JPH05210236A - Original plate for printing, production of printing plate by using this original plate for printing and printing method and printing device using this printing plate - Google Patents

Abstract

PURPOSE:To enhance printing resistance and resolution and to improve the cut of lines, etc., by providing at least a base layer, a release developable photosensitive layer and a release base layer and incorporating a polymerizable compd. into the base layer. CONSTITUTION:This original plate for printing has at least the base layer 2, the release developable photosensitive layer 3 and the release base layer 4 and contains the polymerizable compd. in the base layer 2. This process for production of the printing plate has an image exposing process for forming polymerized parts and unpolymerized parts on the photosensitive layer 3 by subjecting the original plate for printing to image exposing and a release developing process for peeling and removing the unpolymerized parts together with the release base layer 4 and allowing the polymerized parts to remain on the base layer 2. The printing stage has at least a stage for supplying ink to the printing plate and a stage for transferring the ink to a body to be recorded. The printing device has at least an ink supplying means for supplying the ink to the produced and printed printing plate and a transferring means for transferring the ink supplied to the printing plate to the body to be recorded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing original plate and a method for producing a printing plate using the printing original plate. More specifically, it has excellent printing durability suitable for the field of light printing, particularly for office printing. The present invention relates to a printing original plate that provides a printing plate, a method for manufacturing a printing plate using the printing original plate, a printing method using the printing plate, and a printing apparatus.

[0002]

2. Description of the Related Art In general, lithographic printing utilizes the immiscibility of water and oil. A lithographic printing plate is generally provided with a non-printing area showing hydrophilicity and a drawing section showing lipophilicity. ing. Then, during printing, dampening water is applied to the planographic printing plate to increase ink repulsion and held in the non-image area, and then oily ink is applied to dampen the non-image area. The ink does not adhere due to the action of water, the ink adheres only to the image area,
The image on the lithographic printing plate is transferred to paper or the like directly or through a blanket cylinder.

Among the lithographic printing plates used for such lithographic printing, PS plates are used for large-scale printing. The PS plate is prepared by polishing the surface of a metal plate (aluminum, zinc, etc.) of a support or by making it an anode. A photosensitive resin is applied to a material that has been oxidized to impart hydrophilicity, and the area where the lipophilic image area is formed by imagewise exposure and development and the photosensitive resin is removed is hydrophilic It becomes the drawing area.

Further, as a small copy printing plate for office work, a hydrophilic resin layer which is a non-image area is usually formed on a water-resistant support, and a toner is formed on the hydrophilic resin layer by, for example, an electrophotographic method. There are a printing plate on which an image is formed, a printing plate drawn with a ballpoint pen or an oil-based ink, a printing plate on which a printed image is formed by a typewriter or a thermal head, and the like.

[0005]

However, the above
Since the development process of a PS plate or a printing plate by a wet electrophotographic method is a wet process using an organic solvent or water,
Liquid management, maintenance, waste liquid treatment, etc. are complicated and there is a problem of environmental pollution due to solvents.

Further, among the above-mentioned office printing plates, there are those obtained by dry processing, such as a dry electrophotographic printing plate, a typewriter, and a printing plate on which a printed image is formed by a thermal head, but the resolution is low. , Image quality, broken lines, etc. are not completely satisfactory.

Further, in a printing plate which is generally known as an office printing plate and which is manufactured by using a wet or dry electrophotographic system, it is not possible to prevent the toner from scattering, and it is However, there is a problem that it causes dirt.

As a printing plate for solving these problems, a difference in adhesiveness caused by light is used for a printing plate having a photosensitive layer capable of peeling and developing on a support and an upper layer such as polyester on the support. A printing plate produced by a dry developing method using a so-called peel apart process is known. JP-B 38-9663 and JP-B 4
3-22901, JP-A-47-7728,
JP-B-48-43126, JP-A-55-5024
6, JP-A-57-58141 and JP-A-57.
-62046, Japanese Patent Publication No. 64-10055,
Japanese Examined Patent Publication No. 64-10056, Japanese Patent Publication No. 1-45899
It is described in each publication such as Japanese publication.

However, in the above printing plate, the adhesive force between the hydrophilic support and the lipophilic polymerized image portion is weaker than that of the PS plate, that is, the printing durability is poor. Especially when the hydrophilic layer, which is often used for office printing plates, is paper or hydrophilic resin, the adhesive force between the support and the image area is weaker,
The supply of dampening water at the time of printing further promotes the reduction of the adhesive force, and has the drawback that the printing durability is extremely poor.

The problem to be solved by the present invention is to solve the above-mentioned various problems, and it is a simple and quick dry process, has excellent printing durability and resolution, and is good for lithographic printing such as line breaks. Original plate for printing, which can produce a printing plate for
An object of the present invention is to provide a printing plate manufacturing method using the printing original plate, a printing method using the printing plate, and a printing apparatus.

[0011]

The printing original plate of the present invention comprises:
It has at least a base layer, a peelable developable photosensitive layer and a peeling support layer, and contains a polymerizable compound in the base layer.

Further, the printing plate precursor of the present invention has at least a base layer, a peelable and developable photosensitive layer, and a photosensitive silver salt layer containing at least a photosensitive silver halide, an organic silver salt and a reducing agent. The base layer contains a polymerizable compound.

In the method for producing a printing plate of the present invention, the above-mentioned printing plate precursor is image-exposed to form a polymerized portion and an unpolymerized portion in the photosensitive layer, and the unpolymerized portion is exposed. And a peeling and developing step of peeling and removing together with the peeling support layer and leaving the polymerized portion on the base layer.

Further, a method for producing a printing using a printing original plate having a photosensitive silver salt layer comprises an image exposure step of exposing the printing original plate to an image, and a heat development step of heating the printing original plate. , A polymerization exposure step of forming a polymerized portion and an unpolymerized portion in the photosensitive layer by polymerizing and exposing the printing original plate, and peeling and removing the unpolymerized portion together with the photosensitive silver salt layer, And a peeling and developing step of leaving a portion on the layer.

Further, the printing method of the present invention comprises a step of supplying ink to the printing plate manufactured by the above manufacturing method, and a step of transferring the ink supplied to the printing plate to a recording medium. The printing apparatus of the present invention comprises at least an ink supply unit that supplies ink to the printing plate manufactured by the manufacturing method described above, and a transfer unit that transfers the ink supplied to the printing plate to a recording medium. At least.

First, the printing original plate of the present invention will be described.

The printing original plate of the present invention has at least a base layer, a peelable and developable photosensitive layer and a peeling support layer, and the base layer contains a polymerizable compound. Hereinafter, this is referred to as a first mode.

Further, the printing original plate of the present invention has at least a base layer, a peelable and developable photosensitive layer, and at least a photosensitive silver salt layer containing a photosensitive silver halide, an organic silver salt and a reducing agent. The base layer contains a polymerizable compound. Hereinafter, this is referred to as a second mode.

The peelable and developable photosensitive layer means a layer capable of forming a polymerization pattern by so-called peel apart. That is, by exposing in a pattern, a polymerized portion and an unpolymerized portion are formed in the layer according to the exposure pattern, and then the polymerized portion and the unpolymerized portion are separated from each other to peel and develop the layer to be a polymerized pattern. It is called a possible photosensitive layer.

As the printing original plate of the first aspect of the present invention, for example, as shown in FIG. 1, a base layer 2, a peelable and developable photosensitive layer 3, and a peeling support layer 4 are sequentially laminated on a substrate 1. The configuration can be mentioned.

Further, as the printing original plate of the second mode, for example, as shown in FIG.
A configuration in which the photosensitive layer 3, the photosensitive silver salt layer 5, and the protective layer 6 are sequentially stacked, or a configuration in which the intermediate layer 7 is provided between the photosensitive layer 3 and the photosensitive silver salt layer 5 as shown in FIG. be able to.

The substrate 1 used in the printing original plate of the present invention may be selected from a wide range of materials as long as it is a support to which the base layer 2 on the substrate 1 is strongly adhered. Metal plates such as zinc, copper and steel; plastic films such as polyethylene terephthalate, polyvinyl chloride and polycarbonate; resin coated films; paper, wet reinforced paper, resin coated paper, paper coated with aluminum or copper metal foil; rubber Glass;
Further, composites thereof, for example, a metal plate having a rubber elastic layer, a plastic film, glass, paper; a metal plate plated with, vapor-deposited or sputtered with a metal such as aluminum, zinc, copper, nickel, chromium and iron, a plastic film. , Glass, paper and the like can be used. Further, an anchor agent may be applied on the support for the purpose of improving the adhesive strength between the substrate 1 and the substrate 1.

The thickness of the substrate 1 is 1 μm to 5 m.
m, more preferably 5 μm to 3 mm.

Base layer 2 of the printing plate precursor of the present invention
Contains at least a layer-forming polymer substance and a polymerizable compound. By appropriately selecting the layer-forming polymer substance used for the base layer 2, the dampening water can be sufficiently retained in the base layer 2, or the printing ink can be repelled without the immersion water. ..

The layer-forming polymer substance is a polymer substance capable of forming a layered film, and may be appropriately selected from a wide range of resins generally used as a binder depending on the application of the printing plate. However, among these, resins having hydrophilicity are particularly preferable, and specifically, for example, plant-based polymers such as guar gum, locust bean gum, gum arabic, taragant, carrageenan, bectin, mannan, and starch; xanthan gum, dextrin. , Succinoglucan, curdlan, and other microbial polymers; gelatin,
Animal-based polymers such as casein, albumin and collagen;
Cellulosic polymers such as methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, etc., or starch-based polymers such as soluble starch, carboxymethylstarch, methylstarch, etc.
Alginic acid polymers such as propylene glycol alginate and alginate, and semi-synthetic polymers such as other polysaccharide derivatives; polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyacrylamide, poly ( Vinyl-based polymers such as (meth) acrylic acid and polyacrylonitrile; other polyethylene glycols,
Synthetic polymers such as ethylene oxide and propylene oxide block copolymers; Japanese Examined Patent Publication No. 15383/1990;
Japanese Patent Application Laid-Open No. 0472, Japanese Patent Application Laid-Open No. 2-105873, Japanese Patent Application Laid-Open No. 1-238935, Japanese Patent Application Laid-Open No. 2-110119, Japanese Patent Application Laid-Open No. 2-107678, Japanese Patent Application Laid-Open No. 2-27.
In addition to the hydrophilic polymer described in the above publication, a resin containing a functional group which itself is hydrophobic but which is hydrolyzed by an etchant or dampening water or hydrolyzed to form a hydrophilic group is also available. Preferably, JP-A-1-306856, JP-A-1-306855, and JP-A-1-267093.
Examples thereof include resins described in JP-A No. 1-269593. These may be used alone or in combination of two or more as required.

Silicon dioxide, titanium dioxide, silica, clay, a cross-linking agent (waterproofing agent), a surfactant and the like may be added to the above layer-forming polymer substance. The crosslinking agent is
Since many hydrophilic resins are water-soluble, they are added in order to impart water resistance to such water-soluble resins, for example, melamine-formalin resin, urea-formalin resin,
Polyamide polyaminoepichlorohydrin resin, ketone-formalin resin, methylolated polyamide resin, glyoxal, boric acid or polyvalent metal salt can be used.

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-containing oligomer. One or more selected from the group consisting of vinyl group-containing polymers can be used. The reactive vinyl group of these compounds is a styrene-based vinyl group, a (meth) acrylic acid-based vinyl group, an allyl-based vinyl group, a vinyl ether, or other ester-based vinyl group-substituted substitution having polymerization reactivity. Group or an unsubstituted vinyl group. Here, (meth) acrylic acid means methacrylic acid and acrylic acid.

Among the polymerizable compounds, first, as a polymerizable compound having hydrophilicity, a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, an imide group, an amino nitrogen, a sulfone group,
Examples thereof include those containing a hydrophilic group such as an ammonium salt group and a phosphoric acid group, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol monoacrylate, and the like. Hydroxyl group-containing polymerizable compounds such as glycerol mono (meth) acrylate, glycerol di (meth) acrylate, glycerol methacrylate acrylate:
An alkoxy group-containing polymerizable compound such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; t-butylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and the like. Alkoxy group-containing polymerizable compounds; 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. 1: 1 of diol such as (meth) acrylate, polyethylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate and (meth) acrylic acid,
1: 2 adduct: 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 1: of diol / diglycidyl ether such as (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether (meth) acrylate, trimethylolpropane triglycidyl ether di (meth) acrylate and acrylic acid 2 adducts: pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipe Data erythritol mono (meth) acrylate, dipentaerythritol di (meth)
Pentaerythritol derivatives such as acrylate, 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-ptoxy (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, methylene bis (meth) acrylamide,
Acrylamide, glyoxal adduct, acrylamide / methyloethylene urea condensate, 1,3,5-triacryloylhexahydro s-triazine, N, N-diallyl acrylamide, acrylamide / methylol melamine condensate, acrylamide / methylol triazone condensate, acrylamide・ Methylol hydantoin condensate,
Acrylamide / methylol urea, acrylamide derivative such as N, N-diallyl acrylamide; 2- (meth)
Sulfonyl group-containing polymerizable compounds such as acrylamido-2-methylpropanesulfonic acid; (meth) acrylamidopropyltrimethylammonium chloride, (meth)
Ammonium group-containing polymerizable compounds such as acryloyloxyethyl trimethylammonium chloride; Phosphoric acid group-containing polymerizable compounds such as mono (2- (meth) acryloyloxyethyl) acid phosphate; N- (meth) acryloylmorpholine, tetrahydroflur Freel (meth) acrylate, vinyl acetate, acrylonitrile, N-vinylcaprolactam, N-vinylpyrrolidone, etc., and also reactive with the end of hydrophilic oligomer or polymer (for example, the above-mentioned hydrophilic binder). Examples thereof include a polymerizable compound having a vinyl group left, or a polymerizable compound having a reactive vinyl group on the side chain of a hydrophilic oligomer or polymer.

It is also possible to use a lipophilic polymerizable compound which is not hydrophilic, for example, styrene, methylstyrene, chlorostyrene, promostyrene, methoxystyrene, dimethylaminostyrene, cyanostyrene, nitrostyrene, hydroxystyrene, Aminostyrene, carboxystyrene, methyl (meth) acrylate, (meth)
Ethyl acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, vinyl pyridine, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, β-
Monovalent monomers such as chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl vinyl ether and p-chlorophenyl vinyl ether; divinylbenzene, distyryl oxalate, distyryl malonate, distyryl succinate, distyryl glutanate, distyryl adipate, Distyryl maleate, distyryl fumarate, β, β-dimethylglutanate distyryl, 2-promoglutanate distyryl, α, α′-dichloroglutanate distyryl, terephthalate distyryl, oxalate di (ethyl (meth) acrylate), Oxalic acid di (methylethyl (meth) acrylate), malonic acid di (ethyl (meth) acrylate), malonic acid di (methylethyl (meth) acrylate), succinic acid di (ethyl (meth) acrylate)
Acrylate), glutaric acid di (ethyl (meth) acrylate), adivic acid di (ethyl (meth) acrylate), maleic acid di (diethyl (meth) acrylate), fumaric acid di (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-bis ((meth) acryloyloxyethoxycarbamoyl) cyclohexane, bis ((meth) acryloyloxyethoxycarbamoylsocrohexyl) methane, etc. Divalent monomer; cyanuric acid tri (meth) acrylate, 1,1,1
-Trimethylolpropane tri (meth) acrylate,
Cyanuric acid tri (ethyl (meth) acrylate), 1,
1,1-trimethylolpropane tri (ethyl acrylate), cyanuric acid tri (ethyl vinyl ether),
A reaction product of 1,1,1-trimethylolpropane with 3 times mol of toluene diisocyanate and a condensate of hydroxyethyl acrylate, a reaction product of 1,1,1-trimethylolpropane with 3 times mol of hexane diisocyanate, Trivalent monomers such as condensates with p-hydroxystyrene; tetravalent monomers such as pentaerythritol tetraacrylate; hexavalent monomers such as dipentaerythritol hexaacrylate; and oligomers. Or a polymerizable compound in which a reactive vinyl group remains at the end of the polymer,
Alternatively, a polymerizable compound in which a side chain of an oligomer or a polymer has a reactive vinyl group can be exemplified. It is also possible to use two or more of these polymerizable compounds in combination.

The polymerizable compound contained in the base layer 2 preferably has a molecular weight of 80 to 2000, more preferably 100 to 1000.

The polymerizable compound contained in the base layer 2 is preferably one which is difficult to dissolve in water and is in a dispersed state (including one which is separated by leaving it to stand) even when it is dissolved in water. Examples of such a polymerizable compound include 2-hydroxypropyl (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol mono (meth) acrylate. Pentaerythritol derivatives such as acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate,
Examples thereof include trimethylolpropane triacrylate, pentaerythritol tetraacrylate and cipentaerythritol hexaacrylate, with pentaerythritol acrylate being particularly preferred.

The polymerizable compound in the base layer 2 exhibits a strong interaction such as a bond with the polymerized portion of the photosensitive layer 3 which is peelable and developable on the base layer 2, and the polymerized portion of the photosensitive layer 3 is made into the base layer 2.
Firmly adhere to. When the photosensitive layer 3 is imagewise exposed and polymerized, the radical chain of the polymerized portion acts even on the polymerizable compound of the base layer 2 so that the polymerizable compound of the polymerized portion of the photosensitive layer and the polymerizability of the base layer are polymerized. It is thought to be caused by binding with the compound.

The adhesive force between the polymerized portion of the photosensitive layer and the base layer 2 is not solely due to the adhesive force of the base layer 2.

When a polymerizable compound which is not highly soluble in water is used as the polymerizable compound contained in the base layer 2,
Probably, like the bleeding phenomenon of the plasticizer of a plastic product, the polymerizable compound bleeds to the surface of the base layer during the formation of the base layer, and a large amount of the compound is present on the surface. Therefore, the polymerized portion of the photosensitive layer 3 is formed in the base layer 2. Adheres more strongly,
It is considered that printing durability is further improved.

After the unpolymerized portion of the photosensitive layer 3 is peeled off and removed, the polymerizable compound in the base layer 2 is in an unpolymerized state, and if it is left as it is, there is no particular influence at the time of printing, By polymerizing or cross-linking the polymerizable compound in the unpolymerized state, the polymer can be entangled with the layer-forming polymer substance component of the base layer 2 to reduce the solubility in water, As with the case of using the water-proofing agent, it can be made sparingly water-soluble or water-insoluble, and depending on the degree, the water-proofing agent may not be used in some cases.
That is, the polymerizable compound contained in the base layer 2 also has a role of improving the water resistance of the base layer 2.

When the unpolymerized polymerizable compound is polymerized or crosslinked for the purpose of improving the water resistance as described above, the base layer 2 must contain a polymerization initiator.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is used. First, a known one can be used as the thermal polymerization initiator, for example, an azo type initiator or a peroxide type initiator. Can be mentioned. The azo initiator is an organic compound having at least one nitrogen-nitrogen double bond in the molecule, such as azobisisobutyronitrile.
Azobiscyclohexanecarbonitrile, azobismethylphenethylcarbonitrile, azobissec-amylonitrile, azobisphenylethane, azobiscyclohexylpropyronitrile, azobismethylchloroethane, tritylazobenzene, phenylazoisobutyronitrile, 9- (p -Nitrophenylazo) -9-phenyl fluorene and the like can be mentioned. As the peroxide-based initiator, almost all compounds are included as long as they are organic compounds having at least one oxygen-oxygen bond in the molecule. For example, methyl ethyl ketone peroxide,
Cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1'-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexanone, 1,
1'-bis (tertiarybutylperoxy) cyclohexane, n-butyl-4,4-bis (tertiarybutylperoxy) palerate, 2,2'-bis (tertiarybutylperoxy) butane, tert-butylhydro Peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl tamil peroxide, Ditamyl peroxide, α, α′-bis (tertiarybutylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-dimethyl-2,5 -Di (tertiary butyl peroxy) hex Syn-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,
4-dichlorobenzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormal propyl peroxydicarbonate,
Di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di-
(3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate,
Tertiary butyl peroxyisobutyrate, Tertiary butyl peroxy vivarate, Tertiary butyl peroxy neodecanoate, Tertiary butyl peroxy octanoate, Tertiary butyl peroxy-3,5,5-trimethyl hexa Noate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, ditertiary diperoxybenzoate, ditertiary diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane Examples thereof include, but are not limited to, tert-butyl peroxymaleic acid, tert-peroxyisopropyl carbonate, and other known thermal polymerization initiators.

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;
Henzophenones such as 4′-diethylaminobenzophenone and 4,4′-dimethoxybenzophenone; acetophenones such as acetophenone and 4-methoxyacetophenone; benzoylalkyl ethers such as 2-cyclolothioxanthone and 2-5-diethylthioxanthone, Thioxanthone-3-carboxylic acid-β-
Thioxanthones such as methoxyethyl ester; chalcones having dialkylamino groups and styryl ketones; coumarins such as 3,3′-carbonylbis (7-methoxycoumarin) and 3,3′-carbonylbis (7-diethylaminocoumarin) And the like.

Examples of the sulfur compound include dibenzthiazolyl sulfide, decyl phenyl sulfide and other disfides.

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

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, 2
It is also possible to combine more than one species to obtain a more efficient photopolymerization reaction.

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

When the photosensitive layer 3 is laminated (laminated) on the base layer 2, it is preferable that the base layer 2 has a smoothness such that it is adhered when the photosensitive layer 3 is laminated.

Further, the base layer 2 contains a thermal polymerization inhibitor,
Antiseptic, antihalation dye, antifoam, antistatic agent,
A dispersant, an emulsifier, etc. may be appropriately contained as necessary.

If the base layer 2 maintains its own strength, the substrate 1 may not be used.

The content of the layer-forming polymer substance in the base layer 2 is preferably 10 to 98% by weight with respect to the base layer 2.

The polymerizable compound in the base layer 2 is 1 to 1000 parts by weight based on 100 parts by weight of the layer-forming polymer substance,
Further, it is preferable to contain 1 to 700 parts by weight.

When the base layer 2 contains a polymerization initiator, the amount of the polymerization initiator is 0.1 to 30 parts by weight, more preferably 0.3 to 25 parts by weight, based on 100 parts by weight of the polymerizable compound. preferable.

The thickness of the base layer 2 is preferably 2 to 50 μm, more preferably 5 to 30 μm.

The peelable and developable photosensitive layer 3 of the printing original plate of the present invention is a base layer 2 and an upper layer (peeling support layer 4, photosensitive silver salt layer 5 or intermediate layer 7) of the photosensitive layer 3.
By utilizing the fact that the adhesive force to the exposed layer changes between the exposed and unexposed parts, the portion having a large adhesive force to the upper layer of the photosensitive layer 3 is peeled and removed together with the upper layer, and the portion having a large adhesive force to the base layer 2 remains. Then, an image can be formed.

In the present invention, the photosensitive layer 3 and the base layer 2
By selecting the respective compositions of the upper layer and the upper layer, the exposed portion of the photosensitive layer 3 is left on the base layer 2.

The photosensitive layer 3 contains at least a polymerizable compound, a layer-forming polymer substance and a photopolymerization initiator.

Examples of the layer-forming polymer substance contained in the photosensitive layer 3 include the layer-forming polymer substance forming the base layer 2 described above, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, and polymethyl. Methacrylate, polyacrylic acid, polymethacrylic acid, polyacrylic acid alkyl ester (alkyl group is preferably methyl group, ethyl group, butyl group), acrylic acid alkyl ester (alkyl group is preferably methyl group, ethyl group) , Butyl group) and at least one kind of monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene and butadiene, polyvinyl chloride,
Copolymer of vinyl chloride and acrylonitrile, polyvinylidene chloride, copolymer of vinylidene chloride and acrylonitrile, polyvinyl acetate, copolymer of vinyl acetate and vinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone, polyacrylonitrile, acrylonitrile and Copolymer of styrene, copolymer of acrylonitrile with butadiene and styrene, polyvinyl alkyl ether (alkyl group is preferably methyl group, ethyl group, isopropyl group, butyl group), polyethylene, polypropylene, polybutyne, polystyrene, poly -Α-methylstyrene, polyamide (preferably 6-
Nylon, 6,6-nylon, 6,10-nylon),
Poly-1,3-butadiene, polyisoprene, polyurethane, polyester (preferably polyethylene terephthalate, polyethylene isophthalate, linear saturated polyester), chlorinated rubber, polychloroprene, chlorinated rubber, polyvinyl butyral, polyvinyl formal, styrene-butadiene rubber, Poly (chlorosulfonated ethylene)
Etc. are homopolymers or copolymers.

Of the above substances, particularly preferable are chlorinated polyolefins represented by chlorinated polyethylene and chlorinated polypropylene, polymethylmethacrylate, chlorinated rubber, polyvinyl chloride, polyvinyl butyral, polyester (particularly linear polyester). ). These substances may be used alone or in combination of two or more.

When a printing plate is produced using the printing plate precursor of the present invention, a heat treatment may be carried out simultaneously with the image exposure or after the image exposure, which will be described in detail later. When the heat treatment is carried out during the production of the printing plate as described above, the photosensitive layer is thermally deteriorated or the compatibility of the components of the photosensitive layer is changed. May remain, or the surface of the polymerized portion of the photosensitive layer may become uneven. When printing is performed using such a printing plate, a clear image cannot be obtained.

When heat treatment is carried out during the production of the printing plate, particularly before the peeling and development of the photosensitive layer, the layer-forming polymer substance of the photosensitive layer is preferably a mixture of chlorinated polyolefin and linear saturated polyester. .. As the chlorinated polyolefin, for example, chlorinated polyethylene and chlorinated polypropylene are preferable. As the linear saturated polyester, those having a basic skeleton composed of terephthalic acid and ethylene glycol and having a carboxyl group, a hydroxyl group or both of them at both ends of the basic skeleton are preferable. In the basic skeleton of linear polyester, dibasic acid other than terephthalic acid,
Combinations with dihydric alcohols other than ethylene glycol may be included.

Although it is possible to obtain a preferable image by using linear saturated polyester alone as the layer-forming polymer substance of the photosensitive layer 3, it is possible to obtain a higher resolution by mixing a chlorinated polyolefin. It is possible to improve the sharpness of the line and obtain an excellent image. The mixing ratio of linear saturated polyester and chlorinated polyolefin is
0.1 to 300 parts by weight of chlorinated polyolefin, and 0.5 to 10 parts by weight to 100 parts by weight of linear saturated polyester.
0 parts by weight, particularly 1.0 to 50 parts by weight are preferred.

The chlorinated polyolefin / linear saturated polyester system can of course be used even when the heat treatment is not carried out during the production of the printing plate.

The polymerizable compound contained in the photosensitive layer 3 may be the same as the polymerizable compound contained in the base layer 2, but is selected from a wide range of molecular weights from a small molecular weight to a large molecular weight. be able to. The preferred molecular weight range of the polymerizable compound contained in the photosensitive layer 3 is 8
It is 0 to 1,000,000, and more preferably 100 to 600,000.

When the polymerizable compound contained in the photosensitive layer 3 has a large molecular weight, the molecular weight is determined by polystyrene conversion using GPC (gel permission chromatography). When the molecular weight is small, the molecular structure of the polymerizable compound can be determined and the molecular weight can be determined.

The photopolymerization initiator contained in the photosensitive layer 3 may be the same as the photopolymerization initiator contained in the base layer 2.

Further, as the polymerizable compound contained in the photosensitive layer 3, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-, in addition to the above-mentioned polymerizable compound.
Tetrafluoropropyl (meth) acrylate, 1H,
Fluoro (meth) acrylates such as 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate; silicon di (meth) acrylate, silicon hexa (meth) acrylate, etc. Silicon (meth) acrylate can be used. It is preferable to use such a fluoro (meth) acrylate or silicon (meth) acrylate as the polymerizable compound contained in the photosensitive layer 3 because the water repellent property of the polymerized portion of the photosensitive layer 3 is improved.

The content of the layer-forming polymer substance in the photosensitive layer 3 is 20 to 80% by weight, and further 30 to 30% by weight based on the photosensitive layer 3.
70% by weight is preferred.

The polymerizable compound in the photosensitive layer 3 is contained in an amount of 10 to 300 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the layer-forming polymer substance.

The amount of the photopolymerization initiator is 100
0.1 to 30 parts by weight, more preferably 0.
3 to 25 parts by weight is preferable.

Further, various additives such as a thermal polymerization inhibitor for preventing dark polymerization during storage, a colorant and a plasticizer for improving the plate inspection property can be contained in the photosensitive layer 3 if necessary.

As the thermal polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, phenothiazine, pyrogallol, naphthylamine, β-naphthol, tert-butylcatechol and the like can be used.

As the colorant, for example, phthalocyanine type, azo type, methylene blue, crystal violet, rhodamine B and the like can be used.

As the plasticizer, for example, phthalic acid esters such as dicyclohexyl phthalate and dimethyl phthalate, glycol esters such as dimethyl glycol phthalate, and phosphoric acid esters such as triphenyl phosphate can be used.

The thickness of the photosensitive layer 3 is 0.2 μm to 50 μm.
m, preferably 0.3 μm to 20 μm, more preferably 0.3 μm to 10 μm, and particularly preferably 0.5 μm to 5 μm.

The peeling support layer 4 is a layer which is peeled from the printing original plate of the present invention for peeling and developing the photosensitive layer 3 after imagewise exposure, and the material thereof is, for example, polyethylene terephthalate, polypropylene, cellulose diacetate, cellulose triacetate, Cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, cellophane, methyl cellulose, ethyl cellulose, polyvinyl chloride, vinyl chloride copolymers such as vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, polystyrene,
Polyvinyl alcohol, polycarbonate, gelatin,
Polyamide (for example, 6-nylon, 6,6-nylon, 6,10-nylon, etc.) and the like can be mentioned.
Furthermore, it is also possible to use a mixture of two or more of these materials, or a laminate.

When the substrate 1 and the base layer 2 transmit the light having the absorption wavelength of the photopolymerization initiator contained in the photosensitive layer 3, the peeling support layer 4 does not need to be light transmissive. Considering the resolution, it is preferable to use the peeling support layer 4 having light transmittance.

The peeling support layer 4 has a thickness of 0.5 μm to 30 μm.
The thickness is preferably 0 μm, more preferably 2 μm to 50 μm, and when exposure is performed from the side of the release support layer 4, the thinner the film, the better the resolution, which is desirable.

The photosensitive silver salt layer 5 shown in FIGS. 2 and 3 contains at least a photosensitive silver halide, an organic silver salt, and a reducing agent (a so-called 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 the aromatic carboxylic acid include benzoic acid derivative, quinolinic acid derivative, naphthalenecarboxylic acid derivative,
Salicylic acid derivative, gallic acid, tannic acid, phthalic acid,
Examples include phenylacetic acid derivatives and pyromellitic acid.

As the thiocarbonyl group compound having a mercapto group or α-hydrogen, 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, methcaptooxadiazole or 3-amino-5-benzylthio-1,2,
The mercapto compounds described in U.S. Pat. No. 4,123,274, such as 4-triazole, can be mentioned.

Examples of the compound containing an imino group include benzotriazole or its derivatives described in JP-B-44-30270 or 45-18416, such as alkyl-substituted benzotriazoles such as bezotriazole and methylbenzotriazole, 5 -Halogen-substituted benzotriazoles such as chlorobenzotriazole, carboimide benzotriazoles such as butylcarbimide benzotriazole, nitrobenzotriazoles described in JP-A-58-18639, and JP-A-58-115.
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof described in Japanese Patent No. 638, hydroxybenzotriazole and the like, US Pat. No. 4,220,709.
Typical examples include 1,2,4-triazole, 1H-tetrazole, carbazole, saccharin, imidazole and derivatives thereof described in Japanese Patent No.

As the reducing agent, a compound that reduces an organic silver salt to produce silver and forms a blackened image by a silver image, or the reducing agent itself forms an image by an oxidant changed by a reaction with an organic silver salt. Compounds are 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, dihydroxynaphthalene, trihydroxynaphthalene, dihydroxybenzenes, trihydroxybenzenes, tetra Hydroxybenzenes, hydroxyalkyl monoethers, ascorbic acids, 3-pyrazolidones, pyrazolines, pyrazolones, phenylenediamines, hydroxyamines, reductones, hydrooxamic acids, hydrazides, amidoximes, N-
Hydroxyureas may be mentioned, and specific examples of these compounds are described in JP-A-51-22431, US Pat. Nos. 3,615,533 and 3,679,426.
No. 3,672,904, No. 3,751,252
No. 3,751,255, No. 3,782,94
No. 9, No. 3,801,321, No. 3,794,4
55, No. 3,893,863, No. 3,887,
No. 376, Belgian Patent No. 786,086, US Patent Nos. 3,770,448 and 3,819,382.
No. 3,773,512, No. 3,928,68
No. 6, No. 3,839,048, No. 3,887,3
78, JP-B-51-35851, JP-A-50-
36143, U.S. Pat. No. 3,827,889.
No. 3,756,829, JP-A-50-3611
No. 0, JP-A-50-116023, JP-A-5
0-147711, JP-A-51-23721, JP-A-50-99719, and JP-A-51-32.
No. 324, Japanese Patent Laid-Open No. 51-51923, Japanese Patent Laid-Open No. 50-140113, and Japanese Patent Laid-Open No. 52-84727. 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 preferable, and as a reducing agent that forms such oxidant, Aromatic hydroxy compounds are preferred. Hereinafter, the aromatic hydroxy compounds will be described in detail.

In the compounds represented by the following general formulas (1) and (2), the oxidant produced by the redox reaction with the organic silver salt emits light in the absorption wavelength range of the photopolymerization initiator in the photosensitive layer 3. It is an aromatic hydroxy compound that develops the ability to inhibit polymerization by absorption.

[0085]

[Outer 1] (However, in the general formulas (1) and (2), r ¹ , r ² and r ³ are each independently 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, alkoxy Represents a group, m is a positive number of 1 to 3, Y is a monovalent to trivalent linking group, a substituted or unsubstituted aralkyl group, a substituted amino group, an alkylidene group, a substituted or unsubstituted aralkylidene group,
Represents a methine group, and Z represents an alkylidene group or a substituted or unsubstituted aralkylidene group. )

In the above general formulas (1) and (2), the unsubstituted alkyl group is a linear or branched alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl,
Examples thereof include i-propyl, butyl, t-butyl, i-butyl, amine, i-amine, sec-amyl, thexyl, hexyl, heptin, octyl, nonyl, dodecyl, stearyl and the like.

The substituted alkyl group is an alkoxyalkyl group having 2 to 18 carbon atoms, a halogenalkyl 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,
Examples of the alkoxyalkyl group include methoxyethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxymethyl, propoxybutyl, i.
-Propoxypentyl, t-butoxyethyl, hexyloxybutyl and the like can be mentioned.

Examples of the halogen alkyl group include chloromethyl, chloroethyl, bromoethyl, chloropropyl, chlorobutyl, chlorohexyl, chlorooxyl and the like.

Examples of the hydroxyalkyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl,
Examples thereof include 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. The aralkyl group includes 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, ptooxy 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, ethoxyethyl, 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.

As the reducing agent represented by the general formula (1),
For example, 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'-methylidenebis (2-t-butyl-6-methylenephenol), 4,4'-ethyldenbis (2,6-di-t-butylphenol) 4,4'-ethylidenebis (2-t-butyl-6-) Methylphenol), 4,4 '
-Propylidene bis (2,6-di-t-butylphenol), 4,4-butylidene bis (2,6-di-t-butylphenol), 4,4'-butylidene bis (2-cyclohexyl-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.

As the reducing agent represented by the general formula (2),
For example, 4,4-methylenebis (2-methyl-1-naphthol), 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 reducing agents represented by the general formulas (1) and (2) can form a polymer image with good contrast by selecting the photopolymerization initiator in the photosensitive layer 3.

For example, as a reducing agent, 4,4'-methylenebis (2-methyl-6-t-butylphenol), 4,
When 4'-methylenebis (2,6-di-t-butylphenol) or the like is used, a photopolymerization initiator having sensitivity at 380 nm to 390 nm, for example, 2-chlorothioxanthone, 2-methyloxanthone, 2,4 -Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,
4,6-Trimethylbenzoyldiphenylphosphine oxide, benzyl and the like are preferable.

As the reducing agent, 4,4'-methylenebis (2-methyl-1-naphthol), 4,4'-methylenebis (2-ethyl-1-naphthol), 4,4'-methylenebis (2-t) -Butyl-1-naphthol) or the like is used, a photopolymerization initiator having a sensitivity in the range of 400 nm to 500 nm, such as 2,4-dichlorothioxanthone, camphorquinone, 3,3′-carbonylbis (7
-A combination of coumarins such as diethylaminocoumarin) and tris (trichloromethyl) triazine, 2-
A combination of (p-dimethylaminostyryl) -4,5-diphenylthiazole and 3-phenyl-5-isoxazolone, a combination of a merocyanine dye and 3-phenyl-5-isoxazolone, and the like are preferable.

The preferred compounding ratio of the above components of the photosensitive silver salt layer 5 in the printing original plate of the present invention is as follows.

The amount of organic silver salt contained in the photosensitive silver salt layer 5 is 0.3 to 30 g / m ² , particularly 0.7 to 15 g / m ² .
² , more preferably 1.2 to 8 g / m ² .

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.

The thickness of the photosensitive silver salt layer 5 is from 0.05 μm to
It is preferably 1 mm, more preferably 0.3 μm to 30 μm.

A protective layer 6 is preferably provided on the photosensitive silver salt layer 5. The protective layer 6 has a function of preventing the photosensitive silver salt layer 5 from adhering or sticking to another substance, and preventing permeation of moisture in the atmosphere.

As the protective layer 6, the same material as that of the peeling support layer 4 can be used. The thickness of the protective layer 6 is 0.2 μm to 300 μm, more preferably 0.5 μm to 5 μm.
0 μm is preferable, and 0.5 μm to 20 μm is more preferable.

The protective layer 6 may contain a light-absorbing dye to have an effect of filtering light in a designated wavelength region. In addition, additives suitable for the purpose may be added as necessary.

In the second mode, as shown in FIG.
It is also possible to provide an intermediate layer 7 between the photosensitive layer 3 and the photosensitive silver salt layer 5. As the intermediate layer 7, a film having a good light transmittance in the photosensitive wavelength region of the photosensitive layer 3 and having a uniform surface. Is preferably used. The intermediate layer 7 can be made of the same material as the peeling support layer 4. As the thickness of the mid layer 7,
The thickness is preferably 0.5 μm to 300 μm, more preferably 2 μm to 50 μm.

See also An antihalation dye may be contained in the intermediate layer 7 in order to prevent halation, or an antihalation layer may be provided between the intermediate layer 7 and the photosensitive silver salt layer 5.

The intermediate layer 7 prevents mixing of the constituent components of both layers due to thermal diffusion, which may occur when the photosensitive layer 3 and the photosensitive silver salt layer 5 are directly laminated, to improve the storage stability. It has the effect of promoting or preventing the components of both layers from mixing at the time of coating, and since it is possible to prevent the components of both layers from being mixed, the material selection for both layers is facilitated and the selection range Can be extended.

In the present invention, the contact angle of the photosensitive layer 3 (contact angle with water; hereinafter the same) is preferably larger than the contact angle of the base layer 2. The contact angle of the photosensitive layer 3 is 60 ° or more, more preferably 70 ° or more and 130 ° or less. or,
The contact angle of the base layer 2 is 58 ° or less, 50 ° or less, especially 2
It is preferably 0 ° or less and 1 ° or more.

When the contact angle of the photosensitive layer 3 and the contact angle of the base layer 2 are set as described above, it is very effective when printing is performed using a fountain solution described later.

Next, the method for producing the printing plate of the present invention will be described. First, a method for manufacturing a printing plate using the printing original plate of the first aspect will be described.

As shown in FIG. 1, a base layer 2 containing a polymerizable compound was coated on the substrate 1, and a release layer 4 prepared separately was coated with the photosensitive layer 3. The base layer 2 and the photosensitive layer 3 are laminated so as to be in contact with each other to manufacture the printing original plate of the first aspect. When laminating, it is preferable to apply heat, 20 ° C to 150 ° C
C., more preferably 30.degree. C. to 100.degree. C., especially 40.degree.

Further, the base layer 2 and the photosensitive layer 3 are sequentially coated on the substrate 1, and then the release support layer 4 is laminated or coated to manufacture the printing original plate of the first aspect. Good.

Then, in the image exposure step, the photosensitive layer 3 is image-exposed with light having the absorption wavelength of the photopolymerization initiator contained in the photosensitive layer 3 through a desired mask 8 as shown in FIG. The polymerizable compound in the photosensitive layer 3 is polymerized to form a latent image composed of a polymerized portion 3-a and an unpolymerized portion 3-b corresponding to the pattern of the mask 8.

In the case of the printing original plate of the first aspect, the wavelength of light used in the image exposure step is preferably 300 to 600 nm.

As the mask 8, a mask having a light transmitting portion and a non-light transmitting portion is used.

Further, analog exposure other than mask exposure, digital exposure and the like may be used, and examples of the exposure light source include sunlight, a tungsten lamp, a mercury lamp, a halogen lamp, a xenon lamp and a fluorescent lamp. Further, examples of the exposure without using a mask include a liquid crystal shutter array, a CRT, an optical fiber tube and the like. Besides, laser beams, electron beams, X-rays and the like may be used.

In this exposure process, it is very preferable to perform heating at the same time as the exposure, and the effect of increasing the polymerization rate of the polymerizable compound and the relaxation of the matrix of the layer-forming polymer substance of the base layer 2 are obtained. The polymerizable compound contained in the photosensitive layer 3 and the polymerizable compound contained in the photosensitive layer 3 are easily bonded to each other, and the printing durability is further improved.

The heating means is not particularly limited, but it is preferable to use a hot plate, a heat roll, a thermal head or the like.

The heating temperature depends on the composition of the photosensitive layer 3, the composition of the base layer 2 (particularly the layer-forming polymer substance), and is preferably 30 ° C to 150 ° C, more preferably 50 ° C to 120 ° C.

As shown in FIG. 5, the peeling support layer 4 is peeled off from the printing original plate on which the polymerization latent image is formed thus obtained. At this time, the peeling support layer 4 includes the photosensitive layer 3
The unpolymerized portion 3-b of the above is adhered, and the unpolymerized portion 3-b is also peeled and removed at the same time.

Through the above process, a printing plate on which the polymerized portion 3-a of the photosensitive layer remains on the base layer 2 is obtained.

It is of course possible to perform printing using this printing plate, and printing durability is also preferable, but here, this printing plate is further subjected to heat treatment using a hot plate, heat roll, or the like. It is preferable that the printing durability is further improved.

The heating temperature depends on the composition of the photosensitive layer polymerized portion 3-a, the glass transition temperature, the softening temperature, the hydrophilic layer composition, etc., but is preferably 50 ° C. to 200 ° C., more preferably 80 ° C. to 180 ° C.

Further, it is also preferable to subject the printing plate to a pressure treatment using a press, a roll or the like, so that the printing durability can be further improved. Further, both heat treatment and pressure treatment may be performed.

The pressure to be applied is as follows:
It is preferable that a does not collapse, 0.2 kg / cm ² ~
15 kg / cm ² , further 1 kg / m ^{2 to} 10 kg / cm
² is preferable.

Further, it is also preferable to expose the printing plate with the light used in the image exposure step, and this re-exposure improves the printing durability. By this re-exposure, the photopolymerization initiator remaining in the polymerized portion 3-a of the photosensitive layer 3 reacts to react with the unreacted polymerizable compound of the polymerized portion 3-a and the unreacted polymerizability of the base layer 2. It is considered that the compound binds to the compound and contributes to the improvement of printing durability. In this re-exposure step, it is also very preferable to heat or pressurize at the same time as the exposure, which is effective for further improving the printing durability. In particular, in the re-exposure step, heating is performed at the same time as exposure by hot plate,
Thereafter, when heating and pressurizing are further performed by a heat lot roll or the like, printing durability is remarkably improved.

The printing original plate of the second aspect shown in FIG. 2 can be manufactured by sequentially coating or laminating each layer.
The printing original plate shown in FIG. 3 can be manufactured, for example, as follows.

That is, the photosensitive layer 3 is coated and formed on the intermediate layer 7 such as polyethylene terephthalate, and a protective film such as a fluororesin film or a silicone-coated plastic film is temporarily laminated on the photosensitive layer 3. .. This protective film is different from the protective layer 6 shown in FIG. 2 and FIG. 3 and is temporarily laminated so that the photosensitive layer 3 is not scratched or dusted during the process of manufacturing the printing plate precursor. , Immediately before laminating the base layer 2.

The fluororesin system used in this protective film includes, for example, polytetralfluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-hexa. There are fluoropropylene-perfluoroalkyl vinyl ether copolymers and the like.

Next, a photosensitive silver salt layer 5 is formed on the surface of the intermediate layer 7 opposite to the photosensitive layer 3, and a protective layer 6 is further formed on the photosensitive silver salt layer 5.

Separately, the base layer 2 is formed on the substrate 1, and the photosensitive layer 3 from which the protective film is removed and the base layer 2 are laminated. Thus, the printing original plate shown in FIG. 3 is obtained.

A method of manufacturing a printing plate using the printing plate shown in FIG. 3 will be described below, but the same applies to the case of using the printing plate shown in FIG.

First, in the image exposure process, as shown in FIG. 6, a desired image is exposed (hν ₁ ) on the photosensitive silver salt layer 5 by image exposure or digital exposure. As a result, the exposure unit 5
Silver nuclei 9 are formed on the photosensitive silver halide salt in -a, which forms a latent image. The generated silver nuclei 9 serve as a catalyst for the thermal reaction between the organic silver salt contained in the photosensitive silver salt layer 5 and the reducing agent.

Since the printing plate precursor of the second aspect contains the photosensitive silver halide, writing with high sensitivity becomes possible,
Direct drawing is possible by digital processing using laser, LED, etc.

Next, in the thermal development process shown in FIG. 7, when the photosensitive silver salt layer 5 on which the latent image is formed is heated, the exposed portion 5 is exposed.
In −a, the silver nuclei 9 selectively act as a catalyst, the organic silver salt and the reducing agent react, the organic silver salt is reduced to the silver atom 10, and at the same time, the reducing agent becomes the oxidant 11.

The heating temperature in this heat development process cannot be generally determined depending on the composition of the photosensitive layer 3 and the like, but is 60 ° C. to 200 ° C., more preferably 70 ° C. to 150 ° C., and 1 second to 5 minutes. Preferably, the heat treatment may be performed for 3 seconds to 60 seconds. Generally, a high temperature requires a short time, and a low temperature requires heating for a long time. As a heating means, in addition to a method using a hot plate, a heat roll, a thermal head, etc., a heating method by laser light irradiation and the like can be used.

Then, as shown in FIG. 8, in the polymerization exposure process, polymerization exposure (hν ₂ ) is performed from the photosensitive layer 3 side to cleave the photopolymerization initiator contained in the photosensitive layer 3 to remove radical species. generate. The radical species causes a polymerization reaction of the polymerizable compound to form a polymerized portion in the photosensitive layer 3. At that time, in the exposed portion 5-a of the photosensitive silver salt layer 5, the black silver atoms 10 and the oxidant 11 absorb light, so that in the portion of the photosensitive layer 3 corresponding to the exposed portion 5-a, the photosensitive layer is exposed. The polymerizable compound in 3 does not polymerize (unpolymerized part 3-b), but polymerization occurs in the part corresponding to the unexposed part 5-b (polymerized part 3-a), and as a result a polymerization latent image is formed. ..

As the light source used in the image exposure process and the polymerization exposure process, for example, sunlight, a tungsten lamp, a mercury lamp, a halogen lamp, a xenon lamp, a fluorescent lamp, an LED, a laser beam or the like can be used and can be directly drawn or
Exposure can be performed through the same mask as described above, and the wavelengths of light used in these processes may be the same or different. Even when light of the same wavelength is used in both processes, since silver halide usually has a sufficiently higher photosensitivity than a photoinitiator, it is sufficient that the intensity of light is such that photopolymerization does not occur in the image exposure process. You can write a latent image. A sensitizing dye may be added at the time of forming the photosensitive layer according to the color distribution of each light source.

Specifically, the wavelength of light during the polymerization exposure is preferably 300 to 600 nm, and the wavelength of the light during the image exposure is 50 when the photosensitive silver salt layer contains a sensitizing dye.
0 to 1000 nm, particularly 500 to 900 nm is preferable, and when no sensitizing dye is contained, 300 to 500 nm is preferable.

Further, it is preferable to heat the printing plate during the exposure in the polymerization exposure step, and although it may be newly heated or residual heat may be utilized in the above-mentioned thermal development step, the organic silver salt in the photosensitive layer It is necessary to heat under conditions where the redox reaction of the reducing agent does not occur, and the conditions vary depending on the combination of the organic silver salt and the reducing agent, but the heating temperature is approximately 120 ° C or lower, preferably 90 ° C or lower, and more preferably Is 60 ° C. or lower.

As shown in FIG. 9, the intermediate layer 7 is peeled off from the base layer 2 in the peeling and developing process with respect to the printing plate having the polymerization latent image thus obtained. At this time, the unpolymerized part 3-b of the photosensitive layer 3 is adhered to the intermediate layer 7, and the unpolymerized part 3-b is also peeled off at the same time. In this way, a printing plate in which the polymerized portion 3-a of the photosensitive layer 3 remains on the base layer 2 is obtained.

It is of course possible to carry out printing using this printing plate, and printing durability is also preferable, but here, as in the method for producing a printing plate using the printing plate precursor of the first aspect,
It is preferable to subject the manufactured printing plate to re-exposure, heat treatment or pressure treatment, so that printing durability can be further improved.

Using the printing plate produced as described above, it is possible to carry out printing with dampening water and printing ink, or only printing ink without dampening water.

As a printing apparatus using the printing plate according to the present invention, a conventional printing apparatus can be used. For example, a lithographic printing machine can be used, and a desktop type or floor type offset printing machine used in the field of light printing is suitable, but the present invention is not limited to this.

An example of a printing apparatus using the printing plate manufactured by the printing plate manufacturing method of the present invention will be described below with reference to FIG.

In the printing apparatus shown in FIG. 10, the printing plate 13 manufactured by the printing plate manufacturing method of the present invention is attached to the plate cylinder 12. As a mounting method, a chuck used in a normal offset printing machine may be used, but the mounting method is not limited to this.

Ink is supplied to the printing plate 13 by the ink supply means. In the example shown in FIG. 10, a plurality of ink supply rollers 14 are used as the ink supply means, and the ink 16 in the ink fountain 15 is supplied onto the printing plate 13 by the plurality of ink supply rollers 14.

When a lipophilic ink is used as the ink 16, before the ink 16 is supplied to the printing plate 13,
The dampening water 17 is supplied. That is, by the rotation of the plate cylinder 12 in the direction of arrow A, the dampening water 17 is first supplied to the plate cylinder 12, and then the ink 16 is supplied.

By doing so, the dampening water 17 is held and the ink 16 does not adhere to the non-image portion of the printing plate 13, that is, the base layer. On the other hand, the dampening water 17 is repelled and the ink 16 is attached to the image portion of the printing plate 13, that is, the superposed portion of the photosensitive layer. The dampening water 17 is supplied from the dampening water reservoir 19 to the printing plate 13 by a plurality of dampening water supply rollers 18.

The printing plate 13 is contacted with the blanket cylinder 20 which rotates in the opposite direction to the plate cylinder 12, and the blanket cylinder 20
Further, an impression cylinder 21 as a transfer means is in contact with the. Impression cylinder 2
1 rotates in the opposite direction to the blanket cylinder 20. In this way, the ink 16 on the printing plate 13 is first transferred to the blanket cylinder 2
0, and then transfer onto the recording medium 22 passing between the blanket cylinder 20 and the impression cylinder 21 to complete printing.

The recording mediums 22 such as paper and plastic are stored in the cassette 23, and are fed one by one from the cassette 23 by the rollers 24. The recording medium 22 for which printing has been completed is discharged to the tray 25.

The number of the ink supply rollers 14 is not particularly limited, and is about 4 to 20 in consideration of the kneading condition of the ink and the ink thickness. The number of dampening water supply rollers 18 is not limited, and is about 2 to 10.

In some cases, the ink on the printing plate 13 may be directly transferred to the recording medium 22 without providing the blanket cylinder 20, but the durability of the plate and the rough paper (paper with poor smoothness).
In consideration of printing on, so-called offset printing through a blanket cylinder is preferable.

In the example shown in FIG. 10, the ink supply means and the dampening water supply means are provided separately, but the dampening water is supplied onto the ink supply roller 14 to simultaneously supply the ink and the dampening water. It can also be supplied on the printing plate 13. In this way, the apparatus becomes compact, so that it can be used as a desk-top type offset printing machine.

Although the rotary type printing apparatus has been described above, the printing apparatus using the planographic printing plate according to the manufacturing method of the present invention is not limited to this, and may be, for example, a flatbed type printing apparatus. The flatbed type printing apparatus is a printing apparatus in which a printing plate mounting portion (which corresponds to the plate cylinder 12 in FIG. 10) is a flatbed.

In the printing as in the example shown in FIG. 10, as in the case of the desensitizing treatment of ordinary lithographic printing, dampening water, water or a normal etchant is applied to the hydrophilic portion of the printing plate in advance. It is preferable that the plate is kept in a water-retaining state and then attached to the plate cylinder for printing. It is also possible to print after mounting the plate on the plate cylinder and keeping it in a water-retaining state.

In the example of FIG. 10, the lipophilic ink is used for description, but a hydrophilic ink may be used.
In this case, the hydrophilic ink adheres only to the easily wettable portion of the plate for printing.

Further, the printing plate according to the present invention can be a "waterless planographic plate" which does not require dampening water during printing. To make a printing plate according to the present invention a waterless planographic plate,
The base layer 3 shown in FIGS. 3A to 3C may be ink repellent (a property that ink does not adhere). In order to make the base layer 3 ink repellent, a silicone resin or a fluororesin is used as the layer-forming polymer substance contained in the base layer 3, and a silicone (meth) acrylate or a polymerizable compound contained in the base layer 3 is used. Fluoro (meth) acrylate may be used.

When the printing plate according to the present invention is a waterless planographic plate,
The printing apparatus shown in FIG. 10 can be used without the dampening water 17, the dampening water supply roller 18, and the dampening water sump 19.

The ink used in the printing method of the present invention includes:
Usual inks that have been conventionally used for printing can be used. Inks used for printing include lipophilic inks and hydrophilic inks.

The lipophilic ink is an ink composed of dye and pigment, oil, resin, solvent, plasticizer and the like. Examples of oils include vegetable oils, processed oils and mineral oils. Examples of the resin include natural resins such as rosin and shellac, and synthetic resins such as phenol-based and ketone-based resins.
The solvent is preferably a solvent that has appropriate dissolving power and diluting power with respect to the resin contained in the ink, has a desired evaporation rate, and can give necessary viscosity and fluidity to the entire ink. Examples of such a solvent include aliphatic hydrocarbons such as n-hexane, aromatic hydrocarbons such as cyclohexane and toluene, esters such as methyl acetate and ethyl acetate, alcohols such as methyl alcohol and ethyl alcohol, acetone and methyl ethyl ketone. Various solvents such as ketones, glycols such as ethylene glycol, propylene glycol and dipropylene glycol, glycol ethers and glycol ether esters can be used.
Moreover, these can be mixed and used according to a desired characteristic. The plasticizer is flexible to the dry film of the ink,
Provides flexibility and cold resistance. Phthalates such as diptyl phthalate and dioctyl phthalate, esters such as adipic acid and citric acid, chlorinated paraffin, castor oil, epoxy plasticizers, polyester plasticizers, etc. Is used.

Examples of dyes and pigments include inorganic or organic pigments such as titanium oxide, carbon black, bronze powder, diazo yellow and phthalocyanine blue. Further, as a powdery colored developer other than the dye and pigment,
For example, a powder obtained by dispersing a dye or pigment or a metal powder in a polymer compound such as polystyrene can be used. The average particle size of the above-mentioned dyes and pigments and other powdery colored developers is preferably 0.
It is 1 μm to 20 μm, and preferably 1 μm to 5 μm.

The hydrophilic ink contains the above-mentioned desired dyes and pigments, and the like, for example, a water-soluble polymer such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and the like, an auxiliary agent such as a surfactant and water as a solvent. It is a water-soluble ink containing.

As described above, according to the present invention, since the base layer contains the polymerizable compound, it exhibits a strong interaction with the polymerized portion of the photosensitive layer, and is much more durable than the conventional one. It has the effect of improving printability.

Further, according to the present invention, since the photosensitive layer can be peeled off and developed, a printing plate can be produced simply, quickly and by a dry process, and it is excellent in resolution, line breakage, etc. A printing plate having excellent heat resistance can be obtained by using a specific composition.

Furthermore, since a photosensitive dry silver salt layer containing a photosensitive silver halide can be laminated on the printing plate precursor of the present invention, high-sensitivity writing is possible, and a plate can be directly drawn by a laser to make a plate. You can also do it.

[0173]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Moreover, "part" in the following description is part by weight.

Example 1 One side of a high-quality paper having a basis weight of 140 g / m ^{2 and} having excellent sizing degree, water resistance, and smoothness mainly composed of long-fiber pulp (the other side was treated to be water resistant with a polyester resin) Then, a solution having the following composition was applied using a wire bar to a dry film thickness of 15 μm to obtain a base layer.・ Polyvinyl alcohol (Product name Gohsenol NH-1
8, 10% aqueous solution of Nippon Synthetic Chemical Industry Co., Ltd. 10
Part-Colloidal silica (product name Snowtex-O, manufactured by Nissan Chemical Industries, Ltd.) 2.7 part-Pentaerythritol triacrylate (product name KA)
YARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.
4 copies

Next, a polyethylene terephthalate film (trade name: Lumirror T, manufactured by Toray Industries, Inc.) having a thickness of 9 μm was used as a peeling support layer, and a solution having the following composition was dried to a thickness of 2 to 3 μm on the peeling support layer. Thus, coating was performed using a wire bar to obtain a photosensitive layer.・ Chlorinated rubber (Product name: Supercron CR-5, Sanyo Kokusaku Pulp Co., Ltd.) 5.0 parts ・ Oligoester acrylate (Product name: Aronix M
6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2,4-diethylthioxanthone (trade name, KAYA)
CURE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts ・ Ethyl 4-dimethylaminobenzoate (trade name, KAY)
ACURE EPA, manufactured by Nippon Kayaku Co., Ltd.) 0.75
Part-hydroquinone monomethyl ether 0.01 part-copper phthalocyanine pigment 0.1 part-methyl ethyl ketone 15 parts-toluene 15 parts

Further, the base layer and the photosensitive layer are brought into contact with each other and 50
Laminator heated to ℃ (nip pressure 5 Kgf / cm
^The original plate for printing of the present invention was obtained by passing through ² ).

A negative image was used as a mask on the release support layer of this printing original plate, and exposure was carried out through this mask to form a latent image for polymerization. For the exposure at that time, an ultra-high pressure mercury lamp was used as a light source, and the light source was separated from the original plate by about 10 cm.
It went for 0 seconds.

Then, when the polyethylene terephthalate film as the release supporting layer was released, the unexposed portion of the photosensitive layer was also adhered to the polyethylene terephthalate film and released at the same time, and as a result, the exposed portion of the photosensitive layer remained on the base layer. I got a printing plate.

After sufficiently wetting this printing plate with deionized water, it was mounted on the plate cylinder 12 of the printing apparatus shown in FIG. 10, and ink (trade name: BSD New Rubber Ink Silver, Bunshodou Co., Ltd.), dampening water (deionized water) was added, respectively, and the printer was operated.
First, the dampening water is supplied onto the plate via the dampening water supply roller 18, and then the ink is supplied onto the plate via the ink supply roller 14, so that the ink is attached onto the base layer which is a non-image portion. Although not done, ink adhered to the exposed area (polymerized area) of the photosensitive layer which is the image area. Then, by bringing this plate (plate cylinder) into contact with the blanket cylinder 20, the ink is transferred and attached to the blanket cylinder 20, and the plain paper conveyed by the rollers 24 from the cassette 23 is further transferred to the blanket cylinder 20 and the impression cylinder 21. The ink was transferred by the blanket cylinder 20 as it passed between the two, and was ejected to the tray to obtain a printed matter.

The printing speed here was 120 sheets / minute.

In printing 3000 sheets by the above printing, a good black printed image without background stain was obtained, and no remarkable peeling of the image portion was observed, but peeling of the edge portion was not a problem in practical use. It happened to some extent.

Example 2 The printing plate produced in Example 1 was placed on a hot plate heated to 50 ° C., and the light source of Example 1 was used for exposure for 120 seconds. Example 1
When printing was performed in the same manner, the printing durability was improved and 3000
In printing one sheet, a good printed image without background stain was obtained, and peeling of the edge of the image portion did not occur.

Example 3 A solution having the following composition was coated on one surface of the woodfree paper used in Example 1 using a wire bar so as to have a dry film thickness of 15 μm, to obtain a base layer.・ Polyvinyl alcohol (Product name Gohsenol NH-1
8. 10% aqueous solution of Nippon Synthetic Chemical Industry Co., Ltd. 7.
3 parts-Colloidal silica (trade name Snowtex-O, manufactured by Nissan Chemical Industries, Ltd.) 2.7 parts-2-hydroxyethyl methacrylate (trade name, light ester HO, manufactured by Kyoeisha Yushi-Kagaku Co., Ltd.) 4.0
Department

Next, with respect to the photosensitive layer used in Example 1,
The base layer was laminated in the same manner as in Example 1 to obtain the printing original plate of the present invention.

Using this printing original plate, a printing plate was produced in the same manner as in Example 1, and further printing was carried out.
When printing 0 sheets, a good printed image with no background stain was obtained. However, on the 1500th sheet, some peeling of the image area was observed to the extent that there was no practical problem.

Comparative Example 1 The base layer formulation of Example 1 does not contain the polymerizable compound pentaerythritol triacrylate,
Other than that, when a printing original plate and a printing plate were manufactured in the same manner as in Example 1 and printing was performed, peeling was observed in a part of the image portion in printing of only 10 sheets, and in the 50th sheet, The entire image area was peeled off, and a printed image could not be obtained.

Example 4 The printing plate produced in Example 3 was heated on a heat roll (nip pressure, 5 Kgf / cm).
^{After 2} ), when printing was performed in the same manner as in Example 3, the printing durability was improved as compared with Example 3, and a good printed image without scumming was obtained after printing 1500 sheets, No peeling of the image portion was observed, but in the 2000th sheet, peeling of a part of the image portion was observed, but there was no practical problem.

Example 5 In Example 3, in the image exposure process during the production of the printing plate, a printing plate was prepared by using a hot plate at the same time as the image exposure.
After heating at 0 ° C., and then producing a printing plate in the same manner as in Example 2 and performing printing, the printing durability was further improved as compared with Example 4, and there was no scumming when printing 2000 sheets. A clear printed image was obtained, and no peeling of the image part was observed.

Example 6 The printing plate produced in Example 5 was heated on a heat roll (nip pressure, 5 Kgf / cm).
^{After 2} ), a printing plate was produced in the same manner as in Example 5, and printing was carried out. A good printed image free of background stain was obtained after printing 2500 sheets, and the image area was peeled off. I couldn't see it.

Example 7 A solution having the following composition was dried to a thickness of 15 μm on a surface of a 100 μm-thick polyester film (trade name AC- (D), manufactured by Panak Kogyo Co., Ltd.) which had been subjected to the easy-adhesion treatment to give an easily adhered surface. Was applied using a wire bar to obtain a base layer. Acrylonitrile 26 parts of polyoxyalkylene monomer _{(CH 2 = C (CH 3} ) CO- (COH 2 CH 2) 30
OCH ₃ ) 74 parts copolymer 4.2 parts Water-dispersible acrylic resin (manufactured by Nippon Shokubai Kagaku Kogyo KK,
Acrylic EX-15) 33.3 parts-Surfactant (Emulgen 909, manufactured by Kao Corporation)
8.4 parts-Butyl cellosolve 12.1 parts-Deionized water 42.1 parts-Trimethylolpropane triacrylate (trade name K
AYACURE TMPTA, manufactured by Nippon Kayaku Co., Ltd.
0.7 copy

Then, a base layer was laminated on the photosensitive layer used in Example 1 in the same manner as in Example 1 to obtain a printing original plate of the present invention.

Using this printing original plate, a printing plate was produced in the same manner as in Example 1 and further printing was carried out. As a result, 1000 or more good printed images were obtained.

Comparative Example 2 In the formulation of the base layer of Example 7, a printing base plate and a printing plate were prepared in the same manner as in Example 7, except that the polymerizable compound trimethylolpropane triacrylate was not contained. Manufactured and printed, only 1
It was not possible to print 0 sheets, and the entire image area was peeled off.

Example 8 A polyethylene terephthalate film (trade name: Lumirror T, manufactured by Toray Industries, Inc.) having a thickness of 6 μm was used as an intermediate layer, and a solution having the following composition was used on the intermediate layer in the same manner as in Example 1. A photosensitive layer was formed.・ Linear saturated polyester resin (trade name: Byron 200,
4.5 parts by Toyobo Co., Ltd. ・ Chlorinated polyolefin (trade name: Super Klon 51)
0, Sanyo Kokusaku Pulp Co., Ltd. 0.5 part ・ Oligoester acrylate (trade name Aronix M
-6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYAC)
URE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 part ・ Ethyl 4-dimethylaminobenzoate (trade name KAYA)
CURE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Hydroquinone monomethyl ether 0.01 parts Copper phthalocyanine pigment 0.1 parts Methyl ethyl ketone 15 parts Toluene 15 parts

A protective film having a thickness of 25 μm was temporarily laminated on the photosensitive layer. As the protective film, a polyethylene terephthalate film coated with release silicone (trade name: Lumirror Silicone coating, manufactured by Toray Industries, Inc.) was used. -AgBr 0.9 parts-Silver behenate 5.0 parts-Behenic acid 4.0 parts-Phthalazinone 0.1 parts 2-Methyl-4- (3,5-di-tert-butyl-)
4-hydroxybenzyl) -1-naphthol 2.6 parts Polyvinyl butyral (trade name S-REC BM-2,
Sekisui Chemical Co., Ltd. 10 parts ・ Methyl ethyl ketone 90 parts ・ Xylene 50 parts ・ n-Butanol 30 parts

A solution prepared by dissolving 0.001 part of a sensitizing dye compound represented by the following general formula in 1.0 part of N, N-dimethylformamide was added to the above composition in a dark room.

[0197]

[Outside 2] Using a paint shaker, thoroughly dissolve, disperse and mix,
An emulsion for the photosensitive silver salt layer was obtained. This emulsion for a photosensitive silver salt layer was formed on the surface of the intermediate layer opposite to the photosensitive layer to give a dry film thickness of 4
It is coated with a wire bar so as to have a thickness of ˜5 μm to form a photosensitive silver salt layer, and a 10% aqueous solution of polyvinyl alcohol (trade name Gohsenol NH-17Q, manufactured by Nippon Gosei Co., Ltd.) is used as a protective layer on the photosensitive silver salt layer. Chemical Industry Co., Ltd.)
Was coated using a wire bar so as to have a dry film thickness of 2 to 3 μm.

Then, the polyethylene-coated polyethylene terephthalate film laminated on the photosensitive layer was peeled off, and the base layer of the high-quality paper formed on the photosensitive layer in the same manner as in Example 1 was processed in the same manner as in Example 1. Lamination was performed to obtain a printing original plate of the present invention.

A Hem-Ne laser (output: 5 m) was applied to this printing original plate from the protective layer side of the printing original plate using a drum scan type laser beam printer (manufactured by Abe Design Co., Ltd.).
Imagewise exposure was performed at W), then heating was performed at 100 ° C. for 10 seconds, and then the entire surface was exposed for 20 seconds from a distance of 10 cm using a fluorescent lamp having a fluorescent peak at 380 nm. Thus, the photosensitive layer was polymerized in response to image exposure, and then the 6 μm-thick polyethylene terephthalate film as the intermediate layer was peeled off from the printing original plate, and the unpolymerized portion was adhered to the polyethylene terephthalate film and removed.
As a result, a printing plate was obtained in which the polymerized portion of the photosensitive layer remained on the base layer.

[0200] Using this printing plate, printing was carried out in the same manner as in Example 1. A good printed image free of background stains was obtained even after printing 3000 sheets, and no peeling of the image area was observed.

Example 9 Polyethylene terephthalate (trade name: Lumira-T, manufactured by Toray Industries, Inc.) having a thickness of 6 μm was used as a peeling support layer, and a solution having the following composition was prepared on this peeling support layer in the same manner as in Example 1. Was used to form a photosensitive layer.・ Linear saturated polyester resin (trade name: Byron 280,
Toyobo Co., Ltd. 4 parts ・ Chlorinated polyolefin (trade name: Super Klon 51)
0, Sanyo Kokusaku Pulp Co., Ltd. 1 part ・ Oligoester acrylate (brand name Aronix M
-6300, manufactured by Toagosei Kagaku Kogyo Co., Ltd. 3.5 parts 2.4-Diethylthioxanthone (trade name KAYAC)
URE DETX, manufactured by Nippon Kayaku Co., Ltd. 0.75 part ・ Ethyl 4-dimethylaminobenzoate (trade name KAYA)
CURE EPA, manufactured by Nippon Kayaku Co., Ltd. 0.75 parts Hydroquinone monomethyl ether 0.01 parts Copper phthalocyanine pigment 0.1 parts Methyl ethyl ketone 10 parts Toluene 10 parts Cyclohexanone 10 parts

Further, the base layer of Example 1 and the photosensitive layer were laminated in the same manner as in Example 1 to obtain a printing original plate of the present invention.

A negative image was used as a mask on the release support layer of the printing plate precursor, and the film was exposed through the mask. At the same time, the printing plate precursor was heated to 85 ° C. on a hot plate to form a polymerization latent image. For the exposure at that time, an ultra-high pressure mercury lamp was used as a light source, and the light source was separated from the original plate by about 10 cm.
It went for 0 seconds.

Then, when the polyethylene terephthalate film as the release support layer was released, the unexposed portion of the photosensitive layer was also adhered to the polyethylene terephthalate film and released at the same time. As a result, the exposed portion of the photosensitive layer remained on the base layer. I got a printing plate.

The printing plate was exposed and heated in the same manner as in Example 2. However, the exposure time was 60 seconds and the heating temperature was 85 ° C. Thereafter, this printing plate was further used in Example 4.
Pass through a heat roll as above.

Using this printing plate, printing was carried out in the same manner as in Example 1. As a result, a good printed image free of background stain was obtained even after printing 5000 sheets, and peeling of the edge of the image portion did not occur. ..

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a printing original plate of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the printing original plate of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the printing original plate of the present invention.

FIG. 4 is a schematic cross-sectional view showing an example of an image exposure process of the printing plate manufacturing method of the present invention.

FIG. 5 is a schematic cross-sectional view showing an example of a peeling development process of the printing plate manufacturing method of the present invention.

FIG. 6 is a schematic cross-sectional view showing another example of the image exposure process of the printing plate manufacturing method of the present invention.

FIG. 7 is a schematic cross-sectional view showing an example of a heat development step of the printing plate manufacturing method of the present invention.

FIG. 8 is a schematic cross-sectional view showing an example of the polymerization exposure process of the printing plate manufacturing method of the present invention.

FIG. 9 is a schematic cross-sectional view showing another example of the peeling development process of the printing plate manufacturing method of the present invention.

FIG. 10 is a side view showing an example of a printing apparatus that performs printing using the printing plate manufactured by the printing plate manufacturing method of the present invention.

[Explanation of symbols]

 1 Substrate 2 Base Layer 3 Photosensitive Layer 4 Release Support Layer 5 Photosensitive Silver Salt Layer 6 Protective Layer 7 Intermediate Layer 8 Mask 9 Silver Nucleus 10 Silver Atom 11 Oxide 12 Plate Cylinder 13 Printing Plate 14 Ink Supply Roller 15 Inkwell 16 Ink 17 Dampening water 18 Dampening water supply roller 19 Dampening water reservoir 20 Blanket cylinder 21 Impression cylinder 22 Recorded material 23 Cassette 24 Roll 25 Tray

Claims (38)

[Claims] 1. A printing original plate having at least a base layer, a photosensitive layer capable of peeling development, and a peeling supporting layer, wherein the base layer contains a polymerizable compound. 2. The printing original plate according to claim 1, wherein the photosensitive layer contains a layer-forming polymer substance. 3. The printing original plate according to claim 2, wherein the layer-forming polymer substance is a mixture of a chlorinated polyolefin and a linear saturated polyester. 4. The chlorinated polyolefin is added in an amount of 0.1 to 300 with respect to 100 parts by weight of the linear saturated polyester.
The printing original plate according to claim 3, which is mixed by weight. 5. The printing original plate according to claim 1, wherein the base layer contains a polymerization initiator. 6. The printing original plate according to claim 1, wherein a contact angle of the photosensitive layer is larger than a contact angle of the base layer. 7. The printing original plate according to claim 6, wherein the photosensitive layer has a contact angle of 60 ° or more. 8. The printing original plate according to claim 6, wherein the contact angle of the base layer is 58 ° or less. 9. A base layer, a peelable developable photosensitive layer, and at least a photosensitive silver salt layer containing at least a photosensitive silver halide, an organic silver salt and a reducing agent, wherein the base layer is a polymerizable compound. An original plate for printing characterized by containing. 10. The printing original plate according to claim 9, wherein the photosensitive layer contains a layer-forming polymer substance. 11. The printing original plate according to claim 10, wherein the layer-forming polymer substance is a mixture of a chlorinated polyolefin and a linear saturated polyester. 12. The chlorinated polyolefin in an amount of 0.1 to 30 relative to 100 parts by weight of the linear saturated polyester.
The printing original plate according to claim 11, wherein 0 part by weight is mixed. 13. The printing plate precursor according to claim 9, wherein the base layer contains a polymerization initiator. 14. The printing original plate according to claim 9, wherein a contact angle of the photosensitive layer is larger than a contact angle of the base layer. 15. The printing original plate according to claim 14, wherein the contact angle of the photosensitive layer is 60 ° or more. 16. The printing original plate according to claim 14, wherein the contact angle of the base layer is 58 ° or less. 17. The printing original plate according to claim 9, further comprising an intermediate layer between the photosensitive silver salt layer and the photosensitive layer. 18. The printing original plate according to claim 17, wherein the photosensitive layer contains a layer-forming polymer substance. 19. The printing original plate according to claim 18, wherein the layer-forming polymer substance is a mixture of a chlorinated polyolefin and a linear saturated polyester. 20. The chlorinated polyolefin is added in an amount of 0.1 to 30 with respect to 100 parts by weight of the linear saturated polyester.
20. The printing original plate according to claim 19, wherein 0 part by weight is mixed. 21. The printing original plate according to claim 17, wherein the base layer contains a polymerization initiator. 22. The printing original plate according to claim 17, wherein the contact angle of the photosensitive layer is larger than the contact angle of the base layer. 23. The printing original plate according to claim 22, wherein the contact angle of the photosensitive layer is 60 ° or more. 24. The printing original plate according to claim 22, wherein the contact angle of the base layer is 58 ° or less. 25. An image exposure process of exposing the printing plate according to claim 1 to image formation to form a polymerized portion and an unpolymerized portion on the photosensitive layer, and peeling and removing the unpolymerized portion together with a release support layer. And a peeling and developing step of leaving the polymerized portion on the base layer. 26. The method for producing a printing plate according to claim 25, wherein the printing plate is reexposed after the peeling and developing process. 27. The method for manufacturing a printing plate according to claim 25 or 26, wherein the printing plate is subjected to a heat treatment after the peeling and developing process. 28. The method of manufacturing a printing plate as claimed in claim 25, wherein a pressure treatment is applied to the printing plate after the peeling and developing process. 29. The method for manufacturing a printing plate according to claim 25, wherein after the peeling and developing process, the printing plate is subjected to a heat treatment and a pressure treatment. 30. The method for producing a printing plate according to claim 25, wherein after the peeling and developing process, the printing plate is subjected to re-exposure and a first heat treatment, and then a second heat treatment and a pressure treatment. 31. An image exposure process of performing image exposure on the printing original plate according to claim 9, a heat development process of heating the printing original plate, and a polymerization exposure of the printing original plate, A polymerization exposure step of forming a polymerized portion and an unpolymerized portion on the photosensitive layer, and a peeling and developing step of peeling and removing the unpolymerized portion together with the photosensitive silver salt layer and leaving the polymerized portion on the layer. A method for producing a printing plate, comprising: 32. The method for manufacturing a printing plate according to claim 31, wherein the printing plate is re-exposed after the peeling and developing process. 33. The method for producing a printing plate according to claim 31, wherein the printing plate is subjected to a heat treatment after the peeling and developing process. 34. The method for producing a printing plate according to claim 31, wherein the printing plate is subjected to a pressure treatment after the peeling and developing process. 35. The method for producing a printing plate according to claim 31, wherein the printing plate is subjected to a heat treatment and a pressure treatment after the peeling and developing process. 36. The method of manufacturing a printing plate according to claim 31, wherein after the peeling and developing process, the printing plate is subjected to re-exposure and a first heat treatment, and then a second heat treatment and a pressure treatment. 37. At least a step of supplying ink to the printing plate manufactured by the method of claim 25 or 31, and a step of transferring the ink supplied to the printing plate to a recording medium. A printing method characterized by. 38. Ink supply means for supplying ink to the printing plate manufactured by the method according to claim 25, and transfer means for transferring the ink supplied to the printing plate to a recording medium. A printing apparatus comprising at least: