disilazane compound such as hexaalkyldisilazane may be used in combination.

Specific examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(2-methoxyethoxy).
Silane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -methacrylokidipropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and the like. In addition, as titanium coupling agents, isopropyl triisostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate,
Isopropyltri(dioctylpyrophosphate) titanate, Tetraisopropylbis(dioctylphosphite)titanate, Tetraoctylbis(ditridecylphosphite)titanate, Tetra(2,2-diallyloxymethyl-1-butyl)-bis(ditridecylphosphite) phyto) titanate, bis(dioctyl pyrophosphate)-oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and the like.

Among the silane coupling agents described above, 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 linking group to a silicon atom.

In the present invention, the silane coupling agent and/or the titanium coupling agent is preferably contained in a copolymer ratio of 0.01 to 5% by weight in the photosensitive composition constituting the photosensitive layer.

On the other hand, as the photosensitive diazo resin used in the present invention, conventionally known ones can be used as appropriate. Diazo resins or co-condensed diazo resins represented by co-condensates with carbonyl compounds are included, and among these, diazo resins or co-condensed diazo resins that are soluble in organic solvents are preferred.

The co-condensed diazo resin is preferably a co-condensate of an aromatic diazonium salt, an aromatic compound having at least one C0OH group and/or 011 group in the molecule, and an active carbonyl compound.

At least one C00) group and or OH in the molecule
Specific examples of compounds having groups include benzoic acid, 〇-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, phthalic acid, terephthalic acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p- -Methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4-(m-methoxyanilino)benzoic acid, 4-
(p-methoxybenzoyl)benzoic acid, 4-(p-methylanilino) benzoic M, 4-phenylsulfonylbenzoic acid, phenol, (o+m+p) cresol, xylenol, resorcin, α-methylresorcin, (o+m
+p)-methoxyphenol, m-ethoxyphenol, catechol, phloroglycine, p-hydroxyethylphenol, naphthol, pyrogallol, hydroquinone, p-hydroxybenzyl alcohol, 4-chlororesorcin, biphenyl 4.4-diol, 1.2. 4-benzenetriol, bisphenol A, 2.4-dihydroxybenzophenone, 2.3.4-) dihydroxybenzophenone, p-hydroxyacetophenone, 4.
4-dihydroxydiphenyl ether, 4.4-dihydroxydiphenylamine, 4.4-dihydroxydiphenyl sulfide, cumylphenol, (o+m+p)
-Chlorophenol, (09m,p)-bromophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6-propylsalicylic acid, 6-laurylsalicylic acid, 6-stialylsalicylic acid, 4.6- Dimethylsalicylic acid, p-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2.6-dimethyl-4-hydroxybenzoic acid, 2.4-dihydroxybenzoic acid, 2 .4-dihydroxy-6-methylbenzoic acid, 2.
6-dihydroxybenzoic acid, 2,6-hydroxybenzoic acid
-benzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucincarboxylic acid, 2.4.5-) dihydroxybenzoic acid, m- Galoyl gallic acid, tannic acid, m-benzoyl gallic acid, m-(p-)ruyl) gallic acid, protocatechoyl gallic acid, 4,6-cyhydroxyphthalic acid, (2,4-dihydroxyphenyl) acetic acid , (2,6-dihydroxyphenyl)acetic acid, (3,4
, 5-)dihydroxyphenyl)acetic acid, p-<hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4
-(p-hydroxyphenyl)methylbenzoic acid, 4-(
O-hydroxybenzoyl)benzoic acid, 4-(2,4-
dihydroxybenzoyl)benzoic acid, 4-(p-hydroxyphenoxy)benzoic acid, 4-(p-hydroxyanilino)benzoic acid, bis(3-carboxy-4-hydroxyphenyl)amine, 4-(p-hydroxyphenylsulfonyl) ) benzoic acid, 4-(p-hydroxyphenylthio)benzoic acid, etc. Among these, particularly preferred are salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid.

The above aromatic diazonium compounds include, for example,
Diazonium salts such as those listed in No. 48001 can be used, but especially diphenylamine-4
-Diazonium salts are preferred.

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

The co-condensed diazo resins and condensed diazo resins of (a) and (b) above can be prepared by known methods such as Photographic Ink Science and Engineering (Pho
to, Sci,, Eng,) Volume 17, Page 33 (1
973), U.S. Patent No. 2,063,631, U.S. Pat.
, No. 679.498, diazonium salts, aromatic compounds having carboxyl and hydroxyl groups, and aldehydes, such as paraformaldehyde, acetaldehyde, benzaldehyde, or ketones, e.g. Obtained by polycondensing acetone and acetophenone.

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

The molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group to the aromatic diazo compound is 1:0.1 to 0.1:1; preferably 1:0.
．． 5-0.2:1. More preferably 1:1 to 0.2:1
It is. In this case, the total molar ratio of the aromatic compound having at least one of a carboxyl group and a hydroxyl group and the aromatic diazo compound to aldehydes or ketones is usually t:O,S to 1.2, preferably 1. :
A co-condensed diazo resin can be obtained by charging 0.7 to 1.5 and reacting at a low temperature for a short time, for example, about 3 hours.

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

These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids; typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid. , toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-
Aliphatic and aromatic sulfonic acids such as methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5-sulfoisophthalate, 2.2', 4.4-tetrahydroxybenzophenone, 1 , 2.3-) Hydroxyl group-containing aromatic compounds such as IJ hydroxybenzophenone, 2.2', 4-trihydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, C1O*, IO4, etc. Examples include, but are not limited to, perhalogen acids and the like. Among these, particularly preferred are hexafluorophosphoric acid and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid. These diazo resins may be used alone or in combination.

The co-condensed diazo resin of the present invention can have any molecular weight by varying the molar ratio of each monomer and the condensation conditions; however, in order to effectively serve the purpose of the present invention, has a molecular weight of about 400 to io, o
oo can be used, but preferably about 800
A value between 5,000 and 5,000 is suitable.

In addition to the components described above, the photosensitive composition used in the present invention may further include dyes, pigments, coating properties improvers,
Plasticizers and the like can be added.

Examples of the above-mentioned dyes include Victoria Pure Blue BOH (manufactured by Osugaya Kagaku Co., Ltd.) and Oil Blue #603 (
Orient Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B1 Basic Tsuksin, Malachite Green, Oil Red, m-Cresol Purple, Rhodamine B1 Auramine, Examples include triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes represented by 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. .

The dye is usually present in the photosensitive composition in an amount of about 0.5 to about 10% by weight.
, preferably about 1 to 5% by weight.

Examples of coating property improvers include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, and nonionic surfactants (e.g., Pluronic L-64 (manufactured by Asahi Denka)). Examples of plasticizers for imparting flexibility and wear resistance include butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexane phthalate, dioctyl phthalate, tricresyl phosphate, and tributyl phosphate. , trioctyl phosphate, tetrahydrofurfuryl oleate, and oligomers of acrylic acid or methacrylic acid. Examples of the oil-sensitizing agent for improving the oil-sensitivity of image areas include JP-A-55-527.
Examples of stabilizers include polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (acrylic acid, methacrylic acid, , citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5
-sulfonic acid, etc.).

The amount of these additives added varies depending on the purpose of use, but is generally 0.01 to 30% by weight based on the total solid content.

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

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

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

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

It is preferable to use an aluminum plate as the support for the photosensitive lithographic printing plate of the present invention. The surface is grained by electrolytic roughening in nitric acid or an electrolytic solution containing nitric acid as the main component, or hydrochloric acid or an electrolytic solution containing hydrochloric acid as the main component, and preferably further anodized and if necessary. Use one that has undergone surface treatment such as pore sealing.

Electrolytic surface roughening is carried out by immersing an aluminum plate in a bath containing nitric acid or hydrochloric acid at a concentration of 0.1 to 0.5 mol/1, preferably 0.2 to 0.4 rmol/1.
Temperature of 0°C, preferably 25-40°C, current density of 20-40°C
It is preferable to perform electrolytic etching at 200 A/dm for about 10 seconds to 3 minutes. After this grain chamber treatment, if necessary, desmut treatment is performed with an aqueous alkali or acid solution for neutralization, followed by washing with water.

The anodizing treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolyte. The amount of anodic oxide film formed was 1 to 50 mg/
dm" is appropriate, preferably 10 to 40 ■/dm"
It is. Here, the amount of anodized film is determined by replacing the aluminum solution with a phosphoric acid chromic acid solution (35 ml of 85% phosphoric acid aqueous solution).
and 20 g of chromium (VI oxide) dissolved in water (No. 11) to dissolve the oxide film, and measure the change in weight of the plate before and after the film is dissolved.

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

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

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

The developer used in the development of the photosensitive lithographic printing plate of the present invention may be any known developer, but examples include organic solvents such as benzyl alcohol and ethylene glycol monophenyl ether, and alkali metal silicate. and alkaline agents such as organic amine compounds, and those containing water as a main component, those that do not contain organic solvents, and anionic surfactants such as the above alkaline agents, higher alcohol sulfate ester salts and alkylaryl sulfonates. agent,
and those containing organic carboxylic acid as a main component can be used.

After the photosensitive lithographic printing plate of the present invention is imagewise exposed, if it is brought into contact with the above-mentioned developer or rubbed, the photosensitive layer will be exposed to light after 10 to 60 seconds at about lθ°C to 40°C. The photosensitive composition in the non-exposed areas is completely removed without adversely affecting the areas.

〔Example〕

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

First, a synthesis example of a polymer compound having methyl acrylate as a structural unit will be shown.

(Synthesis of copolymer-1) Under a nitrogen stream, 100 g of acetone and 100 g of methanol
In a mixed solvent of, 25 g of p-hydroxyphenylmethacrylamide (HVPMA), 15 g of acrylonitrile (8N), 25 g of methyl acrylate (MA), 60 g of ethyl acrylate (HA), 10 g of methacrylic acid (MAA), and azobisiso 5 g of butyronitrile (AIBN) was dissolved, and the mixture was heated at 60° C. for 8 hours while stirring. After the reaction was completed, the reaction solution was poured into water to precipitate the copolymer, which was vacuum-dried at 50° C. overnight. The weight average molecular weight of this copolymer-1 was 110,000.

(Synthesis of Copolymer-2) The same polymerization reaction was carried out by changing the charging ratio of monomers, etc. in Copolymer-1 as shown below.

H31PM^ 25g, AN20gSMA15gXEA
80g.

MAA 20g, acetone 100g, methanol 100g
g5AIBN7 g.

The weight average molecular weight was 70,000.

(Synthesis of Copolymer-3) The same polymerization reaction was carried out by changing the charging ratio of monomers, etc. in Copolymer-1 as shown below.

HyPMA 25g, ^N60g, HA70g, M
AA 20g 1 acetone 100g, methanol 100g
g.

AIBN7g.

The weight average molecular weight was 60,000.

(Synthesis of Copolymer-4) The same polymerization reaction was carried out by changing the charging ratio of monomers, etc. in Copolymer-1 as shown below.

HyPMA 25g, AN20g, nAloogSMA
A25g 1 acetone 120g, methanol 120g.

AIBN5g.

The weight average molecular weight was 70,000.

(Synthesis of Copolymer-5) The same polymerization reaction was carried out by changing the charging ratio of monomers, etc. in Copolymer-1 as shown below.

HyPMA 30g SAN20g, EA65g, MAA
15g 1 acetone 100g, methanol 100g.

alBN5g.

The weight average molecular weight was 110,000.

(Synthesis of Copolymer-6) The same polymerization reaction was carried out by changing the charging ratio of monomers, etc. in Copolymer-1 as shown below.

uyPMA 45g, AN25g, MA45g, MA
A 20g 1 acetone 100g, methanol 100g.

AIBN5g.

The weight average molecular weight was 110,000.

Next, a synthesis example of a photosensitive diazo resin will be shown.

Synthesis of p-diazodiphenylamine sulfate 14.5 g (50
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 reaction solution. At this time, the reaction temperature is 1
It was added so that the temperature did not exceed 0°C. Thereafter, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 500 mf of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was washed with 100mj! Dissolve in pure water and add 6. to this solution.
A cold concentrated aqueous solution of 8 g of zinc chloride was added. The resulting precipitate was filtered, washed with ethanol, and washed at 150 ml.
mj' was dissolved in pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for 1 day to obtain diazo resin-1.

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

Synthesis of Diazo Resin-2> 3.5 g (0,025 mol) of p-hydroxybenzoic acid and 22.0 g (0,075 mol) of 4-diazo-4'-methoxydiphenylamine sulfate were mixed under water cooling with 9
Dissolved in 0g of concentrated sulfuric acid. After this reaction, 2.7 g of paraformaldehyde (0.09 mol) were added slowly. At this time, the addition was carried out so that the reaction temperature did not exceed 10°C. Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was poured into 1β ethanol under water cooling, and the resulting precipitate was filtered.

After washing with ethanol, this precipitate was dissolved in 200+11 pure water, and to this solution was added a cold concentrated aqueous solution in which 10.5 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and dissolved in 30On+6 pure water.

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

When the molecular weight of this co-condensed diazo resin-2 was measured by GPC, the weight average molecular weight was about 2.300.

(Manufacture of sand grain-1) An aluminum plate with a thickness of 0.24 mm was immersed in a 3% thorium hydroxide aqueous solution, degreased, washed with water, and immersed in a 1% nitric acid aqueous solution.
Electrolytically etched for 5 minutes at a current density of 30 A/dm2 at 5°C, washed with water, immersed in a 0.9% aqueous sodium hydroxide solution, washed with water, etched at 1.5 A/dm2 in a 40% aqueous sulfuric acid solution at 30°C.
Anodized for 2 minutes at a current density of dm2, washed with water, treated with sodium silicate by immersing in a 1% sodium methanate solution for 3 minutes at 85°C, and then soaked in water at 90°C pH 8.5 for 25 minutes.
The sample was immersed for a second, washed with water, and dried to produce grain-1.

(Manufacturing of sand grain-2) An aluminum plate with a thickness of 0.24 m was
After sanding the surface using a 00 mesh pumice stone-water suspension, the sample was thoroughly washed with water and immersed in a 10% aqueous sodium hydroxide solution at 70°C for 60 seconds. followed by 7%
It was anodized in a sulfuric acid aqueous solution at a current density of 40 A/dm for 30 seconds, immersed in a 1% sodium metasilicate solution at 85°C for 3 minutes, then immersed in hot water at 90°C for 2 minutes, washed with water, and dried. Sand grain-2 was created.

〔Example〕

Next, examples will be shown.

(Example 1) A photosensitive liquid having the composition shown in Table 1 below was applied onto the above-mentioned grain-1 to obtain lithographic printing plate samples 1 to 9. The diazo resin and copolymer used were those shown in the synthesis example described above.

A negative original image and a step wedge with a density difference of 0.15 were placed on the obtained samples 1 to 9, and after exposure for 30 seconds with a 2kW metal halide lamp from a distance of 60cm, 5DN-
21 developer (manufactured by Konica, diluted 1:3) at 25℃, 40
After being immersed for a second, it was developed by rubbing lightly with absorbent cotton.

Table 2 shows the number of solid steps of the step wedge.

The stains in the non-image area when the dilution ratio was 1:2 are also shown.

Furthermore, the above sample was printed on a Heidel GTO printing machine using UV ink ("Toka Best Cure" manufactured by Toka Shiki Co., Ltd.) for 10 minutes.
Every time 00 sheets were printed, the plate surface was washed with Tsurfit washing oil (manufactured by Clarei Soprene Chemical ■) and a printing durability test was performed. The results are shown in Table 3. Similarly, prints were made with kerosene using regular ink (Donghua Mark V) for 15,000 yen.
The results of washing each sheet and testing the printing durability are also shown in the same table.

(Comparative Example-1) A solution of 0.1 M vinyltriacetoxysilane was applied to the grain-1 and dried. Furthermore, on top of that, the above sample 1
A photosensitive layer was applied. When this lithographic printing plate was exposed to light, developed, and printed, a tingling ink was found in the non-image areas.

〔Effect of the invention〕

As described above, according to the present invention, developability, printing durability and [
It is possible to obtain products with excellent suitability for IV printing.

Claims (1)

[Claims] (1) In a negative photosensitive printing plate having a photosensitive layer on a support, the photosensitive layer comprises (A) a photosensitive diazo resin, (B) a polymer compound having methyl acrylate as a structural unit, (C) silane. A negative photosensitive printing plate characterized by containing at least one coupling agent selected from a coupling agent and a titanium coupling agent.