JP3475377B2 - Photosensitive materials for lithographic printing plates - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material for a lithographic printing plate, and more particularly to a photosensitive material capable of obtaining a lithographic printing plate having excellent resolution and printing performance by scanning exposure with a laser beam.

[0002]

2. Description of the Related Art Hitherto, many photosensitive materials for lithographic printing plates using a photopolymerization system and methods for preparing lithographic printing plates using the same have been known. A compound capable of addition polymerization or crosslinking and a photopolymerization initiator are known. Further, if necessary, a photosensitive composition comprising a binder component composed of an organic polymer compound or the like is coated on a hydrophilic support to prepare a photosensitive material for a lithographic printing plate, and a desired image is formed on the photosensitive composition layer. Is image-exposed, the exposed portion is cured, and the unexposed portion is dissolved and removed to form a lipophilic image portion to form a lithographic printing plate, which is a conventionally used liquid developing type diazo resin, for example. The one contained is typical.

In recent years, in order to obtain a lithographic printing plate having a high resolution, it has been studied to produce a lithographic printing plate by performing digital exposure with a laser beam based on image information and developing it. For example, a system for forming a printing plate by modulating a light source and directly scanning and exposing a photosensitive material with an image signal transmitted through a communication line and an output signal from an electronic plate making system or an image processing system. Is. This is because a laser is suitable as the light source at this time.

However, the above-mentioned conventional lithographic printing plate material containing a diazo resin is difficult to achieve spectral sensitization and high sensitivity in order to have sensitivity in accordance with the oscillation wavelength of the laser light for exposure. , A material having a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator has been attracting attention for digital exposure by laser light.

[0005]

However, a photosensitive material for a lithographic printing plate in which a layer of a photopolymerizable photosensitive composition containing a compound having an ethylenically unsaturated bond is formed on a hydrophilic support is used as a support. And the adhesiveness to the composition layer is poor, and the image formed on the composition layer is inferior in inking property and printing durability.

It is described in JP-B-50-7481 that a diazo compound is added to the photosensitive composition or an undercoat layer having the diazo compound is provided in order to improve the adhesiveness. According to this, although the adhesiveness is improved, the non-image portion is stained (ground stain).

Further, a technique of performing phosphoric acid treatment as anodizing treatment for graining a hydrophilic support is also known, but there is a problem of generation of scumming.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a lithographic printing plate material which can obtain excellent resolution and printing performance by scanning exposure with a laser, and is particularly photopolymerizable. To improve the adhesiveness between the photosensitive composition layer and the hydrophilic support.

[0009]

The above-mentioned objects of the present invention are described in the following A on the hydrophilic surface of a support having a hydrophilic surface.
The subbing layer having a thickness of 0.01 to 0.5 μm, containing 35% by weight or more of the compound having a hydrophilic ethylenically unsaturated bond selected from the above compounds with respect to the solid content of the subbing layer. When,
A polymer binder, a compound having an ethylenically unsaturated bond and a photopolymerization initiator are contained , and the ethylenically unsaturated bond is contained.
5 to 80 parts by weight based on the total photosensitive layer composition
The composition is applied in the range of amount% and the thickness is 0.1 to 10
and a photopolymerizable photosensitive layer having a thickness of .mu.m in this order, and the ratio of the weight of the compound having a hydrophilic ethylenically unsaturated bond soluble at 25.degree. it is .2 above, the subbing layer may contain a water-soluble or water-dispersible initiator, it undercoat layer further contains a water-soluble resin, thus being achieved. A: (meth) acrylonitrile, (meth) acrylamido
De, (meth) acrylic acid, (meth) acrylic acid soda,
Methyl (meth) acrylate, ethyl (meth) acryl
, N-propyl (meth) acrylate, isopropyl
(Meth) acrylate, n-butyl (meth) acrylate
Acetate, isobutyl (meth) acrylate, t-butyl
(Meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acry
Rate, 2-hydroxybutyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, 2-sia
Noethyl (meth) acrylate, β-ethoxyethyl ether
Rosolve (meth) acrylate, (meth) acrylic
Dehydr, N, N'-methylenebis (meth) acrylic acid
2-hexyloxyethyl-N-methacrylodolphin
Lubamate, allyl (meth) acrylate, acrylic acid-
2-chloroethyl, 2,2-bis [4- (methacryloxy)
Di- (polyethoxy) phenyl] propane, diacrylate
Ethylene glycol ethoxylate, polyethylene glycol
Cold (meth) acrylate, 3- (meth) acrylo
Ilimino-1-phenyl-5-pyrazolone, ω-cal
Boxy-polycaprolactone (n = 2) mono acrylate
DOO, phthalic acid mono hydroxyethyl Le (meth) acrylate
G, monohydroxyethyl succinate (meth) acrylate
G, acrylic acid dimer, 2-hydroxy-3-pheno
Xypropyl acrylate, isocyanuryl ethylene oxy
Side (EO) modified diacrylate, pentaerythritol
Triacrylate, mono (2- (meth) acryloyl
(Loxyethyl) acid phosphate, glycerol
Mono (meth) acrylate, glycerin (meth) acry
Rate, hydroxymethyl vinyl ether, hydroxy
Ethyl vinyl ether, hydroxypropyl vinyl a
Tell, hydroxybutyl vinyl ether

That is, the present inventors believe that the problem of background stain can be solved if the portion corresponding to the unexposed portion of the undercoat layer for imparting the adhesiveness is easily dissolved in the developing solution at the time of development, and further the ethylene stain is solved. A compound having a hydrophilic ethylenically unsaturated bond in the undercoat layer of the photographic material for a lithographic printing plate having a photopolymerizable photosensitive layer containing a compound having a polyunsaturated bond and a photopolymerization initiator. For example, the undercoat layer is polymerized in the exposed area, and excellent solubility can be maintained in the unexposed area, and both adhesiveness, printing durability and resolution are compatible, and a good digital-compatible lithographic printing plate material with no background stains. The present invention has been achieved based on the finding that the above is obtained. In addition, since the undercoat layer of the present invention ensures good developability, it is possible to reduce the necessity of imparting a certain degree of hydrophilicity to the photosensitive layer to obtain developability, and to increase the lipophilicity of the photosensitive layer. It also has an accompanying effect that the scumming does not occur even if the inking property is improved.

As a subbing layer in a conventional lithographic printing plate material containing a photosensitive layer containing a diazo compound, polyvinyl sulfonic acid is used in West German Patent No. 1,621,478. Use of polyacrylic acid for U.S. Pat. No. 433, and use of polyacrylamide for U.S. Pat.
No. 6 describes that a resin containing a sulfonic acid group is used, but all of them are polymers and have good developability, but they do not consider polymerization by exposure.

The present invention will be described in detail below.

The present invention comprises a hydrophilic ethylenically unsaturated bond in the undercoat layer of a lithographic printing plate photosensitive material having a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. It is characterized in that the compound having a is contained in combination.

Examples of the compound having a hydrophilic ethylenic unsaturated bond include ( meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, sodium (meth) acrylate, methyl (meth) acrylate and ethyl (meth). Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxybutyl (meth)
Acrylate, dimethylaminoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, β-ethoxyethyl cellosolve (meth) acrylate, (meth) acrylaldehyde, N, N′-methylenebis (meth) acrylamide, 2-hexyloxyethyl -N-
Methacryloyl carbamate, allyl (meth) acrylate, 2-chloroethyl acrylate, 2,2-bis [4
-(Methacryloxy-polyethoxy) phenyl] propane, diethylene glycol ethoxylate acrylate,
Polyethylene glycol di (meth) acrylate, 3-
(Meth) acryloylimino-1-phenyl-5-pyrazolone, ω-carboxy-polycaprolactone (n =
2) Monoacrylate, monohydroxyethyl (meth) acrylate phthalate, monohydroxyethyl (meth) acrylate succinate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric ethylene oxide (EO) modified diacrylate, penta Erythritol triacrylate, mono (2
- (meth) acryloyloxyethyl) acid phosphate, glycerol mono (meth) acrylate, glycerol (meth) acrylate, hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether include hydroxybutyl vinyl error <br/> over Te Le .

Among these, 25 are particularly preferable.
It has a solubility in water at 20 ° C. of 20 or more, for example, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, sodium (meth) acrylate, methyl (meth) acrylate, ethyl (meth). Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl acrylate, isobutyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl (meth) acrylate,
2-cyanoethyl (meth) acrylate, β-ethoxyethyl cellosolve (meth) acrylate, (meth) acryl aldehyde, N, N′-methylenebisacrylamide, 2,2-bis [4 (methacryloxypolyethoxy) phenyl] propane, polyethylene Examples thereof include glycol di (meth) acrylate, hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and hydroxybutyl vinyl ether, and these are used alone or in combination.

The thickness of the undercoat layer is preferably 1.0 μm or less, more preferably 0.01 to 0.5 μm. If it is too thin, the effect of the present invention may be lowered, and if it is too thick, the sensitivity may be lowered.

The undercoat layer containing a compound having a hydrophilic ethylenic unsaturated bond preferably further contains a water-soluble or water-dispersible photopolymerization initiator from the viewpoint of polymerization. From the viewpoint of formability, it is also effective to contain a water-soluble resin.

Examples of water-soluble photopolymerization initiators that can be used include (2-acryloyloxy) (4-
Benzoylbenzyl) dimethyl ammonium bromide, 2-
(3-Dimethylamino-2-hydroxypropoxy)-
3,4-Dimethyl-9H-thioxanthone-9-one mesochloride, (4-benzoylbenzyl) trimethylammonium chloride, 2 (2'-trimethylammoniumethylamino) -4,6-bis (trichloromethyl)-
Conventionally known compounds such as S-triazine can be mentioned. As the water-dispersible polymerization initiator, a conventionally known organic solvent-soluble polymerization initiator can be obtained as an aqueous dispersion by using an oil protect dispersion method or the like. You can use it.

As the water-soluble resin, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch,
Gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate, polyvinylamine polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, polyethylene glycol and the like can be mentioned, with preference given to polyvinylpyrrolidone and polyethylene glycol.

As the support having a hydrophilic surface (hereinafter referred to as "support") used in the present invention, all known materials for lithographic printing plates are preferably used. Specifically, aluminum, zinc, chromium, copper, magnesium,
Metals such as nickel and iron and alloy plates and sheets mainly containing them, inorganic plates and sheets such as paper, glass and ceramics, plastic plates and sheets such as polyethylene terephthalate whose surface is mattized to make them hydrophilic, plastic plates or A plate or sheet in which a metal layer of aluminum, zinc, chromium or the like is laminated on a sheet, a hydrophilic polymer compound layer provided on an arbitrary support, and the like. As examples of the hydrophilic polymer compound, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene glycol, gelatin, gum arabic and the like are preferably used.

As the printing plate material, an aluminum plate subjected to graining treatment in the above support is particularly preferably used. Aluminum plate (including alumina laminate)
After degreasing the surface, those treated by a known method such as glass bead graining, sandblast graining, electrolytic graining, brush graining, ball graining, and chemical polishing can be preferably used. Particularly preferred is the electrolytic etching method that can obtain deep and uniform grain. When the support material is aluminum, a grained surface further subjected to anodization is also preferably used. The anodic oxidation treatment is performed using, for example, an inorganic salt such as phosphoric acid, chromic acid, boric acid, sulfuric acid or the like, or an organic acid such as oxalic acid, or a mixture thereof.

The thickness of the support is usually in the range of 12 μm or more (preferably 20 μm or more) and 2000 μm or less (preferably 500 μm or less).

In the photosensitive layer of the present invention, an image formed on the surface of a hydrophilic support is used as a printing plate, so that the image portion is preferably lipophilic. In other words, it is important that the image part has a higher ink landing property than the non-image part. In order to impart such characteristics, it is preferable that the contact angles of water between the image portion and the non-image portion differ by 20 degrees or more, preferably 40 degrees or more.

The thickness of the photosensitive layer is usually 0.1 μm or more and 10 μm or less (preferably 5 μm) in view of requirements such as printing durability.
m or less).

The photosensitive layer of the present invention contains a compound capable of being polymerized or cured and, if necessary, a polymerization initiator.

As the polymerizable or curable compound, known compounds can be used without particular limitation, but compounds having at least one ethylenically unsaturated double bond in the molecule are preferably used. Specific compounds include:
For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Acrylate of ε-caprolactone adduct of dioxane alcohol, monofunctional acrylic acid esters such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate,
Crotonate, methacrylic acid in place of maleate, itaconic acid, crotonic acid, maleic acid ester, such as ethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate. , Neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalic acid neopentyl glycol diacrylate ε-caprolactone adduct, 2- ( 2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-
1,3-dioxane diacrylate, tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6
Difunctional acrylic acid esters such as diacrylate of diglycidyl ether of hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate, for example, triester Methylol propane triacrylate, ditrimethylol propane tetraacrylate, trimethylol ethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Ε-caprolactone adduct, pyrogallol triacre , Propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalaldehyde modified dimethylolpropane triacrylate, and other polyfunctional acrylic acid esters, or these acrylates as methacrylates, itaconates, crotonates, maleates. Examples thereof include methallylic acid, itaconic acid, crotonic acid, maleic acid ester and the like.
Among them, acrylic acid ester and methacrylic acid ester compounds can be particularly preferably used. 1 of these compounds
One kind or a mixture of two or more kinds can be used.

In addition, as a compound capable of addition polymerization or cross-linking, an oligomer having an appropriate molecular weight and acrylic acid,
Alternatively, methacrylic acid was introduced to impart photopolymerization property,
A so-called prepolymer can also be preferably used.
These prepolymers may be used alone or in admixture of two or more, or may be used in admixture with the above-mentioned monomers. Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid,
Hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid,
Polybasic acids such as pimelic acid, sebacic acid, dodecanoic acid and tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin Polyester acrylates obtained by introducing (meth) acrylic acid into a polyester obtained by binding a polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, and 1,2,6-hexanetriol, for example, , Bisphenol A / epichlorohydrin / (meth) acrylic acid, phenol novolak / epichlorohydrin / (meth) acrylic acid, etc. Xyacrylates, for example, ethylene glycol / adipic acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalylmethacrylate / xylene diisocyanate, 1,2-polybutadiene. Glycol Tolylene Diisocyanate-2-
Urethane acrylates such as hydroxyethyl acrylate, trimethylolpropane / propylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, in which (meth) acrylic acid is introduced into urethane resin, for example, polysiloxane acrylate, polysiloxane / diisocyanate / Other examples include silicone resin acrylates such as 2-hydroxyethyl acrylate, alkyd-modified acrylates obtained by introducing a (meth) acryloyl group into an oil-modified alkyd resin, and spirane resin acrylates.

The compound capable of being polymerized or cured is 5% by weight or more (preferably 10% by weight or more) in the entire photosensitive layer composition,
It is compounded in the range of 80% by weight or less (preferably 70% by weight or less).

The polymerization initiator is used to cure the photosensitive layer by exposure, and a known photopolymerization initiator or a thermal polymerization initiator can be used in the case of the photothermal conversion type photosensitive layer. "Photopolymer Handbook" as a photopolymerization initiator
(Edited by Photopolymer Society, published by Industrial Research Society, 1989
1) or a combination of 2 or more of the compounds described on pages 39 to 48 of (Year). Examples of the thermal polymerization initiator include cumene hydroperoxide and tertiary
Organic peroxides such as butyl hydroperoxide, dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, etc., for example, azo compounds such as azobisisobutyronitrile, hydrogen peroxide Divalent iron salt, persulfate and sodium hydrogen sulfate,
In addition to redox-type polymerization initiators such as cumene hydroperoxide and divalent iron salts, benzoyl peroxide and dimethylaniline, disulfide compounds and organometallic complexes such as manganese triacetylacetonate and pentacyanobenzyl cobaltate can be used. . The blending amount of these polymerization initiators is not particularly limited, but is preferably 0 to 20 parts by weight (preferably 10 parts by weight or less) with respect to 100 parts by weight of the compound capable of addition polymerization or crosslinking.

A polymeric binder is optionally used in the photosensitive layer of the present invention. As a polymer binder,
Polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, (meth) acrylic resin, styrene resin, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polysulfone , Polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin and the like. Further, a resin having an unsaturated bond in the resin, for example, a diallyl phthalate resin and its derivative, chlorinated polypropylene and the like can be polymerized with the above-mentioned compound that seals the ethylenically unsaturated bond, so that it is suitably used depending on the application. Can be used. These resins are 1
They may be used alone or in combination of two or more. Further, in the present invention, those that dissolve or swell in an alkaline aqueous solution are preferable, and the resin described above, a carboxyl group,
A copolymer resin with a compound having a group such as a sulfonium group which improves the solubility in an aqueous alkaline solution is preferably used.

As a light source for imagewise exposing the light-sensitive material for lithographic printing plate of the present invention, for example, laser, light emitting diode, xenon flash lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure mercury lamp, electrodeless. A light source etc. can be mentioned. When performing batch exposure using a xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, tungsten lamp, high pressure mercury lamp, electrodeless light source, etc., a negative pattern of the desired exposure image is formed on the photosensitive material with a light shielding material. The mask materials may be superposed and exposed.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp or a tungsten lamp is exposed and controlled by an optical shutter material such as liquid crystal or PLZT, an image signal is used. It is possible and preferable to perform appropriate digital exposure. In this case, direct writing can be performed without using a mask material.

The laser is suitable for direct writing without using a mask material, because light can be focused into a beam and scanning exposure can be performed according to image data. Further, when a laser is used as a light source, it is easy to reduce the exposure area to a minute size, and high-resolution image formation becomes possible. As a laser light source, any of an argon laser, a He-Ne gas laser, a YAG laser, a semiconductor laser and the like can be preferably used.

When laser light is used as the light source, a sensitizing dye is preferably added to the photosensitive layer.

Examples of the compound for wavelength sensitizing from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, flugide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane. , Triphenylmethane, polymethine acridine, coumarin, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds and the like, and further, European Patent No. 0568,993 and US Pat. No. 4,50.
The compounds described in No. 8,811, No. 5,227,227 and the like can also be used.

It is also known to combine an onium salt compound and the like with a sensitizing dye to make longer-wave light sensitive. For example, JP-A-60-76740 and JP-A-60-7.
8443, 60-88005, U.S. Pat. No. 4,3.
No. 04,923 and the like disclose a technique of combining with dyes such as cyanine, phthalocyanine and porphyrin.

Among these, cyanine, coumarin, ketocoumarin, squarylium salt, porphyrlphyrin and styryl compounds are preferable, and coumarin, ketocoumarin and squarylium salt compounds are more preferable.

If necessary, the light-sensitive material of the present invention may be provided with an overcoat layer for protecting the photosensitive layer, and a layer such as a photothermal conversion layer in the case of a thermal polymerization system.

Further, in order to obtain a higher-definition printed image using the lithographic printing plate produced from the light-sensitive material of the present invention, a laser beam is generated even when the beam diameter of the exposure laser is narrowed during scanning exposure. It is preferable to physically block the bottom of the beam, and as the method, it is preferable to shape the beam of the laser light by passing through the slit because it is a simple and reliable method.

The developing solution used in the development processing of the lithographic printing plate photosensitive material of the present invention may be any known one, but when contained in the developing solution, the unexposed portion of the photosensitive layer ( It is preferable to use a liquid which can dissolve or swell (non-image part) and has an organic solvent having a solubility in water of 10% by weight or less at 20 ° C., an alkaline agent, and water as essential components.

Examples of the organic solvent include carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl repurinate; ethyl butyl ketone, methyl isobutyl. Ketones, ketones such as cyclohexanone; alcohols such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alkyl substitution of xylene, etc. Aromatic hydrocarbons; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzene; Ether and benzyl alcohol are particularly preferred. The content of the organic solvent in the developer is 1 to
It is about 20% by weight, preferably 2 to 10% by weight.

As the alkali agent contained in the developer, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium or ammonium salt of secondary or tertiary phosphoric acid, sodium metasilicate, Sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanol Amine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediamine and the like, and preferably potassium silicate, sodium silicate, Sodium phosphate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, monoethanolamine, diethanolamine, triethanolamine. The content of the alkaline agent in the developer is usually about 0.05 to 8% by weight, preferably 0.5 to 6% by weight.
Is.

Further, in order to enhance storage stability, printing durability and the like, water-soluble sulfites such as sodium sulfite, potassium sulfite, lithium sulfite and magnesium sulfite are added in an amount of about 0.05 to 4% by weight of the developer composition, Preferably 0.1-1
It is preferably contained in the weight% developer. Further, a solubilizing agent may be included in order to assist the dissolution of the organic solvent in water.

[0044]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Preparation of support >> An aluminum plate (material 1050, temper H16) having a thickness of 0.24 mm was immersed in an aqueous sodium hydroxide solution kept at 65 ° C. and degreased for 1 minute. After that, it was washed with water. The degreased aluminum plate was immersed in a 10% hydrochloric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization and then washed with water. Then, this aluminum plate was placed in a 1.0 wt% hydrochloric acid aqueous solution at a temperature of 25 ° C. and a current density of 100.
After surface-roughening the electric field for 60 seconds with an alternating current under the condition of A / dm ² , a desmut treatment was carried out for 10 seconds in a 5% sodium hydroxide aqueous solution kept at 60 ° C. The desmutted roughened aluminum plate was placed in a 15% sulfuric acid solution at a temperature of 25 ° C., a current density of 10 A / dm ² , and a voltage of 15
Anodizing treatment was performed for 1 minute under the condition of V, and then sealing treatment was performed at a temperature of 90 ° C. with 3% sodium silicate to prepare a support.

<< Preparation of Photosensitive Lithographic Printing Plate Material >> An undercoat layer coating solution having the following composition was coated on the above support using a wire bar to a dry film thickness of 0.2 μm, and then at 80 ° C. It heat-processed for 2 minutes and formed the undercoat layer.

Monomer (dimethylaminoethyl acrylate) 500 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381) 5 parts by weight Water 20,000 parts by weight Next, a photosensitive layer coating solution having the following composition was used with a wire bar. To a dry film thickness of 1.5 μm and heat-treated at 80 ° C. for 2 minutes to form a photosensitive layer.

Binder resin (methyl methacrylate / butyl acrylate / acrylic acid / acrylonitrile = 78/8/6/8) 450 parts by weight Monomer (pentaerythritol triacrylate) 600 parts by weight Ketocoumarin dye (manufactured by Japan Photosensitive Dyes KK; NKX) -846) 20 parts by weight Organic peroxide (3,3 ', 4,4'-tetrabis (t-butyldioxycarbonyl) dioxybenzophenone) 72 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381) 10 Parts by weight methyl cellosolve 5000 parts by weight methyl propylene glycol (manufactured by Nippon Emulsifier Co., Ltd .; MFG) 5000 parts by weight Further, the photosensitive layer was heat-treated at 80 ° C. for 2 minutes under light shielding,
An overcoat layer having the composition shown below was applied onto the photosensitive layer with an applicator so as to have a thickness of 2.0 μm to obtain a lithographic printing plate material.

Polyvinyl alcohol (GL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 97 parts by weight Activator (manufactured by Bayer Co., Ltd .; FT-248) 3 parts by weight Water 1000 parts by weight Example 2 Film thickness of subbing layer Is 0.7 μm, the thickness of the photosensitive layer is 1.0 μm
A lithographic printing plate material was produced in the same manner as in Example 1 except that m was used.

Example 3 A lithographic printing plate material was prepared in the same manner as in Example 1 except that the coating solution for the undercoat layer having the following composition was coated using a wire bar to a dry film thickness of 0.2 μm.

Monomer (2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane manufactured by Shin Nakamura Chemical Co., Ltd .; NK ester BPE-1300) 500 parts by weight Activator (manufactured by Asahi Glass Co., Ltd .; Surflon S) -381) 5 parts by weight Water 20000 parts by weight Example 4 A lithographic plate was prepared in the same manner as in Example 1 except that an undercoat layer coating solution having the following composition was applied to a dry film thickness of 0.2 μm using a wire bar. A printing plate material was prepared.

Monomer (polyethylene glycol diacrylate Toa Gosei Chemical Co., Ltd .; M-260) 500 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381) 5 parts by weight Water 10000 parts by weight Example 5 below A lithographic printing plate material was produced in the same manner as in Example 1 except that the coating solution for the undercoat layer having the composition was applied using a wire bar so that the dry film thickness was 0.2 μm.

Monomer (Polyethylene glycol diacrylate Toa Gosei Chemical Co., Ltd .; M-260) 500 parts by weight Water-soluble resin (Polyvinylpyrrolidone GAF; PVPK-30) 500 parts by weight Activator (Asahi Glass Co., Ltd.) Surflon S-381) 5 parts by weight Water 10000 parts by weight Example 6 Same as Example 1 except that an undercoat layer coating solution having the following composition was applied to a dry film thickness of 0.2 μm using a wire bar. Then, a planographic printing plate material was prepared.

Monomer (polyethylene glycol diacrylate Toa Gosei Chemical Co., Ltd .; M-260) 500 parts by weight Water-soluble resin (polyvinylpyrrolidone GAF; PVPK-30) 500 parts by weight Polymerization initiator (Nippon Kayaku KAYACURE QTX) 20 parts by weight Hydrogen donor (Methyldiethanolamine Nippon Emulsifier Co., Ltd.) 20 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381) 5 parts by weight Water 10000 parts by weight Example 7 A lithographic printing plate material was prepared in the same manner as in Example 1 except that an undercoat layer coating liquid containing the following sensitizing dyes dispersed in oil protect was coated using a wire bar to a dry film thickness of 0.2 μm. .

Coating liquid A Monomer (polyethylene glycol diacrylate Toa Gosei Chemical Co., Ltd .; M-260) 500 parts by weight Water-soluble resin (polyvinylpyrrolidone GAF; PVPK-30) 500 parts by weight Polymerization initiator (Japan KAYACURE QTX manufactured by Kayaku Co., Ltd. 20 parts by weight Hydrogen donor (methyldiethanolamine manufactured by Nippon Emulsifier Co., Ltd.) 20 parts by weight Activator (manufactured by DuPont; Alkanol XC) 60 parts by weight Water 10000 parts by weight Coating solution B sensitization Dye (manufactured by Nippon Senshoku Co., Ltd .; NKX-1766) 70 parts by weight Dioctyl phthalate (manufactured by Daihachi Chemical Co., Ltd .; DOP) 70 parts by weight Methyl ethyl ketone 860 parts by weight Coating liquid A and coating liquid B are in a weight ratio of 5 : 1 so that
Coating solution B was dropped little by little into coating solution A to obtain an undercoat layer coating solution. At this time, the container of the coating liquid A was cooled with ice water to maintain the liquid temperature at 4 to 8 ° C. p.
m. The mixture was stirred with and dispersed by an ultrasonic disperser.

Example 8 An undercoat layer coating solution having the following composition was applied using a wire bar to a dry film thickness of 0.2 μm and heat-treated at 80 ° C. for 2 minutes to form an undercoat layer.

Monomer (Hydroxybutyl vinyl ether IP Japan, HBVE) 500 parts by weight Water-soluble resin (Polyvinylpyrrolidone GAF, PVPK-30) 500 parts Activator (Asahi Glass Co., Ltd.) Surflon S-381) 5 parts by weight Water 10000 parts by weight Next, a photosensitive layer coating solution having the following composition is applied using a wire bar to a dry film thickness of 1.5 μm and heat-treated at 80 ° C. for 2 minutes. Then, a photosensitive layer was formed to obtain a lithographic printing plate material.

Epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 1010) 50 parts by weight Monomer (manufactured by Kyoeisha Oil & Fat Chemical Co., Ltd .; Epolite 100MF) 50 parts by weight Sensitizing dye (manufactured by Nippon Kayaku Co., Ltd .; IR-820B) 3 parts by weight Acid generator (1,3,5-tris [trichloromethyl] -2,4,6-triazine) 3 parts by weight Methyl ethyl ketone 250 parts by weight Methyl propylene glycol (manufactured by Nippon Emulsifier Co., Ltd .; MGF) ) 250 parts by weight Example 9 A photosensitive layer coating solution having the following composition was applied using a wire bar to a dry film thickness of 1.5 μm and heat-treated at 80 ° C. for 2 minutes to form a photosensitive layer. A lithographic printing plate material was prepared in the same manner as in Example 1.

Binder resin (methyl methacrylate / butyl acrylate / acrylic acid / acrylonitrile = 78/8/6/8) 450 parts by weight Monomer (pentaerythritol triacrylate) 600 parts by weight Ketocoumarin dye (manufactured by Japan Photosensitive Dyes KK; NKX) -846) 20 parts by weight Organic peroxide (3,3 ', 4,4'-tetrabis (t-butyldioxycarbonyl) dioxybenzophenone) 72 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381 ) 10 parts by weight Sensitizing agent (diisononyl phthalate) 35 parts by weight Methyl cellosolve 5000 parts by weight Methyl propylene glycol (manufactured by Nippon Emulsifier Co., Ltd .; MGF) 5000 parts by weight Comparative Example 1 A photosensitive layer coating solution having the following composition was applied to a wire. No undercoat layer was formed on the same support as in Example 1 using a bar. And dry film thickness
It was coated so as to have a thickness of 1.7 μm and heat-treated at 80 ° C. for 2 minutes to form a photosensitive layer.

[0060]   Binder resin (methyl methacrylate / butyl acrylate     / Acrylic acid / Acrylonitrile = 78/8/6/8) 450 parts by weight   Monomer (pentaerythritol triacrylate) 600 parts by weight   20 parts by weight of ketocoumarin dye (manufactured by Nippon Senso Dye Co., Ltd .; NKX-846)   Organic peroxide (3,3 ', 4,4'-tetrabis     (T-Butyldioxycarbonyl) dioxybenzophenone) 72 parts by weight   Activator (Asahi Glass Co., Ltd .; Surflon S-381) 10 parts by weight   Methyl cellosolve 5000 parts by weight   Methyl propylene glycol (Nippon Emulsifier Co., Ltd .; MGF)                                                         5000 parts by weight   Next, an overcoat layer having the following composition was formed on the photosensitive layer so as to have a thickness of 2.0 μm. A lithographic printing plate material was applied by applying with a pre-cutter.       

Polyvinyl alcohol (Nippon Gosei Kagaku KK; GL-05) 97 parts by weight Activator (Bayer Co., Ltd .; FT-248) 3 parts by weight Water 1000 parts by weight Comparative Example 2 Photosensitive layer having the following composition Using a wire bar, the coating solution was applied onto a support similar to that in Example 1 without an undercoat layer to give a dry film thickness of 1.
A lithographic printing plate material was produced in the same manner as in Example 1 except that the photosensitive layer was formed by applying the coating solution so as to have a thickness of 7 μm and performing heat treatment at 80 ° C. for 2 minutes.

Binder resin (methyl methacrylate / butyl acrylate / acrylic acid / acrylonitrile = 78/8/6/8) 450 parts by weight Monomer (pentaerythritol triacrylate) 600 parts by weight Ketocoumarin dye (manufactured by Japan Photosensitive Dyes KK; NKX) -846) 20 parts by weight Organic peroxide (3,3 ', 4,4'-tetrabis (t-butyldioxycarbonyl) dioxybenzophenone) 72 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381 ) 10 parts by weight Sensitizing agent (diisononyl phthalate) 35 parts by weight Methyl cellosolve 5000 parts by weight Methyl propylene glycol (manufactured by Nippon Emulsifier Co., Ltd .; MGF) 5000 parts by weight Comparative Example 3 On the same support as in Example 1. The undercoat layer coating solution having the following composition was dried with a wire bar to give a dry film thickness of 0. It was applied so as to have a thickness of 0.2 μm and heat-treated at 80 ° C. for 2 minutes to form an undercoat layer.

Water-soluble resin (polyacrylic acid, manufactured by Nippon Pure Chemical Co., Ltd .; AC-10L) 500 parts by weight Activator (manufactured by Asahi Glass Co., Ltd .; Surflon S-381) 5 parts by weight Water 10000 parts by weight Using a wire bar, apply a photosensitive layer coating solution having the following composition to a dry film thickness of 1.5 μm, and apply at 80 ° C.
And heat-treated for 2 minutes to form a photosensitive layer.

Binder resin (methyl methacrylate / butyl acrylate / acrylic acid / acrylonitrile = 78/8/6/8) 450 parts by weight Monomer (pentaerythritol triacrylate) 600 parts by weight Ketocoumarin dye (manufactured by Japan Photosensitive Dyes Co .; NKX) -846) 20 parts by weight Organic peroxide (3,3 ', 4,4'-tetrabis (t-butyldioxycarbonyl) dioxybenzophenone) 72 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381 ) 10 parts by weight Sensitizing agent (diisononyl phthalate) 35 parts by weight Methyl cellosolve 5000 parts by weight Methyl propylene glycol (manufactured by Nippon Emulsifier Co., Ltd .; MGF) 5000 parts by weight Further, an overcoat layer having the following composition is photosensitive. Apply to the layer with an applicator to make the thickness 2.0 μm. To obtain a planographic printing plate material.

Polyvinyl alcohol (Nippon Gosei Kagaku Co., Ltd .; GL-05) 97 parts by weight Activator (Bayer Co., Ltd .; FT-248) 3 parts by weight Water 1000 parts by weight Comparative Example 4 Undercoat layer of the following composition A lithographic printing plate material was prepared in the same manner as in Comparative Example 3 except that the coating liquid was applied using a wire bar so that the dry film thickness was 0.2 μm.

Monomer (lauryl methacrylate) 500 parts by weight Activator (Asahi Glass Co., Ltd .; Surflon S-381) 5 parts by weight Methyl ethyl ketone 10000 parts by weight <Image forming method> After exposure, 25 in a developing solution having the following composition
An image was obtained by immersing at 45 ° C. for 45 seconds to elute the photosensitive layer in the unexposed area, washing with water and drying.

Benzyl alcohol 360 parts by weight Diethanolamine 210 parts by weight Sodium t-butylnaphthalenesulfonate (manufactured by Kao Corporation; Perex NBL) 180 parts by weight Potassium sulfite 90 parts by weight Water 3000 parts by weight << Evaluation >> Each printing plate obtained The materials were evaluated as follows.

(Sensitivity) Interference filter (Toshiba Glass Co., Ltd.)
Manufactured by Y-47), sharp cut filter (manufactured by Toshiba Glass Co., Ltd .; KL-49), and heat ray absorption filter (HO).
HA-30) manufactured by YA Co., Ltd. is combined and light close to the light of an argon ion laser (oscillation wavelength 488 nm) is extracted from the light source, and the illuminance of this light is set to Advanceds.
Made by t company; Optical Power Meter T
Measurement is performed in the 488 nm mode of Q8210, and a calibration curve of exposure energy and exposure time is prepared.

Each lithographic printing plate material was manufactured by Mika Denshi KK;
The sensitivity is calculated from the number of solid steps after development when a continuous exposure wedge of the Ugra plate control wedge PCW82 is brought into close contact and a constant exposure energy is applied based on the calibration curve.

(Resolution) For each lithographic printing plate material, Mika Denshi Co., Ltd .; Ugra plate control wedge PC
W82 halftone wedge and Smold patch (150 lines / inch) and Eastman Kodak Co .; Kodak Step Tablet No. 2 are brought into close contact with each other, exposed and developed, and Kodak Step Tablet No. The number of solid steps in 2 parts is 4
Samples are made in steps and the reproducibility of halftone wedges and smold patches of these samples is magnified and observed with a magnifying glass.

(Adhesiveness) Each lithographic printing plate material was coated with a mask and a Kodak Step Tablet No. 2 are brought into close contact with each other, exposed and developed
Kodak Step Tablet No. Samples were prepared so that the number of solid steps in 2 parts was 4 steps, and the adhesiveness of the net pattern parts of these samples was manufactured by Nichiban Co., Ltd .; a peeling test using cellophane tape was performed and magnified with a magnifying glass. To do. Furthermore, acid (manufactured by Dainichiseika Co., Ltd .; Uitr
a Plate Cleaner) and an alkali (developing solution), and a peeling test using cellophane tape was performed every 30 minutes, and the difference in adhesiveness was evaluated by observing with a magnifying glass.

Evaluation Criteria ◯: No change Δ: Some missing dots are recognized as magnified with a magnifying glass ×: Some missing dots are visually recognized.

(Printing durability) Ugra was added to each lithographic printing plate material.
An image produced by the plate control wedge PCW82 is produced with an exposure amount such that the continuous tone wedge has four steps, and a printing machine (manufactured by Heidelberg; Heidel GTO)
Then, coated paper (manufactured by Mitsubishi Paper Mills Ltd .; Tokubishi Art), printing ink (manufactured by Toyo Ink Mfg. Co., Ltd .; High Plus M Red) and dampening water (manufactured by Konica Corp .; SEU-3 2.5) % Aqueous solution), and printing is continued until the solid ink on the solid part of the printed matter is defective or ink is attached to the non-image part, and the number of printed sheets is counted to evaluate the printing durability.

(Ink ink receptivity and scumming) Kodak Step Tablet No. 2 are brought into close contact with each other, exposed and developed, and Kodak Step Tablet No. Two
A sample is prepared so that the number of solid steps in the part is four. Gum liquid (manufactured by Konica Corp .; SG)
W-3 PS plate wash gum solution) diluted 2-fold with water is evenly applied with a sponge and air-dried. After that, developing ink (Fuji Film Co., Ltd .; PI
-2 PS plate developing ink) is soaked in a PS sponge, and the ink sample of the above sample is visually evaluated for ink sticking (inking property) and stains on unexposed areas.

Evaluation Criteria (Thickness) ◎: Superior to the printing plate material containing the current diazo compound ○: Equivalent to the printing plate material containing the current diazo compound Δ: Printing plate material containing the current diazo compound Inferior to x: No ink deposit (background stain) ◯: No occurrence Δ: Slightly stain x: Significant stain The above results are shown in Table 1.

[0076]

[Table 1]

[0077]

INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive material for a lithographic printing plate which can improve the adhesiveness between a photopolymerizable layer and a hydrophilic support, has a high resolution suitable for laser exposure and is excellent in printing performance can be obtained. .

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-2-304441 (JP, A) JP-A-2-285349 (JP, A) JP-B 1-332971 (JP, B2) (58) Field (Int.Cl. ⁷ , DB name) B03F ^7/ 00-7/42

Claims (4)

(57) [Claims] 1. A compound having a hydrophilic ethylenically unsaturated bond selected from the compounds described in the following A on the hydrophilic surface of a support having a hydrophilic surface, based on the solid content of the undercoat layer.
Contains 35% by weight or more and has a thickness of 0.01 to 0.5 μm
It contains a subbing layer is a polymeric binder, a compound having an ethylenically unsaturated bond and a photopolymerization initiator, the ethyl
A compound having a lenically unsaturated bond is contained in the entire photosensitive layer composition.
In the range of 5 to 80% by weight, the composition is applied and the thickness is
A photosensitive material for a lithographic printing plate , comprising a photopolymerizable photosensitive layer having a size of 0.1 to 10 μm in this order. A: (meth) acrylonitrile, (meth) acrylamido
De, (meth) acrylic acid, (meth) acrylic acid soda,
Methyl (meth) acrylate, ethyl (meth) acryl
, N-propyl (meth) acrylate, isopropyl
(Meth) acrylate, n-butyl (meth) acrylate
Acetate, isobutyl (meth) acrylate, t-butyl
(Meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acry
Rate, 2-hydroxybutyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, 2-sia
Noethyl (meth) acrylate, β-ethoxyethyl ether
Rosolve (meth) acrylate, (meth) acrylic
Dehydr, N, N'-methylenebis (meth) acrylic acid
2-hexyloxyethyl-N-methacrylodolphin
Lubamate, allyl (meth) acrylate, acrylic acid-
2-chloroethyl, 2,2-bis [4- (methacryloxy)
Di- (polyethoxy) phenyl] propane, diacrylate
Ethylene glycol ethoxylate, polyethylene glycol
Cold (meth) acrylate, 3- (meth) acrylo
Ilimino-1-phenyl-5-pyrazolone, ω-cal
Boxy-polycaprolactone (n = 2) mono acrylate
G, monohydroxyethyl phthalate (meth) acrylate
G, monohydroxyethyl succinate (meth) acrylate
G, acrylic acid dimer, 2-hydroxy-3-pheno
Xypropyl acrylate, isocyanuryl ethylene oxy
Side (EO) modified diacrylate, pentaerythritol
Triacrylate, mono (2- (meth) acryloyl
(Loxyethyl) acid phosphate, glycerol
Mono (meth) acrylate, glycerin (meth) acry
Rate, hydroxymethyl vinyl ether, hydroxy
Ethyl vinyl ether, hydroxypropyl vinyl Agent
Tell, hydroxybutyl vinyl ether 2. The photosensitive material for a lithographic printing plate according to claim 1, wherein the compound having a hydrophilic ethylenically unsaturated bond has a solubility in water at 25 ° C. of 20 or more. 3. The photosensitive material for a lithographic printing plate according to claim 1, wherein the undercoat layer contains a water-soluble or water-dispersible polymerization initiator. 4. The photosensitive material for a lithographic printing plate according to claim 1, 2 or 3, wherein the undercoat layer contains a water-soluble resin.