JPH0594020A - Peeling development type plate making material and plate making method - Google Patents

Abstract

PURPOSE:To obtain the printing plate having a high resolution and excellent printing resistance by successively laminating a photosensitive resin layer, a hydrophilic resin layer, a photosensitive silver salt layer, and a protective layer on a base. CONSTITUTION:This plate making material is constituted in the form of successively laminating the photosensitive resin layer 102 which has a polymerizable compd. and allows peeling development and the hydrophilic layer 103 on the base 101. Further, the hydrophilic layer 103 may have a masking ability to the photosensitive resin layer 102 with a single layer or may have the masking ability with double-layer constitution. The constitution obtd. by successively laminating the hydrophilic resin layer 104, the photosensitive silver salt layer 105 and the protective layer 106 on the photosensitive resin layer 102 is generally used for the double-layer constitution. The elements constituting the photosensitive resin layer 102 consist at least of the polymerizable compd., a layer formable high-polymer material and a photopolymn. initiator. A halation preventive dye corresponding to the photosensitive wavelength of the hydrophilic layer 103 may be incorporated into the photosensitive resin layer 102. The hydrophilic resin layer 104 is formed to 1 to 50mum layer thickness and the photosensitive silver salt layer 105 is formed to 0.5 to 30mum layer thickness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a peeling development type plate-making material and a plate-making method. More specifically, it is excellent in resolution and printing durability by a dry process suitable for the field of light printing, especially for office printing. A plate-making material and a plate-making method for a printing plate having

[0002]

2. Description of the Related Art Normally, lithographic printing utilizes the immiscibility of water and oil, and a lithographic printing plate is generally provided with a non-image area showing hydrophilicity and an image area showing lipophilicity. ing. When printing with this printing plate, dampening water is applied to the plate and held in the non-image area, and when oil-based ink is then supplied, ink does not adhere to the non-image area and Ink adheres to the ink, and the image on the lithographic printing plate is transferred to an image receptor such as paper directly or through a blanket cylinder.

As a lithographic printing plate used for such lithographic printing, there is a PS plate which is preferably used in large quantities. This is a metal plate (aluminum, zinc, etc.) of the support is grained on the surface, or is further anodized to impart hydrophilicity to the surface, and is coated with a lipophilic resin having photosensitivity. After imagewise exposure, the resin remaining after development forms a lipophilic image area, and the portion where the resin is removed by development becomes a hydrophilic non-image area.

Further, what is preferably used for office printing is that by electrophotography on a hydrophilic resin layer containing zinc oxide (ZnO) on a support provided with water resistance. A printing plate that forms a toner image exhibiting lipophilicity, using a silver salt photographic method, after imagewise exposure, developing, to impart hydrophilicity and lipophilicity to the plate, and other hydrophilic inks such as oil-based ink Examples include printing plates which form an image on a permeable support.

Further, stencil printing is known in which a heat-fusible layer of wax or the like is provided on a porous thin paper, and ink-permeable holes are formed by a thermal head or the like for printing.

[0006]

However, the above
A printing plate using a PS plate, an electrophotographic system, or a silver salt photographic system is generally subjected to a wet development process in order to maintain high resolution. Therefore, there is a problem that maintenance such as storage management of the developing solution, disposal of the waste solution, and the like are complicated, and environmental pollution is caused by the use of the solvent.

Further, a printing plate using a dry electrophotographic method which does not use a solvent in the developing step or a printing plate which is perforated by a thermal head has poor resolution and the image quality of the obtained printed matter is satisfactory. It was not something that could be done.

As a printing plate for solving these problems,
As an example, a dry-developable printing plate is known in which a photosensitive resin layer and a transparent support are laminated on a hydrophilic support, which is so-called peeling development treatment, and is disclosed in JP-B-38-9663.
No. 43-22901, JP-A-47-7728,
JP-B-48-43126, JP-A-55-50246
No. 57-58141, No. 57-62046, No. 64-10055, No. 64-10056, and No. 1-45899.

According to the description of the plate making method of the printing plates in these publications, a mask for the photosensitive wavelength of the photosensitive resin layer is prepared in advance, and the entire surface is exposed through the transparent support to expose the photosensitive portion of the photosensitive resin and the unexposed portion. Image of the lipophilic photosensitive resin on the hydrophilic support by peeling development in accordance with the mask image by utilizing the difference in adhesiveness between the hydrophilic support and the transparent support of the part Parts are formed. Alternatively, the image area of the photosensitive resin peeled and developed between the supports is transferred onto another hydrophilic support prepared. These plate making methods are rational and excellent methods, but in the former case, the hydrophilic support to which the photosensitive resin that forms the image area is adhered is sensitive to the mask during the entire exposure. It is located on the opposite side of the resin layer, that is, at a position far from the mask.
Therefore, if the total exposure amount is not properly controlled, the breakage of the image area due to the photosensitive resin deteriorates. That is, the image area is affected by the shake from the proper exposure area,
The image quality of the printed matter deteriorates due to being fat or thin. Further, it has been difficult to realize high resolution because it causes fatal defects such as so-called knurling, chipping, and tear separation that often occur during peeling development. Further, in the latter case, the image quality is deteriorated at the time of transfer, and the apparatus becomes complicated and large in size to be installed as an office printing machine in an office, and further expensive, which is not a preferable form.

The step of forming a mask for the photosensitive wavelength of the photosensitive resin layer in advance is generally a wet silver salt photographic method, which is also not preferable for the above reason.

Further, as described in JP-A-55-50246, a so-called heat-development type dry silver salt mask layer is used.
In the plate-making method of laminating through a transparent support to be integrated, imagewise exposure to the dry silver salt layer, heat development, and peeling development,
There is a problem that the peeling developability is deteriorated by the heat applied to the photosensitive resin layer during the heat development.

The object of the present invention is to solve the above problems,
It is an object of the present invention to provide a peeling development type plate-making material for lithographic printing and a plate-making method which have a high resolution and are preferably used in the field of office printing by a simple dry process.

Another object of the present invention is to enable plate making without image quality deterioration at the time of peeling development which is carried out after the whole surface exposure through a mask to a peelable and developable photosensitive resin layer, and the mask is made of a photosensitive resin. An object of the present invention is to provide a plate-making material and a plate-making method that do not deteriorate the resolution of peeling development even when a mask is heat-developed in a layer structure integrated with layers.

[0014]

The present invention has been completed as a result of intensive studies to solve the above problems.

That is, the present invention is a plate-making material comprising a support, a photosensitive resin layer containing a polymerizable compound and capable of peeling development, and a hydrophilic layer, which are laminated at least in sequence. It is a peeling development type plate-making material having a masking function for a photosensitive resin layer.

The present invention also provides a hydrophilic resin layer having a hydrophilic layer formed on a photosensitive resin layer and having a layer thickness of 1 μm to 50 μm, and at least silver halide and an organic silver salt formed on the hydrophilic resin layer. And a reducing agent-containing photosensitive silver salt layer, and a protective layer formed on the photosensitive silver salt layer. The photosensitive silver salt layer is exposed and developed to form a mask for the photosensitive resin layer. It is a peeling development type plate making material.

Further, it is a peeling development type plate-making material in which the photosensitive silver salt layer is a hydrophilic layer.

The hydrophilic resin layer is joined to the photosensitive silver salt layer via an adhesive layer having a layer thickness of 0.5 μm to 20 μm.

Further, in the plate-making material of the present invention, when the maximum photosensitive wavelength of the photosensitive resin layer is λ ₁ and the maximum photosensitive wavelength of the hydrophilic layer is λ ₂ , the following formula (I) (λ ₂ −λ ₁ ) ≧ 150 nm (I) is established.

The present invention also provides a peeling development type plate-making material containing an antihalation dye for the photosensitive wavelength of the photosensitive silver salt layer in at least one of the hydrophilic resin layer and / or the adhesive layer and / or the photosensitive resin layer. Is.

Further, in the present invention, a step of (a) performing imagewise exposure and / or imagewise heat application from the hydrophilic layer side to the above-mentioned peeling development type plate-making material according to the photosensitive wavelength of the hydrophilic layer. , (B) a step of subjecting the hydrophilic layer to a development treatment, (c) a step of exposing the entire surface of the hydrophilic layer according to the photosensitive wavelength of the hydrophilic resin layer, and (d) a hydrophilic layer A step of peeling and removing the support together with the unpolymerized part of the photosensitive resin layer to leave the polymerized part of the photosensitive resin layer on the hydrophilic layer, and (e) for the polymerized part of the photosensitive resin layer, if necessary. Then, a plate making method in which the steps of post-exposure and / or heating and / or pressurization are sequentially performed.

Alternatively, the hydrophilic layer of the present invention has a contact angle with water of 50 ° or less, preferably 30 ° or less, and more preferably 20 ° or less.

The present invention will be described in more detail below with reference to the drawings.

FIG. 1 is a sectional view schematically showing an example of the layer structure of the peeling development type plate-making material of the present invention.

As shown in FIG. 1, the release-development type plate-making material of the present invention comprises a support 101, a release-developable photosensitive resin layer 102 having a polymerizable compound, and a hydrophilic layer 103, which are laminated in this order. To be done. Further, the hydrophilic layer may be a single layer having a masking ability with respect to the photosensitive resin layer, or may have a multi-layered structure and have a masking ability if necessary. As an example of the multilayer structure, as shown in FIG. 1, on the photosensitive resin layer 102,
Hydrophilic resin layer 104, photosensitive silver salt layer 105, protective layer 10
A structure in which 6 is laminated in order is generally used.

The term "masking ability" as used herein means that light transmission can be controlled, and in the present invention, when the entire surface exposure in the wavelength region corresponding to the photosensitive wavelength of the photosensitive resin layer is performed, Since the image previously formed on the hydrophilic layer blocks light transmission and the non-image forming portion has light transmission, the photosensitive resin layer causes a difference in physical properties between the exposed portion and the unexposed portion, and It means the light transmission controllability that enables peeling development between the hydrophilic layer.

Next, various materials constituting the peeling development type plate-making material of the present invention will be described.

As the support of the present invention, in the relationship between the hydrophilic layer and the photosensitive resin layer, after the entire surface of the photosensitive resin layer is exposed from the hydrophilic layer side having a masking function, the support and the hydrophilic layer are formed. It is peeled and the polymerized portion of the photosensitive resin layer is peeled together with the hydrophilic layer and the unpolymerized portion is peeled together with the support so that good development can be performed. For example, a film made of a polyethylene terephthalate film is preferable in terms of strength, moisture resistance, and availability at low cost. However, it is not limited to this as long as the peeling development is possible as described above. The thickness of this support is generally 3 μm to 100 μm, preferably 8 μm to 50 μm, which is desirable in that it is relatively easily available and has stable properties such as strength, but is not within the above range. However, it can be used. Further, it can be favorably used even if the support is dyed to prevent halation corresponding to the photosensitive wavelength of the photosensitive resin layer. Further, an antihalation layer corresponding to the photosensitive wavelength of the photosensitive resin layer may be separately provided on the support and the photosensitive resin layer and / or on the surface side of the support which is not in contact with the photosensitive resin layer.
Examples of suitable antihalation dyes include cyanine dyes, merocyanine dyes, rhodamine dyes, naphthoquinone dyes and triarylmethane dyes. Of these, cyanine dyes are common in that various absorption wavelengths can be selected. As the cyanine dye, thiocyanine, oxacyanine, quinocyanine, indocyanine, etc. are selected.

As the photosensitive resin layer 102 used in the present invention, the materials described in the above publications can be used. That is, as a constituent of the photosensitive resin layer, at least a polymerizable compound, a layer-forming polymer substance, a photopolymerization initiator, and if necessary, a photoinitiator aid, a thermal polymerization inhibitor, a colorant You may mix additives, such as a plasticizer and a filler. Further, in the present invention, the photosensitive resin layer,
An antihalation dye corresponding to the photosensitive wavelength of the hydrophilic layer may be included.

As the polymerizable compound, a compound having at least one reactive vinyl group in one molecule can be used, and examples thereof include a reactive vinyl group-containing monomer, a reactive vinyl group-containing oligomer and a reactive vinyl group. One or more selected from the group consisting of group-containing polymers can be used.
As the reactive vinyl group of these compounds, a styrene-based vinyl group, a (meth) acrylic acid-based vinyl group, an allyl-based vinyl group, or a vinyl ether or other ester-based vinyl group-containing substitution having polymerization reactivity. Group or an unsubstituted vinyl group. Here, (meth) acrylic acid means methacrylic acid and acrylic acid.

As the polymerizable compound satisfying the above conditions, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyl group-containing polymerizable compound such as hydroxypropyl (meth) acrylate, butanediol monoacrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate: 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl Alkoxy group-containing polymerizable compounds such as (meth) acrylate; amino nitrogen-containing polymerizable compounds such as t-butylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate; polyethylene glycol mono (meth ) Acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate,
A 1: 1, 1: 2 adduct of diol such as neopentyl glycol di (meth) acrylate and (meth) acrylic acid;
Ethylene glycol diglycidyl ether di (meth)
Acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate, polypropylene glycol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane triglycidyl ether di (meth) acrylate and other diol diglycidyl ether 1: 2 adducts with acrylic acid; pentaerythritol mono (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol Distearate (meth) acrylate,
Pentaerythritol derivatives such as dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate; (meth) acrylic acid,
(Meth) acrylic acid metal salt, acrylic acid dimer; (meth) acrylamide, dimethylaminopropyl (meth)
Acrylamide, N-methylol (meth) acrylamide, t-butyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-butoxy (meth) acrylamide, N, N- Dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, ethylene di (meth) acrylamide, propylene di (meth) acrylamide, 1,4-phenylene di (meth) acrylamide, ethylene tetra (meth) acrylamide, propylene Tetra (meth) acrylamide, methylenebis (meth) acrylamide, acrylamide / glyoxal adduct, acrylamide / methylolethyleneurea condensate, 1,3,5-triacryloylhexahydros-tri Acrylamide derivatives such as gin, N, N-diallyl acrylamide, acrylamide / methylol melamine condensate, acrylamide / methylol triazene condensate, acrylamide / methylol hydantoin condensate, acrylamide / methylol urea, N, N-diallyl acrylamide; 2- ( Sulfonyl group-containing polymerizable compounds such as (meth) acrylamido-2-methylpropanesulfonic acid; ammonium base-containing polymerizable compounds such as (meth) acrylamidopropyltrimethylammonium chloride and (meth) acryloyloxyethyltrimethylammonium chloride; mono ( 2-
Phosphoric acid group-containing polymerizable compounds such as (meth) acryloyloxyethyl) acid phosphate; N- (meth) acryloylmorpholine, tetrahydroofurfuryl (meth) acrylate, vinyl acetate, acrylonitrile, N-vinylcaprolactam, N-vinyl. Oligomer or polymer such as pyrrolidone, and further, for example, styrene, methylstyrene, chlorostyrene, bromostyrene, methoxystyrene, dimethylaminostyrene, cyanostyrene, nitrostyrene, hydroxystyrene, aminostyrene, carboxystyrene, methyl (meth) acrylate. , Ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, vinylpyrrolidine, propyl vinyl ether, Monovalent monomers such as vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether, p-chlorophenyl vinyl ether; divinylbenzene, distyryl oxalate, distyryl malonate, distyryl succinate. , Distyryl glutanate, distyryl adipate, distyryl maleate, distyryl fumarate, distyryl β, β-dimethylglutanate, distyryl 2-bromoglutanate, α,
α'-Dichloroglutanate distyryl, terephthalate distyryl, oxalic acid di (ethyl (meth) acrylate), oxalic acid di (methylethyl (meth) acrylate), malonic acid di (ethyl (meth) acrylate), malonic acid diester (Methylethyl (meth) acrylate), succinic acid di (ethyl (meth) acrylate), glutaric acid di (ethyl (meth) acrylate), adipic acid di (ethyl (meth) acrylate), maleic acid di (diethyl (meth)) Acrylate), di (fumarate) ethyl (meth)
Acrylate), β, β-dimethylglutarate di (ethyl (meth) acrylate), 1,4-phenylenebis (oxyethyl (meth) acrylate), 1,4-phenylenebis (oxymethylethyl (meth) acrylate), 1 , 4-bis ((meth) acryloyloxyethoxy) cyclohexane, 1,4-bis ((meth) acryloyloxymethylethoxy) cyclohexane, 1,4
-Bis ((meth) acryloyloxyethoxycarbamoyl) benzene, 1,4-bis ((meth) acryloyloxymethylethoxycarbamoyl) benzene, 1,4
-Divalent monomers such as bis ((meth) acryloyloxyethoxycarbamoyl) cyclohexane and bis ((meth) acryloyloxyethoxycarbamoylsochlorhexyl) methane; cyanuric acid tri (meth) acrylate, 1,1,1- Trimethylolpropane tri (meta)
Acrylate, tri (ethyl (meth) acrylate cyanurate), 1,1,1-trimethylolpropane tri (ethyl acrylate), tri (ethyl vinyl ether) cyanurate, 1,1,1-trimethylolpropane and 3 times mole Trivalent monomers such as a condensate of a reaction product of toluene diisocyanate and hydroxyethyl acrylate, a condensate of a reaction product of 1,1,1-trimethylolpropane and 3-fold molar hexane diisocyanate, and a hydroxystyrene. A tetravalent monomer such as pentaerythritol tetraacrylate; a hexavalent monomer such as dipentaerythritol hexaacrylate; and a polymerizable compound having a reactive vinyl group at the end of an oligomer or polymer, Or reactive vinyls on the side chains of oligomers or polymers And the like can be mentioned polymerizable compound wearing.

It is also possible to use two or more kinds of these polymerizable compounds in combination.

Examples of the layer-forming polymer substance include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polymethylmethacrylate, polyacrylic acid, polymethacrylic acid, polyacrylic acid alkyl ester (wherein the alkyl group is a methyl group). , Ethyl group, butyl group, etc.), acrylic acid alkyl ester (alkyl group is the same as above) and at least one copolymer of acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, etc., polyvinyl chloride, and vinyl chloride. Acrylonitrile copolymer, polyvinylidene chloride, vinylidene chloride and acrylonitrile copolymer, polyvinyl acetate, vinyl acetate and vinyl chloride copolymer, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylonie Ril, a copolymer of acrylonitrile and styrene, a copolymer of acrylonitrile and butadiene and styrene, polyvinyl alkyl ether (as the alkyl group, a methyl group, an ethyl group, an isopropyl group, a butyl group, etc.), polyethylene, polypropylene, polybutyne, Polystyrene, poly-α-methylstyrene,
Polyamide (6-nylon, 6,6-nylon, 6,1
0-nylon, etc.), poly-1,3-butadiene, polyisoprene, polyurethane, polyester (polyethylene terephthalate, polyethylene isophthalate linear saturated polyester, etc.), chlorinated rubber, polychloroprene, chlorinated rubber, polyvinyl butyral, polyvinyl formal,
There are homopolymers or copolymers of styrene-butadiene rubber, poly (chlorosulfonated ethylene) and the like.

The amount of the layer-forming polymer substance is the polymerizable compound 1
20 parts by weight to 1000 parts by weight, more preferably 25 parts by weight to 500 parts by weight, relative to 00 parts by weight.

Of the above substances, preferred ones are:
Chlorinated polyolefin represented by chlorinated polyethylene and chlorinated polypropylene, polymethylmethacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer (vinyl chloride molar content 20 to 80%), vinylidene chloride-acrylonitrile copolymer (Acrylonitrile molar content 10 to 30%), vinyl chloride-acrylonitrile copolymer (acrylonitrile molar content 10 to 30)
%), Polystyrene, polyvinyl butyral, polyvinyl acetate, polyvinyl formal, vinyl chloride-vinyl acetate copolymer, polychloroprene, polyisoprene, chlorinated rubber and poly (chlorosulfonated ethylene), and the particularly preferred one is chlorinated. Chlorinated polyolefins and polyvinyl butyral represented by polyethylene and chlorinated polypropylene.
These substances may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include carbonyl compounds, sulfur compounds, halogen compounds and redox photopolymerization initiators.

Specifically, as the carbonyl compound,
For example, diketones such as benzyl, 4,4′-dimethoxybenzyl, diacetyl, camphorquinone; for example, 4,4′-diethylaminobenzophenone, 4,4′-
Benzophenones such as dimethoxybenzophenone; eg acetophenones, acetophenones such as 4-methoxyacetophenone; eg benzoin alkyl ethers; eg 2-cyclolothioxanthone, 2,5-diethylthioxanthone, thioxanthone-3-carboxylic acid-β-methoxyethyl Thioxanthones such as esters; chalcones and styryl ketones having a dialkylamino group; coumarins such as 3,3′-carbonylbis (7-methoxycoumarin) and 3,3′-carbonylbis (7-diethylaminocoumarin) Is mentioned.

Examples of the sulfur compound include dibenzothiazolyl sulfide and disulfides such as decylphenyl sulfide.

Examples of the halogen compound include carbon tetrabromide, quinolinesulfonyl chloride and S-triazines having a trihalomethyl group.

The redox photopolymerization initiator is 3
With a high-valent iron ion compound (for example, ferric ammonium citrate) and a peroxide, or with a photoreducing substance such as riboflavin or methylene blue and a reducing agent such as triethanolamine or ascorbic acid Things are included.

In the photopolymerization initiator described above,
It is also possible to obtain a more efficient photopolymerization reaction by combining two or more kinds.

Examples of such a combination of photopolymerization initiators include chalcone and styrylstyrylethanes having a dialkylamino group, coumarins and S-triazines having a trihalomethyl group, and camphorquinone.

The amount of the polymerization initiator is 0.1 to 30 parts by weight, and more preferably 0.3 to 100 parts by weight of the polymerizable compound.
It is preferably from 25 to 25 parts by weight.

Examples of the antihalation dye include those mentioned above, and of these, the cation type is more preferable.

As the hydrophilic layer of the present invention, one having a masking ability with respect to the above-mentioned photosensitive resin layer is selected. The hydrophilic layer can be composed of the following hydrophilic resin layer, photosensitive silver salt layer, and protective layer.

As the hydrophilic resin layer 104 used in the present invention, one capable of the above-mentioned peeling development and capable of forming a non-image area showing hydrophilicity in the printing plate is selected.

For example, plant type polymers such as guar gum, locust beam gum, gum arabic, taragant, carrageenan, pectin, mannan, and starch; microbial type polymers such as xanthan gum, dextrin, succinglucan, curdlan; gelatin, caseinarbumin, Animal-based polymers such as collagen; cellulosic polymers such as methylcellulose, hydroxycellulose, ethylcellulose, carboxymethylcellulose; starch-based polymers such as soluble starch, carboxymethylstarch, methylstarch; propylene glycol alginate,
Alginic acid-based polymers such as alginate, semi-synthetic polymers such as other polysaccharide-based derivatives; polyvinyl alcohol,
Polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate,
Vinyl-based polymers such as polyacrylamide, poly (meth) acrylic acid and polyacrylonitrile; other synthetic polymers such as polyethylene glycol, ethylene oxide and propylene oxide block copolymers; silicon dioxide, titanium dioxide, silica , Clay, cross-linking agent, waterproofing agent, surfactant, etc. added; JP-B-2-153
83, JP-A Nos. 2-80472 and 2-105873.
Nos. 1-238935, 2-110119 and 2-107678, and the like, and the like,
Although the product itself is hydrophobic, a resin containing a functional group which is hydrolyzed by an etchant or a fountain solution or which is hydrolyzed to form a hydrophilic group is also preferable. JP-A-1-30685
No. 6, No. 1-306855, No. 1-267093,
Examples thereof include the resins described in No. 1-269593. These may be used alone or in combination of two or more as required. Further, most of the hydrophilic resins are water-soluble, and in order to have water resistance, examples of the cross-linking agent include, for example, melamine formalin resin, urea formalin resin, polyamide polyaminoepichlorohydrin resin, ketone formalin resin, and methylol. Polyamide resin, glyoxal, polyvalent metal salt and the like can be used.

If desired, the above antihalation dye may be incorporated. In this case, an anionic type that is easily dissolved in water is preferable.

The layer thickness of the hydrophilic resin layer is 1 μm to 50 μm.
m, more preferably 2 μm to 30 μm. When the hydrophilic resin layer is thin, the resolution at the time of peeling development of the photosensitive resin is improved, but the strength when used as a printing plate is insufficient and sufficient printing durability cannot be obtained. Just printing makes it unsuitable. On the other hand, when it is too thick, it causes undesired development such as creases and chips, image thickening and thinning during peeling development of the photosensitive resin layer, and resolution and image reproducibility deteriorate, which is not preferable. Further, when the photosensitive silver salt layer is thermally developed, heating at 100 ° C. or higher is usually performed for 3 seconds to 2 seconds.
Since it is carried out for 0 seconds, it becomes a factor of impairing the developability of the peeling development which is carried out subsequently. Therefore, by setting the thickness of the hydrophilic resin layer to 1 μm or more, and more preferably 2 μm or more as described above, deterioration of the peeling developability due to heating can be suppressed.

The photosensitive silver salt layer 105 used in the present invention
Contains at least silver halide, an organic silver salt, and a reducing agent. Generally, this is a heat developable dry silver salt composition.

The photosensitive silver halide may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, and has a multiple structure in which the halogen composition in the grain is uniform or different. May be taken. Further, two or more kinds of silver halides having different halogen compositions, grain sizes, grain size distributions and the like may be used in combination. Further, these may be spectrally sensitized or chemically sensitized with a dye or the like.

The organic silver salt is a silver salt with an aliphatic carboxylic acid, an aromatic carboxylic acid, a thiocarbonyl group compound having a mercapto group or α-hydrogen, an imino group-containing compound and the like.

As the aliphatic carboxylic acid, acetic acid, butyric acid,
There are succinic acid, sebacic acid, adipic acid, oleic acid, linoleic acid, linolenic acid, tartaric acid, palmitic acid, stearic acid, behenic acid, camphoric acid, etc. Therefore, those having an appropriate carbon number are preferable.

Examples of aromatic carboxylic acids include benzoic acid derivatives, quinolinic acid derivatives, naphthalenecarboxylic acid derivatives,
Salicylic acid derivative, gallic acid, tannic acid, phthalic acid,
Examples include phenylacetic acid derivatives and pyromellitic acid.

Examples of the thiocarbonyl group compound having a mercapto group or α-hydrogen include 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, 2 -Mercaptobenzothiazole, S-alkyl thioglycolic acid (alkyl group having 12 to 22 carbon atoms),
Dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearoamide, 5-carboxy-1-methyl-2
-Phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-
1,2,4-triazole, U.S. Pat. No. 4,123,
The mercapto compound described in No. 274 is mentioned.

Examples of the compound containing an imino group include benzotriazoles or their derivatives described in JP-B-44-30270 or 45-18416, such as benzotriazole, methylbenzotriazole and other alkyl-substituted benzotriazoles, and 5-chlorobenzo. Triazole, etc., halogen-substituted benzotriazoles, butylcarbimidobenzotriazole, etc., carboimide benzotriazoles, nitrobenzotriazoles described in JP-A-58-18639, sulfobenzotriazoles, carboxybenzos described in JP-A-58-115638. Triazole or a salt thereof, hydroxybenzotriazole, etc., described in U.S. Pat. No. 4,220,709;
Typical examples are 2,4-triazole, 1H-tetrazole, carbazole, saccharin, imidazole and their derivatives.

As the reducing agent, a compound that reduces an organic silver salt to produce silver and forms a blackened image by a silver image, and / or an image of an oxidant which is changed by the reaction of the reducing agent itself with the organic silver salt. A compound that forms a compound is used, and these reducing agents can be appropriately selected and used according to the type of organic silver salt used. As reducing agents that can be used, monophenols, bisphenols, trisphenols,
Tetrakisphenols, mononaphthols, bisnaphthols, dihydroxynaphthalenes, trihydroxynaphthalenes, dihydroxybenzenes, trihydroxybenzenes, tetrahydroxybenzenes, hydroxyalkyl monoethers, ascorbic acids, 3-pyrazolidones, pyrazoline Examples thereof include pyrazolones, phenylenediamines, hydroxyamines, reductones, hydrooxamic acids, hydrazides, amidoximes, and N-hydroxyureas. No. 51-22431, U.S. Patent Nos. 3,615,533 and 3,679,426.
No. 3, No. 3,672,904, No. 3,751,25
No. 2, No. 3,751,255, No. 3,782,9
No. 49, No. 3,801, 321, No. 3,794.
No. 455, No. 3,893,863, No. 3,88
7,376, Belgian Patent 786,086, US Patents 3,770,448, 3,819,38.
No. 2, No. 3,773,512, No. 3,928,6
No. 86, No. 3,839, 048, No. 3, 887,
No. 378, Japanese Patent Publication No. 51-35851, Japanese Patent Laid-Open No. 50-3
6143, U.S. Pat. Nos. 3,827,889, 3,756,829, JP-A-50-36110, JP-A-50-116023, and JP-A-50-147711.
JP-A-51-23721, JP-A-50-9971
9, JP-A-51-32324, JP-A-51-519.
23, JP-A-50-140113, and JP-A-52-8.
No. 4727 is described in each specification. Here, in order to increase the contrast of the light absorption amount (transmission amount) between the exposed portion and the unexposed portion, an oxidant having a large molar absorption coefficient is desirable, and as a reducing agent that forms such oxidant, Aromatic hydroxy compounds are preferred. Hereinafter, the aromatic hydroxy compounds will be described in detail.

The compounds represented by the following general formulas (1) and (2) inhibit the polymerization because the oxidant formed by the redox reaction with the organic silver salt absorbs light in the absorption wavelength region of the photopolymerization initiator. It is an aromatic hydroxy compound that exhibits the ability to

[0059]

[Chemical 1]

[0060]

[Chemical 2] (However, in the general formulas (1) and (2), r ¹ , r ² and r ³
Each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, r and r ⁴ are each independently a hydrogen atom, A halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, an alkoxy group, m is an integer of 1 to 3, Y is a monovalent to trivalent linking group As a substituted or unsubstituted aralkyl group, a substituted amino group,
An alkylidene group, a substituted or unsubstituted aralkylidene group and a methine group are shown, and Z is an alkylidene group and a substituted or unsubstituted aralkylidene group. In the general formulas (1) and (2), the unsubstituted alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms, and examples thereof include methyl, ethyl, propyl, i-propyl, butyl and t. -Butyl, i-butyl, amine, i-amine, s
Examples thereof include ec-amyl, texyl, hexyl, heptyl, octyl, nonyl, dodecyl and stearyl.

The substituted alkyl group includes an alkoxyalkyl group having 2 to 18 carbon atoms, a halogenoalkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an aminoalkyl group having 1 to 18 carbon atoms, and the like. , For example, as an alkoxyalkyl group, methoxyethyl,
Ethoxyethyl, ethoxyethyl, ethoxypropyl,
Examples thereof include ethoxybutyl, propoxymethyl, propoxybutyl, i-propoxypentyl, t-butoxyethyl and hexyloxybutyl.

Examples of the halogenalkyl group include chloromethyl, chloroethyl, bromoethyl, chloropropyl, chlorobutyl, chlorohexyl and chlorooxyl.

Examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl and the like.

Examples of the aminoalkyl group include aminomethyl, acetylaminomethyl, dimethylaminomethyl, aminoethyl, acetylaminoethyl, dimethylaminoethyl, diethylaminoethyl, morpholinoethyl, piperidinoethyl, diethylaminopropyl, dipropylaminoethyl, acetylaminopropyl. , Aminobutyl,
Examples thereof include morpholinobutyl.

The cycloalkyl group is cyclopentyl, cyclohexyl or cycloheptyl. Aralkyl groups include benzyl, chlorobenzyl, phenethyl and the like.

The aryl group has 6 to 16 carbon atoms, and is preferably phenyl, naphthyl, anthryl, phenanthryl, tolyl, xylyl, cumenyl, mesityl, chlorophenyl, methoxyphenyl, fluorophenyl and the like.

The alkoxyl group has 1 to 1 carbon atoms.
8 and preferably methoxy, ethoxy, propoxy, i-propoxy, butoxy and the like.

Of these, preferred substituents for r ² and r ³ are chlorine atom, bromine atom, methyl, ethyl, i-propyl, t-butyl, sec-amyl, thexyl, ethoxymethyl, methoxyethyl, chloromethyl, Hydroxymethyl, aminomethyl, dimethyl-aminomethyl and benzyl, and particularly preferred substituents are chlorine atom, t-butyl and thexyl. Preferred substituents for r ¹ are
Chlorine atom, methyl, ethyl, i-propyl, t-butyl, amyl, texyl, hydroxyl, chloromethyl,
Hydroxymethyl, benzyl, cyclohexyl,
Particularly preferred substituents are chlorine atom, methyl, t-butyl and thexyl.

Examples of the substituted or unsubstituted aralkyl group of the monovalent linking group include benzyl, p-methoxybenzyl, p-N, N-dimethylaminobenzyl, p-pyrrolidinobenzyl, p-methylbenzyl and p. -Hydroxybenzyl, p-chlorobenzyl, 3,5-dichloro-
4-hydroxybenzyl, o, p-dimethylbenzyl,
2-hydroxy-3-t-butyl-5-methylbenzyl, naphthylmethyl and the like can be mentioned.

Examples of the substituted amino group of the monovalent linking group include methylaminodimethylamino, diethylamino, acetylamino, phenylamino, diphenylamino, triazylamino and the like.

As the alkylidene group of the divalent linking group,
For example, methylene, ethylidene, propylidene, butylidene and the like can be mentioned.

As the aralkylene group of the divalent linking group,
For example, benzylene, p-methyl benzylene, p- dimethylamino benzylene etc. can be mentioned.

A preferable reducing agent in the general formula (1) is 2,6-di-t-butyl-4- (2-hydroxy-).
3-t-butyl-5-methylbenzyl) phenol,
2,6-di-t-butyl-4- (3,5-dichloro-4
-Hydroxybenzyl) phenol, 2-t-butyl-
4 (2-hydroxy-3,5-dimethylbenzyl) -5
-Methylphenol, 4,4'-methylenebis (2,6
-Di-t-butylphenol), 4,4'-methylenebis (2-t-butyl-5-methylphenol), 4,
4'-methylidene bis (2-t-butyl-6-methylenephenol), 4,4'-ethylidene bis (2,6-di-t-butylphenol), 4,4'-ethylidene bis (2-t-butyl-) 6-methylphenol), 4,4 '
-Propylidenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (2cyclohexyl-6-methylphenol), bis ( 3,5-
Di-t-butyl-4-hydroxyphenyl) phenylmethane, bis (3,5-di-t-butyl-4-hydroxyphenyl) (4-methoxyphenyl) methane, bis (3,5-di-t-butyl) -4-hydroxyphenyl (4-dimethylaminophenyl) methane, tris (3,3
5-di-t-butyl-4-hydroxyphenyl) methane.

Preferred reducing agents in formula (2) include 4,4'-methylenebis (2-methyl-1-naphthol) and 4,4'-methylenebis (2-t-butyl-1).
-Naphthol), 4,4'-methylenebis (2-t-butyl-6-methyl-1-naphthol), 4,4'-ethylidenebis (2-methyl-1-naphthol), 4,4 '.
-Ethylene bis (2-t-butyl-1-naphthol),
Bis (4-hydroxy-3-methyl-naphthyl) phenylmethane.

The preferred blending ratio of the above components of the photosensitive silver salt layer is as follows.

The photosensitive silver halide is preferably contained in an amount of 0.001 to 2 mol, more preferably 0.05 to 0.4 mol, per mol of the organic silver salt. Further, the reducing agent is preferably 0.2 mol to 3 mol, and more preferably 0.7 mol to 1. mol per mol of the organic silver salt.
It is desirable to contain 3 mol.

These materials are described in more detail in JP-A-50-99719, JP-A-51-23721 and JP-A-5-23721.
It is described in JP-A No. 1-232324, JP-A No. 2-210353 and the like.

The layer thickness of the photosensitive silver salt layer is 0.5 μm to 30 μm.
m, more preferably 1 μm to 20 μm.

This is because if the photosensitive silver salt layer is too thin,
O. This is because the D and (optical density) values cannot be obtained, which makes it unsuitable as a mask for the photosensitive resin layer, and when it is too thick, the image becomes dull and a clear image cannot be obtained, which is also unsuitable as a mask.

If necessary, an adhesive layer may be provided between the hydrophilic resin layer and the photosensitive silver salt layer for strengthening the adhesiveness of both layers. This adhesive layer may contain the above-mentioned antihalation dye to function as an antihalation layer. The thickness of this adhesive layer is 0.2 μm to 10 μm.
μm is desirable.

Further, in the present invention, it is preferable to provide a protective layer 106 on the photosensitive silver salt layer 105. This protective layer has a function of preventing the photosensitive silver salt layer from adhering or sticking to other substances, and also preventing permeation of water in the atmosphere. Further, the protective layer is substantially transparent to the photosensitive wavelengths of the hydrophilic layer and the photosensitive resin layer. Materials used for such a protective layer include polyethylene terephthalate, polypropylene, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, cellophane, methyl cellulose, ethyl cellulose, polyvinyl chloride, Examples thereof include vinylidene chloride copolymer, vinyl chloride copolymer such as vinyl chloride vinyl acetate copolymer, polyvinylidene chloride, polystyrene, polyvinyl alcohol, polycarbonate, gelatin, polyamide and the like. Furthermore, these may be used as a mixture of two or more kinds, or may be used by being laminated. The thickness of this protective layer is 0.
2 μm to 100 μm, preferably 0.5 μm to 50 μm
used in m. Moreover, various additives can be contained as needed.

[0082] Further, the present invention includes a maximum photosensitive wavelength lambda ₁ of the photosensitive resin layer, is between the maximum sensitive wavelength lambda ₂ of the hydrophilic layer,
(Λ ₂ −λ ₁ ) ≧ 150 nm is selected. This is an imagewise exposure to a hydrophilic layer having a masking function for a photosensitive resin layer (for example, semiconductor laser, LED,
It prevents light from a light source that has an output peak in the high wavelength region such as He-Ne laser) from reaching the photosensitive resin layer and causing photopolymerization of the non-image portion of the photosensitive resin layer to deteriorate the peeling developability. It depends on the purpose. The distance between wavelength λ ₁ and wavelength λ ₂ is λ
It is desirable that the relation of ₁ <λ ₂ is satisfied from the relation of the energy amount of the irradiated light. That is, by setting the photosensitive wavelength of the hydrophilic layer to be longer than the photosensitive wavelength of the photosensitive resin layer, it is possible to prevent the above-mentioned deterioration of the peeling developability.

In the present invention, the hydrophilic resin layer and / or the photosensitive resin layer may contain the antihalation dye corresponding to the photosensitive wavelength of the hydrophilic layer. The antihalation dye, O. at the wavelength lambda ₂ D value is
It is used in a range of 0.1 to 1.0, preferably 0.2 to 0.5.

The antihalation dye may be either a cation type or an anion type, but the hydrophilic resin layer 104
When it is added to the photosensitive resin layer 102, an anionic type which is easily dissolved in water is preferable, and when it is contained in the photosensitive resin layer 102, a cationic type is preferable.

Next, the plate making method of the present invention will be described.

FIG. 2 is a conceptual diagram showing an example of the plate making method of the present invention, but the present invention is not limited to this.

As shown in FIG. 2, the support 201, the photosensitive resin layer 202, the hydrophilic resin layer 204, and the photosensitive silver salt layer 20.
5. The peelable development type plate-making material in which the protective layer 206 is sequentially laminated is subjected to a) imagewise exposure from the light source A to form a silver latent image 207 in the photosensitive silver salt layer 205. As the light source A, one having an output wavelength corresponding to the photosensitive wavelength of the photosensitive silver salt layer is selected. For example, a CRT, a semiconductor laser, an LED array, a He-Ne laser, a shutter array such as an LCD or PLZT, and the like, which have an output peak in a high wavelength region, are preferable. When the light source A has an output wavelength range within the photosensitive wavelength range of the photosensitive resin layer, light from the light source may be removed by a filter (not shown) before exposure.

B) Then, the photosensitive silver salt layer 205 is uniformly heated or imagewise heated by the heating source B to carry out the developing treatment. A mask image 208 corresponding to the silver latent image 207 is formed. The heating source B can be heated and controlled to a temperature at which the photosensitive silver salt layer can be thermally developed, such as a flat heating element, a thermal head, a heating roller having a halogen heater, energization heating, heating by microwaves or infrared rays. What is preferable is. The heating temperature is 80 ° C to 150 ° C, preferably 90 ° C.
~ 130 ° C.

C) The entire surface is exposed from the side of the hydrophilic layer with respect to the light source C to form an exposed portion and an unexposed portion on the photosensitive resin layer 202 to form a polymerized portion and an unpolymerized portion. As the light source C, one corresponding to the photosensitive wavelength of the photosensitive resin layer, which is selected so as to be in a wavelength range shorter than the photosensitive wavelength of the photosensitive silver salt layer, is used.
For example, a fluorescent lamp, a high pressure mercury lamp, a halogen lamp, a tungsten lamp, a xenon lamp, an LED, a laser or the like can be used.

D) The support 201 is peeled off from the hydrophilic layer 203 together with the unpolymerized portion of the photosensitive resin layer, and the printing plate 211 is removed.
And The peeling may be carried out manually by previously providing a peeling end (not shown) on the support and / or the hydrophilic layer, or a separate peeling device may be prepared and used.

Further, e) If necessary, the printing plate 211 is heated by a light source C.
Using the heat source b, post-exposure and / or heating and / or
Or press the roller (not shown) to apply pressure to the printing plate.
It is advisable to further fix the image formed by the polymerized portion of the light-sensitive resin. Addition
Heat and / or pressure is applied to the extent that it does not deform the image.
It The heating temperature is preferably 20 ° C to 100 ° C, more preferably
Preferably, the temperature is 30 ° C to 80 ° C, and the pressure is 0.01 to 1k.
gf / cm ² , More preferably 0.1-0.5 kgf / cm
² Done in.

[0092]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part by weight" is abbreviated as "part".

Example 1 (1) A polyethylene terephthalate (PET) film having a thickness of 25 μm (manufactured by Panak Co .; Lumirror 25S) was used as a support, and a solution having the following composition was used to form a dry coating thickness of 6 μm using a wire bar. Apply and 80 in the oven
After drying at 10 ° C for 10 minutes, a photosensitive resin layer capable of peeling development was obtained. The maximum photosensitive wavelength λ ₁ of this photosensitive resin layer is 390 nm
Met. (2) Then, the following composition solution 64 parts of the above solution and the following general formula (A):

[0094]

[Chemical 3] A solution prepared by dissolving 0.001 part of the image-sensitizing dye compound represented by 1. in 1.0 part of N, N-dimethylformamide is sufficiently dissolved, dispersed, and mixed using a paint shaker in a dark room to prepare a photosensitive silver salt. A layer emulsion was obtained. The emulsion was coated on a 25 μm-thick PET film (Lunmirror 25S, manufactured by Panac Co., Ltd.) using a wire bar to obtain a photosensitive silver salt layer having a dry film thickness of 6 μm.

Then, a solution having the following composition, Was prepared and coated on the photosensitive silver salt layer using a wire bar, and then dried in an oven at 95 ° C. for 5 minutes to obtain a hydrophilic resin layer having a dry film thickness of 9 μm. The contact angle of water on the surface of the hydrophilic resin layer was 19 °.

(3) The films prepared in (1) and (2) were laminated so that the drying resin layer and the hydrophilic resin layer faced each other to obtain a plate-making material of the present invention.

(4) Drum scan type laser beam printer (manufactured by Abe design) from the protective layer side of the above plate-making material
Was used to perform image exposure with a He-Ne laser (output 5 mW). Then, heat development was carried out at 100 ° C. for 10 seconds to form a silver latent image on the exposed portion of the photosensitive silver salt layer.

Next, from the protective layer side, an ultra-high pressure mercury lamp (50
Full exposure with 0 W, Mikasa (approx. 120 mJ / cm ²⁾
at 365 nm) for 30 seconds to form a polymerized image consisting of polymerized parts / unpolymerized parts corresponding to the mask by the silver latent image on the photosensitive resin layer.

Next, together with the unpolymerized portion of the photosensitive resin layer,
The support was peeled off from the process product to obtain a printing plate. The resolution of this printing plate was 900 dpi.

(5) Using the printing plate prepared in (4),
Printing was performed according to the following procedure.

First, the above printing plate was sufficiently wet with deionized water and then mounted on the plate cylinder 301 of the printing apparatus shown in FIG. Ink 30 in the ink scale 304 and dampening water reservoir 308
5 (brand name BSD New Rubber Ink Silver, manufactured by Bunshodo Co., Ltd.) and fountain solution 306 (deionized water) were supplied, and the printing apparatus was operated. First, the dampening water 306 was supplied onto the printing plate through the dampening water supply roller 307, and then the ink 305 was supplied onto the printing plate through the ink supply roll 303. Next, the ink attached to the polymerized portion of the photosensitive resin layer was transferred to the blanket cylinder 309. Further, the recording medium 311 made of plain paper is transferred from the cassette 312 to the roller 313.
The ink is transferred by passing through the gap between the blanket cylinder and the impression cylinder 310, and the ink is normally transferred from the blanket cylinder onto the blanket cylinder.
I got a print.

Under the condition of a printing speed of 80 sheets / min, 1000 sheets of black images without background stains were obtained. At this time, no peeling of the photosensitive resin polymerized portion from the hydrophilic resin was observed.

Comparative Example 1 A dampening plate-making material shown in FIG. 4 was prepared in the following manner.

(1) First, a photographic emulsion similar to that used in Example 1 (2) was prepared, and the PET film 40 having a thickness of 9 μm was prepared.
4 was coated in the same manner as in Example 1 to obtain a photosensitive silver salt layer 405. Then, a 10% aqueous solution of polyvinyl alcohol (PVA: trade name Gohsenol GL-05) was coated on the photosensitive silver salt layer 405 with a wire bar to give a dry film thickness of 4
A protective layer 406 having a thickness of μm was obtained. Then, a solution similar to that of Example 1 (1) was prepared and applied to the surface of the PET film opposite to the surface in contact with the photosensitive silver salt layer, and the peelable and developable photosensitive resin layer 403 having a dry film thickness of 6 μm. Got

Here, the PET film is the intermediate support 404.
Used as.

(2) Weighed value 140 g / m ² which is mainly composed of long fiber pulp and is excellent in sizing degree, water resistance and smoothness.
A high-quality paper was prepared and a hydrophilic resin layer 402 was provided thereon in the same manner as in Example 1. Here, the high-quality paper is the substrate 401.
Used as.

(3) The film prepared in (1) and (2) was laminated so that the photosensitive resin layer 403 and the hydrophilic resin layer 402 were in contact with each other to obtain a plate-making material.

(4) A printing plate was prepared from the above plate-making material in the same manner as in Example 1. As a result, the edge portion of the image is not well cut due to the polymerized portion on the hydrophilic resin layer, and a crease that often occurs at the time of peeling and development accompanies the image.

(5) Using the printing plate prepared in (4),
When printing is performed in the same manner as in Example 1, the resolution is 600d.
It was about pi.

Examples 2 to 6 Comparative Examples 2 to 3 A printing plate was prepared in the same manner as in Example 1 except that the film thickness of the hydrophilic resin layer was changed from 2 μm to 100 μm and the imagewise exposure conditions were adjusted appropriately. Printing was performed, and the resolution and printing durability of the printing plate were examined. The results are shown in Table 1.

[0111]

[Table 1] *) Peeling and development could not be performed on the hydrophilic resin layer. (It can be considered that heating during the heat development of the photosensitive resin layer has a bad influence.) From Table 1, it is understood that the film thickness of the hydrophilic resin layer is preferably in the range of 2 μm to 50 μm.

Example 7 As the image-sensitizing dye compound contained in the photosensitive silver salt layer, the following general formula (B),

[0113]

[Chemical 4] A compound represented by 3,3 ′, 9-triethyl-5,
A plate-making material was prepared in the same manner as in Example 1 except that 5′-diphenyl-2,2′-oxacarbocyanine iodide was used instead. The maximum photosensitive wavelength of this photosensitive silver salt layer is 540n.
It was m.

Then, when a printing plate was formed in the same manner as in Example 1, the resolution was about 900 dpi. However, the breakage of the image area was lower than that in Example 1.

Comparative Example 4 A plate-making material and a printing plate were prepared in the same manner as in Example 1 except that the antihalation dye was not contained in the hydrophilic resin layer. As a result, the resolution of the printing plate is 600 dpi,
The effect of the antihalation dye in the present invention was confirmed.

Comparative Example 5 The photosensitive silver salt layer was made to have a composition containing no sensitizing dye compound,
A plate-making material and a printing plate were prepared in the same manner as in Example 1 except that the imagewise exposure was changed as follows.

Imagewise exposure is performed by using a tungsten tamper (100 W) through a mask made of a commercially available wet film.
1000 lux for 3 seconds.

During the peeling development of the printing plate thus prepared, unpolymerized portions remained on the hydrophilic resin layer in places. Then
When printing was performed in the same manner as in Example 1, the image of the printed matter was significantly deteriorated as compared with Example 1.

Example 8 (1) In the same manner as in Example 1, a photosensitive resin layer was formed on the PET film.

(2) On another PET film, instead of polyvinyl butyral of the emulsion for the photosensitive silver salt layer of Example 1, polyvinyl alcohol having a saponification degree of 60% was used,
A hydrophilic layer was obtained by coating and drying in the same manner as in Example 1 except that 40 parts of toluene and 40 parts of IPA were used as the solvent. The contact angle of this hydrophilic layer with water was 30 °.

(3) The film prepared in (1) and (2) was laminated so that the photosensitive resin layer and the hydrophilic layer faced each other to obtain a plate-making material of the present invention.

(4) The above plate-making material was subjected to image exposure, heat development, whole surface exposure and peeling development in the same manner as in Example 1 to obtain a printing plate. The resolution of this printing plate was 900 dpi.
Further, there were no creases or tears that often occur during peeling development.

[0123]

As described above, according to the present invention, since the entire surface is exposed from the hydrophilic layer side, it is possible to obtain a high resolution printing plate without deterioration of image quality during peeling development. .. In addition, since the adhesive interface with the hydrophilic resin layer can be placed closer to the entire exposure light source side, the binding force between the hydrophilic resin layer and the polymerized portion of the photosensitive resin layer becomes stronger, and printing durability is improved. Also has.

Further, according to the present invention, it is possible to carry out plate making by writing using a light source having a relatively small output such as a laser.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing an example of a layer structure of a plate-making material of the present invention.

FIG. 2 is an explanatory view schematically showing a plate making method of the present invention.

FIG. 3 is a schematic cross-sectional view showing the configuration of the printing apparatus used in this embodiment.

FIG. 4 is a cross-sectional view showing a layer structure of a conventional plate-making material.

[Explanation of symbols]

 101, 201 support 102, 202 photosensitive resin layer 103, 203 hydrophilic layer 104, 204, hydrophilic resin layer 105, 205 photosensitive silver salt layer 106, 206 protective layer 207 silver latent image 208 mask image 209 unpolymerized portion 210 Polymerization unit 301 Plate cylinder 302 Printing plate 303 Ink supply roll 304 Ink balance 305 Ink 306 Dampening water 307 Dampening water supply roll 308 Dampening water reservoir 309 Blanket cylinder 310 Impression drum 311 Recording medium 312 Cassette 313 Roll 314 Tray 401 Substrate 402 hydrophilic resin layer 403 photosensitive resin layer 404 intermediate support 405 photosensitive silver salt layer 406 protective layer

Front Page Continuation (72) Inventor Akihiro Mohri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (10)

[Claims] 1. A plate-making material comprising a support, a photosensitive resin layer containing a polymerizable compound and capable of peeling development, and a hydrophilic layer, which are at least sequentially laminated, wherein the hydrophilic layer is the photosensitive resin layer. A peeling development type plate-making material having a masking ability with respect to. 2. The peelable plate-making material according to claim 1, wherein the hydrophilic layer contains at least silver halide, an organic silver salt and a reducing agent. 3. A photosensitive silver containing a hydrophilic layer formed on a photosensitive resin layer, and at least a silver halide formed on the hydrophilic resin layer, an organic silver salt and a reducing agent. The peeling according to claim 1, comprising a salt layer and a protective layer formed on the photosensitive silver salt layer, and forming a mask for the photosensitive silver salt layer by exposing and developing the photosensitive silver salt layer. Development type plate making material. 4. The layer thickness of the hydrophilic resin layer is 1 μm to 50.
The peeling-development type plate-making material according to claim 3, which is in the range of μm. 5. The peeling development type plate-making material according to claim 3, wherein the hydrophilic resin layer is bonded to the photosensitive silver salt layer via an adhesive layer. 6. The layer thickness of the adhesive layer is 0.5 μm to 20 μm.
6. The peelable development type plate-making material according to claim 5, wherein 7. The maximum photosensitive wavelength λ of the photosensitive resin layer₁ And hydrophilic
Maximum photosensitive wavelength of layer λ ₂ And the following equation (I) (λ₂ −λ₁ ) ≧ 150 nm (I) is satisfied, the peel development type product according to claim 1.
Plate material. 8. The antihalation dye for the photosensitive wavelength of the photosensitive silver salt layer is contained in at least one of the hydrophilic resin layer and / or the adhesive layer and / or the photosensitive resin layer. 7. The peeling development type plate-making material as described in 7 above. 9. The release-development type plate-making material according to claim 1, wherein (a) the hydrophilic layer side, imagewise exposure and / or imagewise heat application according to the photosensitive wavelength of the hydrophilic layer. And (b) performing a development treatment on the hydrophilic layer, if necessary, (c) exposing the entire surface of the hydrophilic layer according to the photosensitive wavelength of the hydrophilic resin layer, and (d) A plate making method comprising the steps of peeling and removing the support together with the unpolymerized portion of the photosensitive resin layer from the hydrophilic layer, and leaving the polymerized portion of the photosensitive resin layer on the hydrophilic layer. 10. After the step (d) according to claim 9, (e) a step of subjecting the polymerized part of the photosensitive resin layer and / or the hydrophilic layer to post-exposure and / or heating and / or pressurization A plate-making method comprising: