JPH0862831A - Damping-waterless planographic printing plate and its formation - Google Patents

Abstract

PURPOSE: To provide a damping-waterless planographic printing plate and the forming method capable of improving the picture quality (staining due to insufficient resolution and ink repulsing property) and the plate wear. CONSTITUTION: (1) An ink repulsing layer is provided on a substrate and an ink receiving metallic image is formed on the surface thereof or adjacent thereto. (2) The ink receiving metallic image is formed on the exposed part or unexposed part of an ink repulsing photosensitive layer without eluting the ink repulsing photosensitive layer by image exposing and developing a material having the ink repulsing photosensitive layer on the substrate. (3) The ink-receiving metallic image is formed on the ink-repulsing layer corresponding to the unexposed part by allowing a material having the ink-repulsing layer, in which a heavy metallic colloid is dispersed, on the substrate to come into closely contact with an image exposed silver halide emulsion layer through a developer containing a silver halide solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate that does not require fountain solution and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, an image made of an oleophilic photosensitive resin is formed on a lithographic printing plate using dampening water, that is, a substrate (usually an aluminum plate) which has been subjected to a hydrophilic treatment, and this plate surface is formed. Due to emulsification of ink by dampening water in lithographic printing in which dampening water and oil-based ink are alternately supplied to wet the hydrophilic non-image area with water and ink is applied only to the lipophilic image area for printing. A lithographic printing plate that does not require dampening water is known in order to improve problems such as background stains and difficulty in balancing the supply of ink and dampening water.

As such a technique, Japanese Examined Patent Publication Sho 61-9624
In the publication, a fountain solution-free lithographic printing plate having an ink repellent layer photopolymer photosensitive layer (silicone rubber having a polymerization reaction group) on a substrate, the photosensitive layer of the unexposed portion is eluted by a post-exposure development treatment, The exposed area is ink repellent, and the unexposed area (photosensitive layer is dissolved away and the substrate surface is exposed) becomes ink-receptive, so printing can be performed simply by supplying ink without using fountain solution. A plate version is disclosed. Japanese Patent Publication Nos. 44-27242, 48-30562 and U.S. Pat. No. 3,728,114 have a hydrophilic silver halide photosensitive layer on a substrate, and a silver image (metal image ) Is formed, dampening water is supplied to the non-image area, and ink is supplied to the image area (forbidden image area) to perform printing. U.S. Pat.Nos. 3,083,097 and 3,161,508 disclose that a sheet having a hydrophilic layer containing a colloidal metal on a substrate is exposed to a silver halide photosensitive layer through an eluate of silver halide to make the hydrophilic layer hydrophilic. A lithographic printing plate is disclosed that forms a metal image on the layer.

[0004]

However, in the above, since the image portion is formed by elution and removal, there is a problem that side etching occurs and the image quality is deteriorated. In the above, since the polymer layer containing water in the non-image area is used, the ink repelling property is insufficient, the background stain easily occurs by printing, and the printing durability is insufficient. In the above,
Since a polymer layer containing water in the non-image area is used in the same manner as described above, there are problems that the ink repulsion is insufficient, scumming easily occurs due to printing, and the printing durability is insufficient. are doing.

Therefore, firstly, an object of the present invention is to provide a planographic printing plate which does not require a fountain solution and a method for producing the same, which improves image quality (background stains due to insufficient resolution and ink repulsion). Is to provide. Second, to provide a fountain solution-free lithographic printing plate having improved printing durability and a method for producing the same.

[0006]

The constitutions of the present invention for achieving the above object are as follows.

A fountain solution-free lithographic printing plate comprising a non-hydrophilic ink repellent layer on a substrate, and an ink-receptive metal image formed on the surface and / or in the vicinity of the surface.

A fountain solution-free photosensitive lithographic printing plate having a non-hydrophilic ink repellent photosensitive layer on a substrate is imagewise exposed and developed to form an ink on the exposed or unexposed portion of the ink repellent photosensitive layer. A method for preparing a lithographic printing plate not requiring a fountain solution, which comprises forming an ink-receptive metal image without eluting the repellent photosensitive layer.

The ink repellent layer of a lithographic printing plate material having a non-hydrophilic ink repellent layer in which a heavy metal colloid is dispersed on a substrate and the image-exposed silver halide emulsion layer contain a silver halide solvent. Close contact with a developing solution
A method for preparing a lithographic printing plate not requiring a fountain solution, which comprises forming an ink-receptive metal image on the ink repellent layer corresponding to the unexposed area of the image exposure.

[0010]

In the lithographic printing plate of the present invention which does not require fountain solution, the image portion and the non-image portion are formed in the same layer, and therefore the problem of side etching which occurs in the method of forming an image by eluting the photosensitive layer does not occur. High image quality (resolution) can be obtained. Further, since the ink repellent material for the non-image area used in the present invention is a material having a low surface energy such as silicone rubber or fluororesin, a hydrophilic resin is used for the non-image area and a fountain solution is contained therein. The problem of the ink repellent layer is a problem, and the background stain and the printing durability are improved due to the insufficient ink repellent property.

The present invention will be described in detail below.

Examples of the ink repellent layer of the lithographic printing plate requiring no fountain solution of the present invention include a silicone rubber layer and a fluororesin layer.

As the silicone rubber for forming the silicone rubber layer, a hydroxyl group is contained in the main chain having a repeating unit represented by the following general formula [1] and having a molecular weight of several thousand to several hundred thousand, or a terminal of the main chain. Those containing a linear organic polysiloxane as a main component are preferred.

General formula [1]

[0015]

Embedded image

Here, n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group,
It is preferably an alkoxyl group, a vinyl group, an aryl group or a silanol group (OH group), and 60% or more of R is a methyl group. The silanol group (OH group) may be in the main chain or at the end of the main chain, but is preferably at the end.

Examples of the silane coupling agent (or silicone crosslinking agent) include RnSiX _4-n (wherein n is an integer of 1 to 3 and R is alkyl, aryl, alkenyl or a monovalent combination thereof. Represents a group, and these groups are halogen, amine, hydroxy,
It may have a functional group such as alkoxy, aryloxy and thiol. X is

[0018]

Embedded image

Represents a substituent such as Here, R ² and R ³ each represent the same as the above R, and R ² and R ³ may be the same or different. Ac represents an acetyl group. ) Is a silane compound.

Specific examples of the silane coupling agent include:
_{HN [(CH 2) 3 Si} (OMe) 3] 2, vinyltriethoxysilane, Cl
(CH ₂ ) ₃ Si (OMe) ₃ , CH ₃ Si (OAc) ₃ , HS (CH ₂ ) ₃ Si (OMe) ₃ , vinyltris (methylethylketoxime) silane and the like can be mentioned.

Useful silicone rubbers are those obtained by the condensation reaction of such silicone base polymers with the silicone crosslinking agents listed above.

The above silicone rubber is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. Another useful silicone rubber is a reaction of the above-mentioned base polymer with a silicone oil having a repeating unit represented by the following general formula [2], or about 3% of R is a vinyl group. It can also be obtained by addition reaction of silicone with a base polymer, or reaction of the silicone oils.

[0023]

[Chemical 3]

(In the formula, R has the same meaning as R which is a substituent of the polymer represented by the general formula [1], m is an integer of 2 or more, and n is an integer of 0 or 1 or more.) In order to obtain a silicone rubber by various crosslinking reactions, the crosslinking reaction is carried out using a catalyst. This catalyst includes tin, zinc, cobalt, lead, calcium, manganese,
Organic carboxylic acid salts of metals such as dibutyltin laurate, tin (II) octoate, cobalt naphthenate, and chloroauric acid are used.

Further, in order to improve the strength of the silicone rubber and to obtain the silicone rubber which can withstand the frictional force generated during the printing operation, a filler can be mixed. The silicone rubber in which the filler is mixed in advance is commercially available as a silicone rubber stock or a silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating, RTV is used.
Alternatively, the LTV silicone rubber version is preferably used. An example of such a material is a silicone rubber dispersion for paper coating such as Syl Off 23, SRX-257, SH237 manufactured by Torre Silicone.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve the adhesiveness. Preferred silane coupling agents include, for example, the following. .

(A) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ (b) H ₂ NCH ₂ CH ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (CH ₃ ) ( c) Specific examples of the fluororesin forming the H ₂ N (CH ₂ ) ₃ Si (OEt) ₃ fluororesin layer include polyperfluoroalkyl (meth) acrylate and polyperfluoropolyether (meth) acrylate. It is preferably used.

Further, a polymer obtained by polymerizing or copolymerizing a monomer represented by the following general formula is also preferable.

[0029]

[Chemical 4]

(In the formula, Rf is a substituted fluorine alkyl group or a substituted fluorine polyether group, and R is a hydrogen atom or an alkyl group.) As such a fluorine-containing acrylic monomer, the following monomers are more preferable.

[0031]

[Chemical 5]

It is also preferable that the following monomers are copolymerized with the above monomers. Examples of the monomer include styrene, methyl methacrylate (MMA), butyl acrylate, acrylonitrile and ethyl acrylate.

The thickness of the ink repellent layer is preferably
It is 0.5 to 100 μm, more preferably 1 to 20 μm.

Preferred metals for forming an ink-receptive metal image formed on the surface of the ink repellent layer and / or in the vicinity of the surface include silver and mercury, and these metal images include silver halide, silver nitrate, nitric acid first It can be formed by using mercury, mercury sulfide or the like as a supply source.

To form an ink-receptive metal image on the surface of the ink repellent layer and / or in the vicinity thereof, for example, a development nucleus is provided on the surface of the ink repellent layer and / or in the vicinity thereof,
It can be formed by reducing and precipitating a metal on the development nucleus from a solution containing a soluble metal salt and a reducing agent (for example, a developing agent). More specifically, for example, after imagewise exposing a silver halide photosensitive material, a silver halide emulsion surface of the photosensitive material and a fountain solution-free lithographic printing plate material provided with an ink repellent layer on a substrate The surface provided with development nuclei on the surface of the ink repellent layer is brought into close contact with a developer containing an appropriate amount of a solvent for silver halide between these two surfaces for dissolution physical development. A method of reducing and depositing metallic silver on the development nuclei to form a silver image can be used. As a developer used for development for forming an ink-receptive metal image, a silver salt diffusion transfer developer or a physical developer can be preferably used.

The physical development nuclei include fine particles of heavy metals and their sulfides, such as Au, Ag, Cu, Se, Cd, Zn, Pd, Cu.
Fine particles such as S, Ag ₂ S, HgS, PdS, and ZnS can be used.For example, fine particles such as heavy metals having a diameter of 200 to 1000 μm or sulfides thereof are uniformly and planarly arranged at intervals of about 1000 to 3000 μm. It is possible to use a dispersion layer distributed in the above. Such a dispersion layer can be formed by vacuum vapor deposition, cathode sputtering,
It can be obtained by a coating method or the like. When using the vacuum deposition method, use a so-called island-shaped structure film that appears at the initial stage of the deposition film formation when silver etc. is evaporated and deposited under a reduced pressure of 10 ^-3 to 10 ^-6 Torr as a physical development nucleus. You can In the coating method, a layer of physical development nuclei can be formed by preparing a hydrosol such as silver having a size of about 500 μm and applying it by an appropriate method such as a dipping method. Alternatively, a substrate having an ink repellent layer provided thereon may be dipped in an aqueous solution of silver nitrate to impregnate the vicinity of the surface of the ink repellent layer with silver nitrate as a physical development nucleus.

The ink repellent photosensitive layer according to claim 2 is such that the ink repellent layer is impregnated with an alkali metal halide and then with silver nitrate to produce silver halide. It can be produced by a method such as containing a water-soluble diazonium salt (for example, diazosulfonate, diazothioether, diazocyanide, etc.). Specifically, in the former case, the ink repellent layer is applied to the support and dried, and the sheet is immersed in an aqueous solution in which an alkali metal halide is dissolved for a certain period of time and then dried, and then further immersed in an aqueous solution of silver nitrate and dried. Thus, a photosensitive silver halide can be formed in the ink repellent layer. The concentration of the photosensitive silver halide formed in the ink repellent layer can be controlled by the concentration of solute in each dipping solution, the dipping temperature and the dipping time. In the latter case, the diazonium salt is dissolved or dispersed in the solvent used for applying the ink repellent layer to form the ink repellent photosensitive layer. The amount of photosensitive compound in the ink repellent layer is 0.1.
-30 wt%, preferably 2-15 wt%. When a diazonium salt is used, a metal colloid latent image is formed by the reducing property of a phenol compound or a trans form which is a photolysis product of the diazonium salt, and physical development is performed to form a metal image.

In order to form an ink receptive metal image on the ink repellent photosensitive layer, the ink repellent layer described above may be formed on the surface of the ink repellent photosensitive layer and / or in the vicinity thereof. Similarly, development nuclei may be provided, image exposure may be performed on the ink repellent photosensitive layer, and then development with a physical developer may be performed. Image exposure of the ink repellent photosensitive layer may be performed with light having a wavelength corresponding to the properties of the photosensitive material used and the exposure amount.

In the invention according to claim 3, in the ink repellent layer in which a heavy metal colloid is dispersed, the surface layer of the ink repellent layer is impregnated with an alkali metal halide,
It can then be impregnated with silver nitrate to produce. As the silver halide emulsion layer which is brought into close contact with the ink repellent layer, the silver halide emulsion layer of a normal black-and-white silver halide photographic light-sensitive material can be applied. In order to form an ink receptive metal image on the ink repellent layer corresponding to the unexposed area by bringing the ink repellent layer containing a heavy metal colloid into contact with the image-exposed silver halide emulsion layer, a known silver salt is used. The technique of diffusion transfer method can be applied.

The substrate used in the lithographic printing plate requiring no fountain solution of the present invention is not particularly limited and includes paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloy), zinc, copper. Metal plates such as, cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl acetal and other plastic films, the above-mentioned metal laminated or vapor deposited paper or Examples include a plastic film, a copper plate plated with aluminum or chrome, and the like.

A plumer layer can be provided between the substrate of the photosensitive lithographic printing plate requiring no fountain solution of the present invention and the ink repellent layer or the ink repellent photosensitive layer.

Examples of the primer layer include those made of the following resin compositions.

(1) Epoxy Resin and Resin Composition Containing It A typical example of the epoxy resin used in the primer layer is a reaction product of epichlorohydrin and a polyhydric phenol such as bisphenol A. The epoxy resin may be mixed with other components to give a three-dimensional structure, or may be modified with other components. An example of its usage is as follows.

Thermosetting resin composition containing an epoxy resin obtained by mixing one or two or more thermosetting resins such as phenol resin, urea resin and melamine resin, amines, polyamides, acid anhydrides, etc. A room temperature or heat-curable resin composition containing an epoxy resin obtained by adding as a curing agent, phenol, melamine, urea or a resin thereof,
Epoxy resins obtained by precondensing one or more of amines, polyesters, polyamides, polysulfides, etc., and epoxy resin esters obtained by esterification with fatty acids.

These epoxy resins can be appropriately mixed and used, or can be further mixed and used with vinyl resin, acrylic resin, amino resin, alkyd resin, urethane resin and the like within a range in which compatibility is allowed. is there.
Upon curing the curable resin containing these epoxy resins, a curing reaction accelerator such as p-toluenesulfonic acid or boron trifluoride monoethylamine may be appropriately added and used.

(2) Composition composed of a resin obtained by photo-curing a layer made of a photo-duplication type photo-curable resin The photo-duplication type photo-curable resin is a polymer having a main chain or a side chain.

[0047]

[Chemical 6]

Polyesters, such as, polycarbonates, polyamides, polyacrylic acid esters, polyvinyl alcohol derivatives, etc. are included, and the molecular weight thereof is not limited as long as it is soluble in a solvent, but generally 1000 to
It is advantageous to choose from the range of tens of thousands. Particularly preferred such polymers include, for example, US Pat.
3,030,208 and 3,707,373, a photosensitive polymer containing a photosensitive group in the polymer main chain, for example, a photosensitive polyester composed of p-phenylenediacrylic acid and a diol, U.S. Pat.No. 2,956,878. And a photosensitive polymer as described in each specification of JP-A-3,173,787, for example, a photosensitive polyester derived from a 2-properidenemalonic acid compound such as cinnamylidenemalonic acid and a bifunctional glycol. U.S. Pat.No. 2,690,966
No. 2,752,372, No. 2,732,301, and the like, photosensitive polymers such as cinnamic acid esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose and the like. And those which are insolubilized by the action of actinic rays are included.

A pigment or dye is added as a colorant to the above polymer. For example, Phthalocyanine Blue (CI74
160), Carmine 6B (CI15850), Rhodamine B Lake (CI45170) and the like are preferable, but dyes such as Oil Blue BO (CI74350) can also be used. The addition amount naturally varies depending on the conditions such as the coating amount, but 1 to 50% by weight, and particularly preferable range is 2 to 15% by weight based on the polymer.

The above-mentioned polymer preferably contains a sensitizer. Such sensitizers include, for example, US Pat.
2,610,120, 2,670,285, 2,670,286, 2,67
0,287, 2,690,966, 2,732,301, 2,835,656
No. 2, No. 2,956,878, No. 3,023,100, No. 3,066,177,
3,141,770, 3,173,787, 3,357,831, 3,4
09,593, 3,418,295, 3,453,110, 3,475,61
No. 7, No. 3,561,969, No. 3,575,929, No. 3,582,327,
Those described in No. 3,647,470, No. 3,721,566, No. 3,737,319, etc. are included. Specific examples of particularly useful sensitizers include 2-benzoylmethylene-1-methyl-β-naphthothiazoline, 5-nitroacenaphthene, β-chloroanskinone, 1,2-benzalanthraquinone, p, p. ′ -Tetraethyldiaminodiphenyl ketone, p, p′-dimethylaminobenzophenone, 4-nitro-2-chloroaniline and the like are included. The ratio of sensitizer used is 0.5 to 15 with respect to the polymer.
A weight% range is preferred, but a particularly preferred range is 2-8.
Is the weight.

(3) Using gelatin as a binder As gelatin, so-called photographic gelatin, which is obtained from bovine bone or hide by acid treatment or alkali treatment, is mainly used. In addition to this, it is represented by the following general formula. Any gelatin can be used as long as it is a natural polymer compound in which various amino acids are condensed.

[0052]

[Chemical 7]

The following hardeners are used as hardeners for hardening (that is, crosslinking) gelatin.

(A) Inorganic hardener, chromium alum, aluminum alum, etc. (B) Organic hardener, compounds described in JP-A-63-305360, page 4, lower right column to page 5, lower right column (B-1) to (B-12).

The amino acids in gelatin that can be used in the hardening reaction differ depending on the type of hardening agent used, and the composition of amino acids also differs depending on the gelatin used. Therefore, the optimum addition amount of hardener varies depending on the type of gelatin used and the type of hardener, but generally gelatin is used.
The hardener may be added in an amount of 1 to 200 mmol, preferably 5 to 100 mmol, based on 100 parts by weight.

(4) Composition Containing Diazo Resin and / or Photopolymerizable Photosensitive Composition The diazo resin includes various kinds, but is preferably represented by a condensate of p-diazodiphenylamine and formaldehyde. Diazo resins which are water-insoluble and soluble in organic solvents, preferably JP-B Nos. 47-1167 and 57-43.
Water-insoluble ones and ordinary organic solvent-soluble ones as described in JP-A No. 890 are used. Particularly preferred is a diazo resin represented by the following general formula [3].

[0057]

Embedded image

(In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents PF ₆ or B.
Indicates F _4, Y is -NH -, - shows S- or -O-. ) Examples of the diazo monomer in the diazo resin include 4-diazo-diphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4- N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4- N-benzylaminobenzene, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy
-4-p-Tolylmercaptobenzene, 1-diazo-2-ethoxy
-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-morpholinobenzene,
1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene,
1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N -Diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene,
1-diazo-2-chloro-4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4 Examples include-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3- (isopropoxy) -4-diazodiphenylamine and the like.

Examples of the aldehyde used as the condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde and the like.

Further, as the anion, a water-soluble diazo resin can be obtained by using chlorine ion, tetrachlorozinc acid, etc., and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4 Diazo resin soluble in organic solvent by using 4,4'-biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc. Can be obtained. Particularly preferably, a diazo resin composed of hexafluorophosphoric acid is used.

The diazo resin is a film-forming resin such as polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate resin. It is used as a mixture with a copolymer, a phenoxy resin, a polyurethane resin, a polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate or the like, but it is particularly preferably used as a mixture with a lipophilic polymer compound having a hydroxyl group. Examples of such lipophilic polymer compounds include a monomer having an aliphatic hydroxyl group in the side chain, for example, a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and another copolymerizable monomer. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin and the like may be added if necessary.

In addition to these, various polymer compounds can be used as the binder used in combination with the diazo resin, but a monomer having an aromatic hydroxyl group as described in JP-A-54-98613 is preferable. Monomers such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene,
Copolymers of o-, m-, or p-hydroxyphenyl methacrylate with other monomers, mainly containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as described in U.S. Pat. No. 4,123,276. Polymer containing a repeating unit consisting of, shellac, natural resins such as rosin, polyvinyl alcohol, polyamide resin described in U.S. Pat.No. 3,751,257, linear polyurethane resin described in U.S. Pat.No. 3,660,097, As a phthalated resin of polyvinyl alcohol, an epoxy resin condensed from bisphenol A and epichlorohydrin, and an alkali-soluble resin, novolak resin, vinyl polymer having a phenolic hydroxyl group, and JP-A-55-57841 are described. Polyphenols and aldehydes or ketones And the like of the condensation resin. Examples of the novolac resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-57841, and JP-A-55-127553. P as described
-Examples include copolycondensation resins of substituted phenol and phenol or cresol and formaldehyde.

These binders are contained in the solid content of the resin composition.
The content is 10 to 95% by weight, preferably 40 to 80% by weight. The diazo resin is 5 to 80% by weight, preferably 15 to 60% by weight
Contained.

The photopolymerizable photosensitive composition is preferably
(A) A vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator, and (c) a polymer compound as a binder.

As the vinyl monomer as the component (a), those described in JP-B Nos. 35-5093, 35-14719 and 44-28727 are used, for example, an acrylic polyol. Acids or methacrylic acid esters, namely diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol triester
(Meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., or methylene bis (meth) acrylamide, bis (meth) acrylamides such as ethylene bis (meth) acrylamide, or an unsaturated monomer containing a urethane group, Reaction products of diol mono (meth) acrylate and diisocyanate such as di- (2′-methacryloxyethyl) -2,4-tolylenediurethane, di- (2-acryloxyethyl) trimethylenediurethane, etc. Etc.

As the photopolymerization initiator of the above component (b),
For example, carbonyl compounds, organic sulfur compounds, superfluids, redox compounds as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar,
Examples include azo and diazo compounds, halogen compounds, and photoreducible dyes. More specifically, it is disclosed in British Patent No. 1,459,563.

Further, as the binder of the component (c),
As well as the binder resin which can be used in combination with the diazo resin, various known polymers can be used. Details of specific binders are described in US Pat. No. 4,072,527.

The components (a), (b) and (c) are contained in the solid content of the photopolymerizable composition in such a manner that (a) is 20 to 80% by weight of the solid content of the photopolymerizable composition.
It is preferable that 0.1 to 20% by weight and (c) are contained in 20 to 80% by weight.

Further, these photopolymerizable compositions may contain a thermal polymerization inhibitor, a plasticizer, a dye or a pigment.

In the primer layer containing the resin of the above (1) to (4), if necessary, an oil-sensitizer, a surfactant, an organic acid, an acid anhydride, a compound capable of generating an acid upon exposure, Additives such as plasticizers, anchor agents (silane coupling agents, silicone primers, organic titanates, etc.), dyes, pigments, and other coloring agents are added. It is suitable to add 0.01 to 20% by weight, preferably 0.05 to 10% by weight, to the composition.

A protective layer may be provided on the ink repellent layer or the ink repellent photosensitive layer of the photosensitive lithographic printing plate not requiring fountain solution of the present invention. As the protective layer, one that is transparent to ultraviolet rays and has transparency such as polypropylene film is preferably used, and the film thickness thereof is 1 to 20 μm.
m, more preferably 1 to 10 μm.

As a proofing machine and a proofing machine using the lithographic printing plate requiring no fountain solution of the present invention, a flatbed calibrating machine (circular pressure type)
A mode in which an offset sheet-fed printing machine is used for this machine is mentioned. The printing machines are LITHRONE26 (made by Komori Printing Machinery Co., Ltd.) as a sheet-fed press, Heidel GTO Z52, and LITHOPIA-BT3S-600 (made by Mitsubishi Heavy Industries, Ltd.) as an offset rotary press, OA-
B3T-400 (manufactured by Toshiba Machine Co., Ltd.), calibration machine is KF-123-GL,
KF-124-GL, KF-122-E (above Dainippon Screen Mfg. Co., Ltd.)
Company) can be used.

The ink is, for example, TOKYO KING Mark V (manufactured by Toyo Ink Manufacturing Co., Ltd.), SPACE COLOR CAPS (manufactured by Dainippon Ink and Chemicals, Inc.), Diatone 2001 (manufactured by Sakata Inx Co., Ltd.), paper. For example, art paper, coated paper, high-quality paper, etc. can be used. The printing pressure and blanket tailoring differ depending on the type of printing machine, but appropriate conditions can be selected as appropriate. The printing speed of the proofing machine is 0
1000 sheets / hour, preferably 100 to 300 sheets / hour.

[0074]

EXAMPLES Next, the present invention will be described more specifically by way of examples.

Example 1 A smooth aluminum plate that had been degreased by a conventional method was coated with a primer layer having the following composition so that the film thickness after curing was 15 μm and dried, and then a high pressure mercury lamp (output 80 W / cm). Was exposed to light and cured. In the following, “part” means “part by weight”.

[Primer layer composition] Copolymer having a molar ratio of 2-hydroxyethyl methacrylate and methyl methacrylate of 40/60 100 parts trimethylolpropane triethoxytriacrylate 80 parts 2,4-diethylthioxanthone 4 parts p- Dimethylaminobenzoic acid ethyl ester 4 parts Yellow pigment (KET-YEllOW402, Dainippon Ink & Chemicals, Inc.) 8 parts White pigment (zinc oxide, FINEX-25, Sakai Chemical Co., Ltd.) 25 parts Propylene glycol monomethyl ether 600 parts Next An ink repellent layer coating solution having the following composition was applied onto the primer layer and dried at 100 ° C. for 2 minutes to form an ink repellent layer having a thickness of 2 μm.

(1) 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate [CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F], 2-hydroxyethyl methacrylate, methacrylic acid Resin in which 2-methacryloyl oxyethyl isocyanate [CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ NCO] is added to 50% of the hydroxy groups in the copolymer resin having a molar ratio of methyl of 80:10:10. Parts (2) Coronate EH (polyisocyanate manufactured by Nippon Polyurethane Co., Ltd.) 3.5 parts (3) dibutyltin dilaurate 0.05 parts (4) Freon-113 500 parts (5) methyl ethyl ketone 20 parts The obtained sheet having a fluororesin film is chlorinated When the sheet is dipped in an aqueous solution of sodium and dried, and then the sheet is dipped in an aqueous solution of silver nitrate, silver chloride is produced in the film.

On the photosensitive layer surface of the thus-prepared substrate having the ink-repellent photosensitive layer, a small vacuum deposition apparatus was used to reduce the pressure to 5 × 10 ⁻⁵ Torr and the width was 7 cm and the length was 7 cm.
While moving the photosensitive sheet of 10 m at a speed of 20 cm / min, the molybdenum boat was resistance-heated to evaporate the silver sulfide powder and vapor-deposit it to an average film thickness of about 10Å. This silver sulfide nucleus vapor-deposited film was taken out into the air, cut into an appropriate length, passed through a document, and contact-printed, and then developed using the following processing solutions.

Deionized water 1000 ml Sodium sulfite 80 g Hydroquinone 35 g Sodium thiosulfate 15 g Sodium hydroxide 28.5 g Potassium bromide 2.5 g 0.5% Penzotriazole in water 25 ml As a result, an ink-receptive silver image was formed on the unexposed area. A waterless lithographic printing plate was obtained. When this printing plate was printed using an offset printing machine, the results shown in Table 1 were obtained.

Example 2 The same procedure as in Example 1 was carried out except that a silicone resin film prepared by using the following ink repellent layer forming coating liquid was used in place of the fluororesin film in Example 1. However, the results shown in Table 1 were obtained.

Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: 52000) 100 parts Triacetoxymethylsilane 10 parts Dibutyltin laurate 0.8 part Isopar G (manufactured by Esso Chemical Co., Ltd.) 900 parts Example 3 The primer layer used in Example 1. The coating liquid for the ink repellent layer of Example 2 was applied to an aluminum plate to which the above was applied and dried, and further immersed in an aqueous dispersion in which silver nitrate was adsorbed on colloidal silica to impregnate the silicone resin film with colloidal silver. It was

The ink repellent layer surface of the sheet thus prepared and the photosensitive layer surface of the silver halide photosensitive sheet coated with the exposed silver chlorobromide emulsion were used in Example 1 for the silver complex salt diffusion transfer treatment liquid. Then, the silver halide photosensitive sheet was peeled off to obtain a printing plate. Printing was carried out in the same manner as in Example 1 using this printing plate, and the results shown in Table 1 were obtained.

Example 4 An aluminum plate having a primer layer of Example 1 was coated with a coating solution for ink-repellent photosensitive layer having the following formulation to give a dry film thickness of 2 μm.
It was applied so as to be m.

(1) 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate [CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F], 2-hydroxyethyl methacrylate, methacrylic acid Resin in which 2-methacryloyl oxyethyl isocyanate [CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ NCO] is added to 50% of the hydroxy groups in the copolymer resin having a molar ratio of methyl of 80:10:10. Parts (2) Coronate EH (manufactured by Nippon Polyurethane Company, polyisocyanate) 3.5 parts (3) dibutyltin dilaurate 0.05 parts (4) CFC-113 500 parts (5) benzenediazosulfonate 0.5 parts (6) methyl ethyl ketone 20 parts A photosensitive sheet having an ink-repellent photosensitive layer on the substrate prepared by performing image exposure was treated with the following latent image forming solution and physical developing solution to obtain a printing plate with a silver image formed on the exposed area. It was When printing was performed in the same manner as in Example 1 using this printing plate, the results shown in Table 1 were obtained.

<Latent image forming liquid> Mercury nitrate 1.5 g Silver nitrate 0.5 g Nitric acid 0.1 g Water 1000 g <Physical developer> Metol 2.5 g Silver nitrate 1.6 g Citric acid 3.0 g Dodecylamine acetate (Armac 12D: Armour & Co.) 0.2 g Water 1000 g Example 5 The same experiment as in Example 4 was conducted except that the following coating liquid was used as the coating liquid for the ink repellent photosensitive layer, and the results shown in Table 1 were obtained.

Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: 52000) 100 parts Triacetoxymethylsilane 10 parts Dibutyltin laurate 0.8 part Benzene diazosulfonate 10 parts Methyl ethyl ketone 400 parts Isopar G (manufactured by Esso Kagaku) 500 parts Comparative Example 1 Implementation The same experiment as in Example 1 was carried out except that the silver chloride gelatin emulsion was coated on the aluminum plate provided with Example 1 and the primer layer instead of the fluororesin film, and the results shown in Table 1 were obtained. Background stains on non-image areas during printing and printing durability performance deteriorated.

Comparative Example 2 The same experiment as in Example 3 was carried out except that a crosslinked gelatin film was used instead of the silicone resin film in Example 3, and the results shown in Table 1 were obtained. Background stains and printing durability deteriorated during printing.

Comparative Example 3 When printing was carried out in the same manner as in Example 1 using a printing plate prepared according to Experiment No. 3 of JP-B-61-9624,
The results shown in Table 1 were obtained.

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[Table 1]

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According to the present invention, there is provided a lithographic printing plate which does not require a fountain solution and a method for producing the same, which improves image quality (background stain due to insufficient resolution and ink repulsion) and printing durability. Provided.

Claims (3)

[Claims] 1. A planographic printing plate not requiring a fountain solution, which comprises a non-hydrophilic ink-repellent layer on a substrate and has an ink-receptive metal image formed on the surface and / or in the vicinity of the surface. . 2. A photosensitive lithographic printing plate requiring no fountain solution having a non-hydrophilic ink repellent photosensitive layer on a substrate is subjected to image exposure and development treatment to expose or unexpose the ink repellent photosensitive layer, A method for preparing a lithographic printing plate not requiring a fountain solution, which comprises forming an ink-receptive metal image without eluting the ink repellent photosensitive layer. 3. A silver halide solvent in which the ink repellent layer and the image-exposed silver halide emulsion layer of a lithographic printing plate material having a non-hydrophilic ink repellent layer in which a heavy metal colloid is dispersed on a substrate. Adhered via a developer containing
A method for preparing a lithographic printing plate not requiring a fountain solution, which comprises forming an ink-receptive metal image on the ink repellent layer corresponding to the unexposed area of the image exposure.