JPH02186354A - Photosensitive planographic printing plate treated with anionic surfactant - Google Patents

Abstract

PURPOSE:To prevent the remaining of a film after development, to render superior water retentivity and to further render superior resistance to treating chemicals and printing by treating a pretreated support with an aq. soln. contg. an anionic surfactant. CONSTITUTION:The surface of a pretreated support is treated with an aq. soln. contg. an anionic surfactant before a photosensitive layer is formed on the surface. By the treatment, the stain of a non-image area is prevented and the water retentivity is improved. The photosensitive layer is formed on the resulting hydrophilic support. The remaining of a film after development is prevented and the non-image area maintains satisfactory water retentivity. High resistance to printing and treating chemicals are rendered and the non- image area is not stained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate whose support surface has been treated. Concerning an excellent photosensitive lithographic printing plate.

[Prior Art J Conventionally, a photosensitive lithographic printing plate, such as a positive-working photosensitive lithographic printing plate, has an ink-receptive photosensitive layer provided on a wood-philic support. When the photosensitive layer of a lithographic printing plate is subjected to image exposure and then the exposed photosensitive layer is developed using a developer, the photosensitive layer in the exposed areas is removed and the surface of the hydrophilic support is exposed, while the non-photosensitive layer is exposed. The photosensitive layer in the exposed areas remains on the surface of the support to form ink-receptive image areas, thereby obtaining a lithographic printing plate.

Such a lithographic printing plate utilizes the property that water and oil repel each other for printing. Specifically, after moistening the non-image area of the printing plate with water, applying ink to the printing plate,
Since the ink is repelled by the dampening water in the non-image area, the ink selectively adheres only to the image area.

When the ink in the image area is transferred to a transfer object, a printed matter having an image corresponding to the image area is obtained.

Therefore, as a support for obtaining such a lithographic printing plate, it is necessary to use a support that is wood-philic and has excellent water retention properties when wetted with water, and has good adhesion to the photosensitive layer that forms the image area that receives printing pressure. It has to be something. In addition, as a photosensitive layer,
It is necessary to have ink receptivity, high sensitivity to exposure, etc., and the most important condition is that it must have high resistance to 91 strength.

An aluminum plate is the best support that satisfies these conditions, and in order to obtain sufficient adhesion between the aluminum plate and the photosensitive layer, surface treatment to mechanically roughen the surface of the support is required. administered. This surface treatment method includes:
For example, various methods such as ball graining, wire graining, and brush graining were
It is described in Japanese Patent Publication No. 047, Japanese Patent Publication No. 51-48003, etc.

Also, Japanese Patent Publication No. 48-28123, U.S. Patent No. 4,0
No. 87,341, Japanese Patent Application Laid-Open No. 53-67507, etc., describe an electrolysis method in which a uniform and dense grain shape is formed on the surface of an aluminum plate by direct current or alternating current using a hydrochloric acid bath, a nitric acid bath, etc. A surface roughening method is described. Furthermore, JP-A-56-150595 describes a method of controlling the adhesion between the support and the photosensitive layer by subjecting the surface of the support to a sealing treatment using hot water, a sealing treatment using a silicate, or the like. ing.

Is there enough space between the support and the photosensitive layer like this? In order to provide J adhesion and improve wood affinity and water retention, the support such as an aluminum plate is further surface treated. For example, Japanese Patent Publication No. 36-22063, US Pat. No. 246.683, No. 3,160,5
The specification of No. 06 describes that the hydrophilicity and water retention of the metal surface can be improved by chemically treating the metal surface with potassium fluorozirconate to form a film. Further, JP-A-53-131102 describes a support whose hydrophilicity and water retention are improved by treating it with an aqueous potassium fluorozirconate solution and then with an aqueous sodium silicate solution.

However, although these methods are effective in preventing contamination of the non-image areas of the lithographic printing plate obtained by development, the printing durability and treatment chemical resistance of the lithographic printing plate are reduced. Even if these printing durability and processing chemical resistance are sufficient, if these photosensitive lithographic printing plates are imagewise exposed and then developed, the non-image areas of the resulting lithographic printing plates will be Substances contained in the photosensitive solution are strongly adsorbed to the plate surface, and during the development process, they are not easily removed by the developer and remain, leaving clear traces of correction, resulting in an uneven plate surface. Become. Therefore, when a burning treatment, which is commonly carried out as a means of improving printing durability, such a phenomenon appears conspicuously in the lithographic printing plate obtained from the support treated by the above method. is no longer suitable for practical printing use.

Therefore, as a result of extensive research in view of the above-mentioned problems, the inventors of the present invention have found that by treating the surface of a support such as aluminum with a specific treatment liquid, it is possible to improve treatment chemical resistance and high printing durability. The present inventors have discovered that it is possible to obtain a photosensitive lithographic printing plate that maintains its properties, maintains sufficient water retention in non-image areas, and does not cause staining in non-image areas, and has completed the present invention.

[Objective of the Invention] Accordingly, the first object of the present invention is to prevent the components of the photosensitive layer from remaining in the non-image area after exposure and development, that is, to prevent a film from remaining after development, and to provide sufficient water retention in the non-image area. An object of the present invention is to provide a photosensitive lithographic printing plate that retains its properties.

A second object of the present invention is to provide a photosensitive lithographic printing plate that has high printing durability and processing chemical resistance and does not cause stains in non-image areas.

[Configuration of the Invention] The above-mentioned object of the present invention is to treat the surface of the pretreated support by
This was achieved using a photosensitive lithographic printing plate characterized in that a photosensitive layer was provided on the surface after treatment with an aqueous solution containing an anionic surfactant.

[Function] In the present invention, after pre-treating the surface of the support, this surface is further treated with an aqueous solution containing an anionic surfactant, so that the printing plate obtained by developing the photosensitive lithographic printing plate is ,
In the non-image area, no components of the photosensitive layer remain, so stains do not occur.

[Detailed description of the invention] The present invention will be explained in more detail below.

The present invention is characterized in that, before forming a photosensitive layer on the surface of a pretreated support, the surface is treated with an aqueous solution containing an anionic surfactant, thereby preventing staining of non-image areas. Ru.

The anionic surfactant used in the present invention includes:
Alkyl sulfate, polyoxyethylene alkyl ether sulfate, N-acyl amino acid and its salt, N-acylmethyl taurate, polyoxyethylene alkyl ether acetate, alkyl sulfocarboxylate, α-olefin sulfonate, alkyl phosphoric acid There are salts, polyoxyethylene alkyl ether phosphates, etc., such as Emar NC, Lebenol WZ (manufactured by Kao Atlas Co., Ltd.), and NIKKOL-5BL.
-3N-27, polyoxyethylene alkyl ether sulfate such as NIKKOL-3NP-4N (manufactured by Nikko Chemicals), Neoperex F-60, Neoperex F-25 (manufactured by Kao Atlas Company), NIKKOL-LSA
, alkyl sulfonates such as NIKKOL-O3-14 (manufactured by Nikko Chemicals) and electrostripper N
, Electro Stripper K (manufactured by Kao Atlas Co., Ltd.), N
I KKOL-3LP-N%N I KKOL-DD
Examples include phosphoric acid ester salt-based anionic surfactants such as p-to (manufactured by Nikko Chemicals).

Of course, two or more types of these surfactants can be used in combination.

The aqueous solution containing the anionic surfactant used in the present invention is generally an aqueous solution containing 0.5% to 1% by weight of the anionic surfactant.

When treating the surface of the support with the above treatment liquid, the treatment conditions include immersing the pretreated support for 30 seconds to 3 minutes at a temperature range from room temperature to about 80°C, or soaking the pretreated support in the treatment liquid for 30 seconds to 3 minutes. Preferably, it is applied to a support.

The support treated with the aqueous solution containing the anionic surfactant is then preferably dried.

Additives such as water-soluble polymers can be added to the aqueous solution containing the anionic surfactant, if necessary.

The support used in the present invention is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metal plates such as aluminum, magnesium, zinc, chromium iron, copper, and nickel; Examples include alloy plates of these metals, and metal plates coated with chromium, zinc, copper, nickel, aluminum, iron, etc. by plating or vapor deposition. Among these, preferable supports are aluminum or aluminum. It is an alloy.

The support used in the present invention is pretreated before being treated with an aqueous solution containing an anionic surfactant.
This pretreatment includes degreasing treatment and surface roughening treatment that are commonly employed in this technical field.

Among the surface roughening treatments, the grain type treatment is a method of mechanically roughening the surface, and is called a so-called mechanical surface roughening method, such as ball polishing, brush polishing, blast polishing, puff polishing, etc. There is. In addition, the so-called electrical roughening method, which electrically roughens the surface, can also be used for surface roughening treatment.
For example, the support can also be electrolytically treated by alternating current or direct current in an electrolytic solution containing hydrochloric acid or nitric acid.

Scots are formed on the surface of the support obtained by the above-mentioned grain type treatment, so it is generally preferable to carry out appropriate treatments such as water washing or alkali etching to remove these scotts. Examples of such treatments include the alkali etching method described in Japanese Patent Publication No. 48-28123 and the sulfuric acid descott method described in Japanese Patent Application Laid-open No. 53-12739.

After the support used in the present invention is pretreated as described above, an oxide film is usually formed on the support by anodic oxidation in order to improve wear resistance, chemical resistance, and water retention. . Generally, in this anodization, a method is preferably used in which an aqueous solution containing sulfuric acid and/or phosphoric acid at a concentration of 10 to 50% is used as an electrolyte, and electrolysis is performed at a current density of l to lO^/dm'. Patent No. 1,412,768
There are a method of electrolyzing in sulfuric acid at a high current density as described in the specification of US Pat. No. 3,511,861, and a method of electrolyzing using phosphoric acid as described in the specification of US Pat.

The most preferred support for use in the present invention is an aluminum support with an anodized coating.

The treatment applied to the support itself in order to improve the adhesion of the support to the photosensitive layer is not particularly limited, and a brimer layer or the like may be provided as necessary.

The brimer layer includes, for example, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin. , polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

In addition, as the anchor agent constituting the above-mentioned brimer layer,
For example, silane coupling agents, silicone primers, etc. can be used, and organic titanates and the like are also effective.

In the photosensitive lithographic printing plate of the present invention, a photosensitive layer is provided on the hydrophilic support obtained as described above, but the photosensitive material used in this photosensitive layer is not particularly limited. It is not a standard material, but various materials commonly used in photosensitive lithographic printing plates, such as those listed below, can be used.

1) Photocrosslinkable photosensitive resin composition The photosensitive component in the photocrosslinkable photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule, for example as described in US Pat. ．． Specification No. 030,208, No. 3,
No. 435.237 and No. 3.622,320
A photosensitive resin containing 100-CH-C- as a photosensitive group in the main chain of the polymer, and polyvinyl cinnamate having a photosensitive group in the side chain of the polymer, etc., as described in the specification etc. can be given.

2) Photopolymerizable photosensitive resin composition A photopolymerizable composition containing an addition polymerizable unsaturated compound, comprising a monomer having a double bond, or a monomer having a double bond and a polymer binder. Typical such compositions are disclosed, for example, in U.S. Pat. No. 2,780,88.
It is described in Specification No. 3 and Specification No. 2,791°504 of the same.

- For example, compositions containing methyl methacrylate, compositions containing methyl methacrylate, polymethyl methacrylate, compositions containing methyl methacrylate, polymethyl methacrylate and polyethylene glycol dimethacrylate monomers, methyl methacrylate, alkyd resins and Photopolymerizable compositions such as compositions containing polyethylene glycol dimethacrylate monomers are used.

This photopolymerizable photosensitive resin composition contains photopolymerization initiators commonly known in this technical field (for example, benzoin derivatives such as benzoin methyl ether, benzophenone derivatives such as benzophenone, thioxanthone derivatives, anthraquinone derivatives, acridone derivatives, etc.). ) is added.

3) Photosensitive composition containing a diazo compound The diazo compound in this photosensitive composition is, for example, a diazo resin preferably represented by a condensate of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferred are salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as reaction products of hexafluoroborophosphates, tetrafluoroborates, perchlorates or periodates with said condensates. diazo resin inorganic salt, and U.S. Patent No. 3
, 300, 309,
Examples include diazo resin organic salts which are reaction products of the above condensates and sulfonic acids. The diazo resin is preferably used together with a binder. Various polymer compounds can be used as such a binder, but monomers having an aromatic hydroxyl group such as those described in JP-A No. 54-98613, such as N-(4 −
hydroxyphenyl) acrylamide, tho(4-hydroxyphenyl)methacrylamide, 0-1■-1 or p-hydroxystyrene, 0-1■-1 or p-
Copolymers of hydroxyphenyl methacrylate, etc. and other monomers, with hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in U.S. Pat. No. 4,123,276 Containing polymers Shellac, natural resins such as rosin, polyvinyl alcohol, U.S. Patent Nos. 3 and 7
51.257, linear polyurethane resins as described in U.S. Pat. No. 3,860,097, phthalated polyvinyl alcohol resins, bisphenol A Included are epoxy resins condensed from and epichlorohydrin, cellulose derivatives such as cellulose acetate, and cellulose acetate phthalate.

4) Photosensitive composition containing O-quinonediazide compound In the photosensitive composition containing O-quinonediazide compound used in the present invention, it is preferable to use the O-quinonediazide compound and an alkali-soluble resin together.

Examples of O-quinonediazide compounds include ester compounds of O-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones.

Examples of the phenols include phenol-J, 0
-Taresol, proverb -cresol, p-cresol, 3.
Examples include monohydric phenols such as 5-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. Examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol-formaldehyde resin, intestinal-cresol-formaldehyde resin, m-+I'-mixed cresol-formaldehyde resin, resorcinol-benzaldehyde resin, pyrogallol-acetone resin, and the like.

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

Further, as the O-quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, known 1,2-benzoquinonediazide sulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, l,2-benzoquinonediazide sulfonic acid amide, 1,2-naphthoquinonediazide sulfonic acid amide, etc. Quinonediazide compounds, more specifically J.
``Light-Sensitive Systems J (
Light-5ensistive Systems)
Pages 339-352 (1965) John Wllley & Sons
(New York) and W. S. Da Forest, Photoresist J (Photoresi-st) No. 50jI!
(1975), Pineclaw Hill (McGra Stomach H
1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1,2.1',2'-di(benzoquinonediazide-4-sulfonyl)-dihydroxybiphenyl, 1.
2-benzoquinonediazide-4(N-ethyl-M-β-
naphthyl)-sulfonamide, 1,2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1
-(1,2-naphthoquinodiazide-5-sulfonyl)-
3,S-dimethyl and lazole, 1,2-naphthoquinodiazide-5-sulfonic acid-4'-hydroxydiphenyl-
4'-Azo-β-naphthol-ester, N,N-di(l,2-naphthoquinonediazide-5-sulfonyl)-
Aniline, 2'-(1,2-nafdoquinonediazide-
5-sulfonyloxy)-1-hydroxy-anthraquinone, 1,2-naphthoquinodiazide-5-sulfone-2
, 4-dihydroxybenzophenone ester, 1,2-
Naphthoquinodiazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 2 moles of 1.2-naphthoquinonediazide-5-sulfonic acid chloride and 4.
Condensate with 1 mol of 4'-diaminobenzophenone, 1.
2-naphthoquinonediazide-5-sulfonic acid chloride 2
condensate of 1 mole of 4.4'-dihydroxy-1,1'-diphenylsulfone, 1 mole of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 1 mole of purbrogalin, 1.2- Naphthoquinone diazide-5
Examples include 1°2-quinonediazide compounds such as -(N-dihydroabiethyl)-sulfonamide. Also, Special Publication No. 37-1953, No. 37-3627,
No. 37-13109, No. 40-26126, No. 40
-3801, 45-5604, 45-2734
No. 5, No. 51-13013, JP-A-48-98575
1,2-quinonediazide compounds described in Japanese Patent Application No. 48-63802 and Japanese Patent No. 48-63802 can also be mentioned.

Among the above 0-quinonediazide compounds, 0-quinonediazide is obtained by reacting 1,2-benzoquinonediazide sulfonyl chloride or 1,2-naphthoquinonediazide sulfonyl chloride with pyrogallol acetone condensation resin or 2,3,4-trihydroxybenzophenone. Ester compounds are particularly preferred.

As the O-quinonediazide compound 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 the 0-quinonediazide compound used in the present invention in the photosensitive composition is preferably 5 to 60% by weight,
Particularly preferably, the amount is 10 to 501i%.

Examples of alkali-soluble resins used in the photosensitive composition of the present invention include novolac resins, vinyl polymers having phenolic hydroxyl groups, and polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. Examples include condensation resins with.

Examples of the novolac resin used in the present invention include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-57841, Examples include copolymer resins of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 55-127553.

The molecular weight (polystyrene standard) of the novolak resin is:
Preferably, the number average molecular weight Mn is 3.00x 10” to 7
．． SOx 10', weight average molecular weight Mw is 1.00X
10' to 3, OOx 1.0' More preferably Mn is 5.00x 10' to 4, OOx 10'
Mw is 3.00X 103 to 2.00X 10'.

The above novolak resins may be used alone or in combination of two or more.

The proportion of the novolak resin in the photosensitive composition of the present invention is 5 to 95% by weight.

Furthermore, the vinyl polymer having a phenolic hydroxyl group used in the present invention is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and has the following formula [
A polymer containing at least one structural unit of 11 to [V] is preferred.

- Formula [1] General formula [i! ] General formula [II+] General formula [IV] General formula [V] H [wherein R3 and R2 each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom, R
5 represents a hydrogen atom, a halogen atom or an alkyl group,
Preferably represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents a nitrogen atom or an oxygen atom and an aromatic group. represents an alkylene group that may have a substituent and connects to a carbon atom, Akebono represents an integer from 0 to 1O, and B represents a phenylene group that may have a substituent or a phenylene group that may have a substituent. The polymer used in the photosensitive composition of the wood invention preferably has a copolymer-type structure, and is represented by the above-mentioned formula [I] to formula [V], respectively. Examples of monomer units that can be used in combination with the structural unit include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, p-
Styrenes such as methylstyrene and p-chlorostyrene,
For example, acrylic acids such as acrylic acid and methacrylic acid,
For example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, maleic anhydride, etc., such as methyl acrylate,
Ethyl acrylate, 〇-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-acrylate
Esters of α-methylene aliphatic monocarboxylic acids such as chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, 5 ethyl methacrylate, nitriles such as acrylonitrile, methacrylonitrile, etc., e.g. acrylamide Amides such as acrylanilide, p-chloroacrylanilide, ■-nitroacrylanilide, ■-methoxyacrylanilide, etc., vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. , vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as l-methyl-1-methoxyethylene,
1.1-dimethoxyethylene, l,2-dimethoxyethylene, 1.1-dimethoxycarbonylethylene, 1-
Ethylene derivatives such as methyl-1-nitroethylene, such as N-vinylvirol, N-vinylcarbazole, N
- There are N-vinyl monomers such as vinyl indole, N-vinylvirolone, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are therefore preferred.

These monomers may be bound in either a block or random manner in the polymer used in the present invention.

The proportion of the vinyl polymer used in the present invention in the photosensitive composition is 0.5 to 70% by weight.

As the vinyl polymer used in the present invention, the above-mentioned polymers may be used alone, or a combination of two or more thereof may be used. Moreover, it can also be used in combination with other polymer compounds.

A printout material can be added to the photosensitive composition that upon exposure to light forms a visible image. The printout material is made of an organic dye that changes its color tone by interacting with a compound that generates an acid or a free radical when exposed to light. 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A No. 36209, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A No. 53-36223, and trihalomethyl-triazine described in JP-A-55-6244. There is 0-
Ester or amide compound of naphthoquinonediazide-4-sulfonic acid chloride and phenols having electron-withdrawing substituents or anilic acid, JP-A-55
Examples include halomethylvinyloxadiazole compounds and diazonium salts described in JP-A-77742 and JP-A-57-148784.

In addition, examples of the organic dyes include Victoria Pure Blue BOH (manufactured by Sakudogaya Chemical Co., Ltd.), Batent Via Blue (manufactured by Jujuokoku Chemical Co., Ltd.), and Oil Blue #60.
3 (manufactured by Orient Chemical Industry Co., Ltd.), Sudan Blue II (manufactured by BASF), crystal violet, malachite green, Tsukushin, methyl violet, ethyl violet, methyl orange, brilliant green, Congo red, eosin, rhodamine 6G, etc. Can be done. In addition to the above-mentioned materials, a plasticizer, a surfactant, an organic acid, an acid anhydride, and the like can be added to the photosensitive composition as needed.

Furthermore, the photosensitive composition used in the present invention may contain, for example, p-tert- to improve the oil sensitivity of the photosensitive composition.
It is also possible to add butylphenol formaldehyde resin, p-n-octylphenol formaldehyde resin, or a resin in which these resins are partially esterified with an 0-quinonediazide compound.

The photosensitive lithographic printing plate of the present invention can be produced by dissolving each of these components in the following solvents and coating and drying the solution on the surface of the support used in the present invention to provide a photosensitive layer.

Examples of solvents that can be used to dissolve the photosensitive composition used in the present invention include methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol methyl ether,
Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol methyl ethyl ether, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethyl formamide, dimethyl sulfoxide,
Dioxane, acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, diacetone alcohol, acetylacetone, r-butyrolactone and the like can be mentioned. These solvents can be used alone or in combination of two or more.

The coating method used in coating the surface of the support with the photosensitive composition used in the present invention includes conventionally known methods, such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, and blade coating. and curtain coating, etc. are used. At this time, the coating amount varies depending on the application, but a coating amount of, for example, 0.05 to 5.0 g/+e'' in terms of solid content is preferable.

When using the photosensitive lithographic printing plate thus obtained,
Conventional methods can be applied, such as exposing a transparent original image with a line image, halftone image, etc. in close contact with the photosensitive surface, and then using an appropriate developer to develop the non-image areas. A relief image is obtained by removing the photosensitive layer. As a light source suitable for exposure, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, etc. are used, and as a developer used for development, an alkaline aqueous solution is preferable, such as sodium silicate, potassium silicate, etc. There are alkaline aqueous solutions such as aqueous solutions of sodium hydroxide, potassium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, etc. The concentration of the alkaline aqueous solution at this time varies depending on the photosensitive composition and the type of alkali, but is generally in the range of 0.1 to 10% by weight, and the acid-alkaline aqueous solution may contain a surfactant or Organic solvents such as alcohols can also be added.

In the following margin [Examples] The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Examples 1 to 4 [Preparation of support l] 0.3 mm thick aluminum plate (material 1050. Tempered H
16) was immersed in a 5% caustic soda aqueous solution, degreased at a temperature of 65° C. for 1 minute, and then washed with water.

This degreased aluminum plate was neutralized by immersing it in a lθ% nitric acid aqueous solution at 25° C. for 1 minute, and then washed with water. Next, this aluminum plate was heated in a 0.3 mol/f nitric acid aqueous solution at 30°C with an alternating current density of 50^/dm2 for 30 minutes.
After performing electrolytic surface treatment for 0 seconds, desmutting treatment was performed at 60° C. for 10 seconds in a 5% caustic soda aqueous solution. Then, in a 20% sulfuric acid solution at a temperature of 20°C and a current density of 3A/d.
a' The surface of the aluminum plate was anodized under conditions of a treatment time of 1 minute, and further subjected to a sealing treatment for 20 seconds with hot water at 80°C.

1% Emar N
The support was immersed in an aqueous solution of C (anionic surfactant, manufactured by Kao Atlas Co., Ltd.) at 60° C. for 1 minute, and the treated support was designated as Support 1.

[Preparation of Supports 2 to 6] In the preparation of Support 1 described above, all of Support 1 was prepared except that the aluminum plate was immersed in the aqueous solution listed in Table 1 instead of the 1% Emar NC aqueous solution. Supports 2 to 6 were produced in the same manner as described above.

Margin below Table 1 *Comparative examples were crushed for 15 seconds at ambient temperature.

[Sample 1 of photosensitive lithographic printing plate. -1 Preparation] A coating solution (1) of a photosensitive composition having the following composition was applied to the support 1 prepared as described above using a wire bar, and dried at 80° C. for 2 minutes. A photosensitive lithographic printing plate having a dry coating thickness of 2.2 g/i' was obtained.

[Coating liquid of photosensitive composition (1)] In novolac resin 6.7 go-quinonediazide compound ◆8 1.5 g Surfactant base 0.28 Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.08 g Compound 1 that generates halogen free radicals 0.15 g Methyl cellosolve 100 mIL Next, using a W metal halide lamp in 2 as a light source, the obtained photosensitive lithographic printing plate was exposed by irradiating it with 8 mW/Cl112 for 60 seconds. .

This exposed photosensitive lithographic printing plate was prepared using a commercially available developer (SDR-1, manufactured by Konica Co., Ltd., diluted 5 times, developing time 3
Sample I of the lithographic printing plate
'-1 was obtained.

[Samples 1-2 to 1 of photosensitive lithographic printing plates. -Preparation of It]
A coating solution of the photosensitive composition (1
) to obtain samples I-2 to I-6 of photosensitive lithographic printing plates.

Then, exposure and development were carried out in the same manner as described above to obtain lithographic printing plate samples 1'-1 to ■'-6.

The following compounds were used as the compounds *A to *D.

*A; Novolac resin [copolycondensation resin of phenol, ■-cresol, p-cresol, and formaldehyde (
The molar ratio of phenol, ■-cresol and p-cresol is 2.0=4.8:3.2, Mw-
6,500, M+y/Mn-5,4) ]]*B;0
-Quinonediazide compound C: Surfactant Emulgen 120 (polyoxyethylene lauryl ether, manufactured by Kao Corporation) *D: Compound that generates halogen free radicals 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4 −
Oxadiazole (compound described in Example 1 of JP-A No. 54-74728) The obtained lithographic printing plate sample 1'-1-I'-6 was evaluated using the evaluation method described below. We conducted an evaluation.

The results obtained are shown in Table 2.

[Evaluation method] (Stain test due to residual film) After forming 5 image areas (5wm x 15c+e) on the planographic printing plate obtained under the above exposure and development conditions, an erasing liquid (SIR-15, manufactured by Konica Corporation) was applied. ) to erase the image area.

The erasing time was divided into 5 levels (shown in Table 2), and fringe stains due to erasing at that time were checked using developing ink CSOP-I (manufactured by Konica).

Evaluation: ○...Good △...Erased marks appear (ink does not stick, but can be clearly seen by visual inspection) ×...Stains (ink sticks) (processing chemical resistance) The above-mentioned exposure and After plate making according to development conditions, ink for development ink (SAP-T, manufactured by Konica, manufactured by PI Fuji Photo Film) and plate cleaners used during printing (Ultra Plate Cleaner (UPC), ABC) are added.
(manufactured by Chemical Co., Ltd.) for a certain period of time, and the state of the photosensitive layer on the plate at that time was evaluated.

evaluation: O: No change.

Δ: The solid surface is eroded by chemicals.

×: The solid portion is eroded and disappears.

(Half dot reproducibility) The planographic printing plate obtained under the above exposure and development conditions was coated with coated paper printing ink (
Printing was performed using Toyo Ink Mfg. Co., Ltd., New Bright Red) and dampening water (SEU-3, 2.5%, Konica Co., Ltd.).

The state of halftone dot reproduction of the dark part of the halftone dot image (wi point area ratio 97%) of the thus obtained printed matter was evaluated using a 25x magnifying glass.

Evaluation: ○...Reproduced (no smearing) ×: Not reproduced (stains smeared) (Printing durability) Poor inkling in the solid area of the image area of a printed matter printed under the same conditions as those used for halftone reproducibility Printing was continued until these appeared or the ink was deposited on the non-image areas, and the number of printed sheets was counted at the time these appeared.

Examples 5 to 8 [Preparation of sample n-1 of photosensitive lithographic printing plate] On the support 1 prepared in Example 1, a coating solution (2) of the photosensitive composition having the following composition was applied using a whirler. Apply and heat at 90℃ for 1
Dry for a minute. Sample H-1 of a photosensitive lithographic printing plate having a dry coating film thickness of 1.7 g/la' was obtained.

[Coating liquid of photosensitive composition (2)] Copolymer◆E5゜Og Diazo resin *FO, 5g Jurimer^C-10L (manufactured by Nippon Pure Chemical Industries, Ltd.) 0.0
5g Victoria Pure Blue BO) I (manufactured by Hodokugaya Chemical Co., Ltd.) 0.1g Methyl Cellosolve Exposure was performed by irradiating for 60 seconds.

This exposed photosensitive lithographic printing plate was developed with a commercially available developer (SDN-21, manufactured by Konica, diluted 4 times, development time 20 seconds, development temperature 27°C), and a sample of the lithographic printing plate was developed. 1
AIV-1 was obtained.

[Preparation of sample rows 2-I (-6 of photosensitive lithographic printing plate) Samples I--6 of Example 1 were applied to supports 2-6 treated with the respective aqueous solutions prepared in Examples 2-4 and Comparative Examples 5-6. Coating liquid (2) of the photosensitive composition is applied in the same manner as in the preparation of step 1,
Samples of photosensitive lithographic printing plates +12 to 11-6 were obtained.

Then, exposure and development were carried out in the same manner to obtain lithographic printing plate samples +1'-1 to I+'-6.

The obtained lithographic printing plate samples +1'-1 to II'-6 were evaluated using the evaluation methods described in Examples 1 to 4.

The results obtained are shown in Table 3.

In addition, copolymer IE used in the coating solution (2) of the photosensitive composition
The following F in the diazo resin was used.

*E; Eutectic p-hydroxyphenylmethacrylamide/acrylonitrile/ethyl acrylate/methacrylic acid-10/3
0/[10/6 eutectic body (Mw=60°*F Nidiazo Resin Table Table [Effects of the Invention] The present invention further provides a pretreated support with an aqueous solution containing an aniosurfactant. Through the treatment, the resulting lithographic printing plate does not leave any film after development and has excellent water retention properties.Furthermore, it has excellent treatment chemical resistance and printing durability.

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate, characterized in that the surface of a pretreated support is treated with an aqueous solution containing an anionic surfactant, and then a photosensitive layer is provided on the surface.