JP2003118252A - Lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lithographic printing original plate, which develops no scumming as an offset original plate, with which a large number of sheets of printed matter having clear images without omission nor distortion of the images can be printed, and which has favorable water retention. SOLUTION: In the lithographic printing original plate having an image receiving layer on a water resistant support, the image receiving layer has a surface graft hydrophilic layer including a bonding resin made of a composite of porous filler particles, a resin including bonds connecting metal atoms and/or semimetal atoms together through oxygen atoms and an organic polymer including a group being formable a hydrogen bond with the resin under the condition that a polymer compound having at least one hydrophilic functional group is chemically bonded to the image receiving layer.

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 precursor, and more particularly, to a lithographic printing plate precursor capable of printing a large number of printed matters with clear images free of background stain, particularly direct drawing. The present invention relates to an original plate for planographic printing.

[0002]

2. Description of the Related Art At present, lithographic printing plates used mainly in the field of light printing include (1) a water-resistant support,
(2) An original plate provided with a hydrophilic image-receiving layer, (2) Direct drawing on an original plate provided with an image-receiving layer (lipophilic) containing zinc oxide on a water-resistant support, and then the non-image area is desensitized A printing plate that is desensitized with a chemical treatment liquid, (3) An electrophotographic light-sensitive material having a photoconductive layer containing photoconductive zinc oxide on a water-resistant support is used as an original plate, and after image formation A non-image area is desensitized with a desensitizing solution to form a printing plate,
(4) A silver salt photographic type original plate in which a silver halide emulsion layer is provided on a water-resistant support is exemplified.

With the recent development of office equipment and the development of office automation, in the printing field, the lithographic printing plate precursor described in (1) above is subjected to plate making by various methods such as an electrophotographic printer, a thermal transfer printer, and an inkjet printer. That is, there is a demand for an offset lithographic printing method in which an image is formed) and a printing plate is directly produced without performing a specific process for forming a printing plate.

In the conventional lithographic printing plate precursor, a surface layer serving as an image receiving layer is provided on both sides of a support such as paper via a back layer and an intermediate layer. The back surface layer or the intermediate layer is composed of a water-soluble resin such as PVA and starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The image receiving layer is usually composed of an inorganic pigment, a water-soluble resin and a waterproofing agent.

Examples of the inorganic pigment include kaolin, clay, talc, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate and alumina. Examples of the water-soluble resin include polyvinyl alcohol (PVA), modified PVA such as carboxy PVA, starch and its derivatives, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer. Water-soluble resins such as polymers and styrene-maleic acid copolymers are mentioned.

[0006] Further, glyoxal is used as a water resistance agent,
Examples thereof include aminoplast initial condensates such as melamine formaldehyde resins and urea formaldehyde resins, modified polyamide resins such as methylolated polyamide resins, polyamide / polyamine / epichlorohydrin adducts, polyamide epichlorohydrin resins, and modified polyamide polyimide resins. In addition, it is also known that ammonium chloride, a crosslinking catalyst for a silane coupling agent, and the like can be used in combination.

Further, as a binder used in the image receiving layer of the lithographic printing plate precursor, it has a functional group capable of generating a carboxyl group, a hydroxyl group, a thiol group, an amino group, a sulfo group or a phosphono group upon decomposition, and has a heat / heat content. Pre-crosslinked resins containing a functional group that is cured by light are used (JP-A-1-226394, 1-269593, 1-
No. 288488), a combination of the above-mentioned functional group-containing resin and a heat / photocurable resin (JP-A-1-266546, 1-275191, 1-309068),
The functional group-containing resin and a crosslinking agent are used in combination (JP-A 1-2).
No. 67093, No. 1-271292, No. 1-3090.
No. 67), the improvement of the hydrophilicity of the non-image area, the improvement of the film strength of the image receiving layer, and the improvement of the printing durability have been investigated.

Further, in the image receiving layer, resin particles having a fine particle diameter of 1 μm or less containing a hydrophilic group such as a carboxyl group, a sulfo group and a phosphono group are contained together with an inorganic pigment and a binder (Japanese Patent Laid-Open No. Hei 10 (1999) -58242). 4-201387, 4-2
No. 23196), or fine resin particles containing a functional group that produces a hydrophilic group as described above by decomposition (Japanese Patent Laid-Open Nos. 4-319491 and 4-353).
No. 495, No. 5-119545, No. 5-58071
JP-A-5-69684) to improve the hydrophilicity of the non-image area.

However, in the conventional printing plate thus obtained, the hydrophobicity is increased by increasing the addition amount of the waterproofing agent or using the hydrophobic resin in order to improve the printing durability. However, there is a problem that the printing durability is improved, but the hydrophilicity is reduced to cause printing stains. On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is deteriorated.

In particular, under a use environment at a high temperature of 30 ° C. or higher, the surface layer is dissolved in the immersion water used for offset printing, and there are drawbacks such as deterioration of printing durability and occurrence of printing stains. Furthermore, in the case of a direct-drawing type lithographic printing plate precursor, an oil-based ink or the like is drawn as an image portion on the image receiving layer, and if the adhesion between the receiving layer of the printing plate and the oil-based ink is not good,
Even if the non-image area has sufficient hydrophilicity and the above-mentioned printing stains do not occur, the oil-based ink in the image area is lost during printing, resulting in a decrease in printing durability. It has not reached the point where it is resolved to.

On the other hand, a plate comprising a hydrophilic layer containing titanium oxide, polyvinyl alcohol and hydrolyzed tetramethoxysilane or tetraethoxysilane as an image receiving layer (JP-A-3-42679, 10-268583).
No.) are known. However, when the plate was actually made and printed as a printing plate, the printing durability of the image was insufficient.

[0012]

As described above, in order to increase the hydrophilicity of the image receiving layer, it has been known that it is necessary to increase the water retention amount in the image receiving layer. However, if an attempt is made to increase the water retention amount, there is a problem that the swelling property of the film becomes large, the structure of the film becomes weak and the film strength decreases, or the adhesion between the support and the image receiving layer deteriorates. .

The present invention improves the above-mentioned problems of the conventional lithographic printing plate precursor. Therefore, an object of the present invention is to provide an excellent lithographic printing plate precursor that does not cause spot stains as well as uniform stain stains on the entire surface as an offset printing plate. Another object of the present invention is to provide a lithographic printing plate precursor that provides a printing plate that is capable of printing a large number of clear image-printed materials that are free from scumming and have no image defects or distortions.

[0014]

As a result of various investigations, as a result of various investigations, it was found that a hydrophilic surface graft polymer is used as an image receiving layer in which a polymer compound having a hydrophilic functional group is chemically bonded to the surface. The inventors of the present invention have found that the above problems can be solved and have reached the present invention. This has a structure in which the hydrophilic polymer chain in the surface-grafted hydrophilic layer of the present invention has no constraint other than bonding to the image-receiving layer surface,
It is presumed that this is due to the fact that water easily enters and the amount of water retention is large. While such a surface-grafted hydrophilic polymer absorbs a large amount of water and can be largely swelled, the surface-grafted hydrophilic polymer has a polymer chain chemically bonded to the surface of the image-receiving layer, so that the surface-grafted hydrophilic polymer can swell even if an image The adhesion with the receiving layer does not deteriorate. In this way, it is possible to simultaneously exhibit water retention and image adhesion, which are in a trade-off relationship in the conventional technique. That is, the above object of the present invention is achieved by the following configurations.

(1) In a lithographic printing plate precursor having an image-receiving layer on a water-resistant support, the image-receiving layer has porous filler particles and metal atoms and / or metalloid atoms connected to each other through oxygen atoms. A binder resin comprising a complex of a resin containing such a bond and an organic polymer containing a group capable of forming a hydrogen bond with the resin, and at least one hydrophilic functional group in the image receiving layer. A lithographic printing plate precursor comprising a surface-grafted hydrophilic layer chemically bound to a polymer compound.

(2) The polymer compound having at least one hydrophilic functional group is linked to the image receiving layer either directly or through a trunk polymer compound chemically bonded to the image receiving layer. The lithographic printing plate precursor as described in (1) above, which is a linear polymer compound chemically bonded at the terminal.

(3) The lithographic printing plate precursor as described in (1) or (2) above, wherein the average pore size distribution of the porous filler particles is 1Å to 1 μm.

[0018] (4) the average specific surface area of the porous filler particles is characterized by a ^{0.05m 2 / g~5000m 2 / g (} 1) ~ lithographic according to any one of (3) Original version.

(5) The mixing ratio of the binder resin and the total filler in the image receiving layer is as follows: binder resin / total filler = 80/20 to 5
/ 95 (mass ratio), wherein (1) to
The lithographic printing plate precursor as described in any of (4).

(6) A resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom is obtained by hydrolytic cocondensation of at least one compound represented by the following general formula (I). The lithographic printing plate precursor as described in any one of (1) to (5) above, which is a polymer to be used.

The general formula (I) (R ⁰ ) _n M ⁰ (Y) _zn

[In the general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group,
M ⁰ represents a metal or metalloid having a valence of 3 to 6, z represents the valence of M ⁰ , and n represents ⁰ , 1, 2, 3 or 4. However, z
-N is 2 or more. ]

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. First, the image receiving layer having the surface-grafted hydrophilic layer of the present invention will be described.

The surface-grafted hydrophilic layer of the present invention comprises a polymer compound having at least one hydrophilic functional group chemically bonded to the image-receiving layer and covers the surface of the image-receiving layer thinly. Form a hydrophilic layer. In the present invention, the terminal of the polymer compound having at least one hydrophilic functional group is directly or through another polymer compound in the image receiving layer of the lithographic printing plate (hereinafter, the polymer compound for binding is In particular, it may be referred to as a "stem polymer compound"), and is chemically bound.

The polymer compound having a hydrophilic functional group which constitutes the above graft portion is not particularly limited, but is preferably a linear polymer compound. As the hydrophilic functional group, an amide group, a carboxyl group, a sulfonic acid group, a phosphoric acid, a phosphonic acid or an amino group or a salt thereof,
2-Trimethylaminoethyl (meth) acrylate or its hydrohalide and the like can be mentioned. It suffices that at least one of these hydrophilic functional groups is contained in the polymer compound constituting the graft portion, and for example, the end of the linear polymer compound on the side opposite to the bonding portion with the image receiving layer. When the linear polymer has a hydrophilic functional group, the linear polymer may contain a hydrophilic monomer as a polymerization component or a copolymerization component.

The hydrophilic monomer that can be used in the present invention is not particularly limited as long as it has the above-mentioned hydrophilic functional group. Examples of particularly useful hydrophilic monomers include (meth) acrylic acid or its alkali metal salt or amine salt, itaconic acid or its alkali metal salt or amine salt, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide. , N
-Monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide or allylamine or its hydrohalide, 3-vinylpropionic acid or its alkali metal salt or amine salt, vinylsulfonic acid or its alkali metal salt or amine salt ,
Vinylstyrenesulfonic acid or its alkali metal salt or amine salt, 2-sulfoethylene (meth) acrylate or 3-sulfopropylene (meth) acrylate or its alkali metal salt or amine salt, polyoxyethylene glycol mono (meth) acrylate or 2 Examples thereof include acrylamido-2-methylpropanesulfonic acid or its alkali metal salt or amine salt, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate or allylamine or its hydrohalide salt.

The surface-grafted hydrophilic layer of the present invention can be easily produced by a means generally called surface graft polymerization. Graft polymerization gives an active species on the polymer chain, thereby polymerizing another monomer to start,
This is a method for synthesizing a graft (grafting) polymer, and is called surface graft polymerization, particularly when a polymer chain that gives an active species forms a solid surface. The surface graft hydrophilic layer of the present invention can be easily obtained by performing surface graft polymerization on the surface of the image receiving layer.

As the surface graft polymerization method for realizing the image receiving layer of the present invention, any known method described in the literature can be used.
10, edited by The Society of Polymer Science, 1994, published by Kyoritsu Shuppan Co., Ltd., P135, surface graft polymerization methods such as photograft polymerization method, plasma irradiation graft polymerization method, adsorption technology handbook NTS
Radiation irradiation graft polymerization method such as γ-ray and electron beam described in p203, p695, supervised by Takeuchi, 1999.2, p. Further, as a specific method of the photograft polymerization method, the methods described in JP-A-10-296895 and JP-A-11-119413 can be used.

In addition to these methods, the surface-grafted hydrophilic layer of the present invention may be prepared by adding reactive functional groups such as trialkoxysilyl groups, isocyanate groups, amino groups, hydroxyl groups and carboxyl groups to the ends of the polymer compound chain. It is also possible to cite a method in which a group is provided and the group is formed by a coupling reaction between the group and a functional group on the surface of the image receiving layer of the planographic printing plate.

A linear polymer having a trunk polymer compound chemically bound to the surface of the image receiving layer and a hydrophilic functional group bound to the trunk polymer compound at the end of the polymer chain. In the case of producing a hydrophilic image-receiving layer comprising a compound, a functional group capable of undergoing a coupling reaction with a functional group on the surface of the image-receiving layer is added to the side chain of the trunk polymer compound, and a hydrophilic functional group as a graft chain It can be formed by synthesizing a graft type polymer compound in which a polymer compound chain having a is incorporated and coupling reaction between the polymer and the functional group on the surface of the image receiving layer. Specific examples of such a trunk polymer compound include the same ones as the organic polymers forming a complex with the (semi) metal-containing resin described later.

Among the above-mentioned photograft polymerization method, plasma irradiation graft polymerization method, radiation irradiation graft polymerization method, and coupling method, the plasma irradiation graft polymerization method and the radiation irradiation graft polymerization method are particularly excellent in terms of production suitability. .
Specifically, in the plasma irradiation graft polymerization method, in the radiation irradiation graft polymerization method, the above-mentioned literature, and Y.Ik
ada et al., Macromolecules vol. 19, page 1804 (198)
It can be created by the method described in 6). It can be obtained by treating the surface of the image receiving layer with plasma or an electron beam to generate radicals on the surface and then reacting the active surface with a monomer having a hydrophilic functional group.

The thickness of the surface graft hydrophilic layer of the present invention is preferably in the range of ^{0.01g / m 2 ~10g / m 2} , more preferably in the range of 0.1g / m ² ~5g / m ² . Within this range, the effects of the present invention can be sufficiently exhibited, further good printing durability can be obtained, and fine line reproducibility of printed matter is also good,
preferable.

Next, the porous filler particles used in the image receiving layer of the present invention will be described. The porous filler of the present invention may be inorganic particles or organic particles as long as it is porous and is not particularly limited. As the inorganic porous filler,
Examples include metals, oxides, complex oxides, hydroxides, carbonates, sulfates, silicates, phosphates, nitrides, carbides, sulfides, and complex compounds of at least two or more thereof.
Specifically, silica, glass, titanium oxide, zinc oxide, alumina, zircon oxide, tin oxide, potassium titanate, aluminum borate, magnesium oxide, magnesium borate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, basic Magnesium sulfate, calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, silicon carbide, titanium carbide, zinc sulfide, zeolite, and at least 2 of these. Examples include complex compounds of two or more species. Preferably, silica, glass, titanium oxide, alumina, zeolite, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium phosphate, calcium sulfate and the like can be mentioned. To be

Examples of the organic porous filler include carbon compounds, polymer compounds, celluloses, and composites of at least one of these compounds and an inorganic compound. Specifically, charcoal, activated carbon, polymer porous Examples thereof include sintered bodies, resin foams, silicon porous bodies, and super absorbent resins. Preferably, charcoal, activated carbon, polymer porous sintered body,
Superabsorbent resins and the like can be mentioned.

With respect to the size of the porous filler, the average particle diameter is preferably 0.03 μm to 20 μm, more preferably 0.05 μm to 15 μm, and further preferably 0.1 μm.
10 to 10 μm. The pore diameter of the porous filler has an average pore diameter distribution of preferably 1Å to 1 µm, more preferably 10Å to 500 nm, and further preferably 50Å to 300 n.
m. Surface area of the porous filler has an average specific surface area, preferably 0.05m ² / g~5000m ² / g, more preferably 1m ² / g~3000m ² / g, more preferably 10m ² / g~1000m ² / It is g.

In the present invention, it is not necessary that all the fillers used in the image receiving layer are porous fillers, and the amount of the porous filler is preferably 25% by mass or more of the total amount of the fillers in the image receiving layer. , More preferably 50% by mass or more of the total amount of filler, and further preferably 75
It is at least mass%.

The filler that can be used in combination with the above-mentioned porous filler may be inorganic particles, organic particles, or a composite material thereof, and is not particularly limited. Examples of the inorganic particles include metal powders, metal oxides, metal nitrides, metal sulfides, metal carbides and their composites, and the like, preferably metal oxides and metal sulfides, and more preferably Is glass, SiO ₂ , TiO ₂ , ZnO, Fe ₂ O ₃ , ZrO ₂ ,
Particles of SnO ₂ , ZnS, CuS and the like can be mentioned. The organic particles include, for example, synthetic resin particles and natural polymer particles, preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethyleneimine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide. , Carboxymethyl cellulose, gelatin, starch, chitin, chitosan and the like, more preferably resin particles of acrylic resin, polyethylene, polypropylene, polystyrene and the like.

The mixing ratio (mass ratio) of the composite (binder resin) and all the filler components is preferably 80/20 to 5/95, more preferably 70/30 to 5 in the binder resin / all fillers.
/ 95, and more preferably 60/40 to 5/95.

Next, the binder resin used in the image receiving layer of the present invention will be described. The binder resin of the present invention includes a resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom (hereinafter, also referred to as “(semi) metal-containing resin”), and this resin. It is a resin comprising a complex with an organic polymer containing a group capable of forming a hydrogen bond with.

The "composite of (semi) metal-containing resin and organic polymer" is used to mean a sol-like substance and a gel-like substance. The (semi) metal-containing resin refers to a polymer mainly containing a bond composed of "oxygen atom-metal atom or semimetal atom-oxygen atom". Here, the (semi) metal-containing resin is
It may contain both metal atoms and metalloid atoms.
Preferred are resins containing only semi-metal atoms and resins containing semi-metal atoms and metal atoms.

The (semi) metal-containing resin has the following general formula (I):
It is preferably a polymer obtained by hydrolysis-cocondensation of a compound represented by General formula (I) (R ⁰ ) _n M ⁰ (Y) _zn [In the general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M ⁰ Is 3-6
Represents a valent metal or metalloid, z represents the valence of M ⁰ , and n
Represents 0, 1, 2, 3, or 4. However, z-n is 2
That is all. Here, the hydrolytic cocondensation is a reaction in which a reactive group repeats hydrolysis and condensation under acidic or basic conditions to polymerize. The above compounds are used singly or in combination of two or more kinds to produce a (semi) metal-containing resin.

Next, the (semi) metal compound represented by the general formula (I) will be described in detail. R in the general formula (I)
⁰ is preferably an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, Octyl group, nonyl group, decyl group, dodecyl group, etc .; groups which can be substituted by these groups include halogen atom (chlorine atom, fluorine atom, bromine atom), hydroxy group, thiol group, carboxy group, sulfo group, cyano group Group, epoxy group, -OR 'group (R' is a hydrocarbon group such as methyl group, ethyl group, propyl group,
Butyl group, hexyl group, heptyl group, octyl group, decyl group, propenyl group, butenyl group, hexenyl group, octenyl group, 2-hydroxyethyl group, 3-chloropropyl group, 2-cyanoethyl group, N, N-dimethylamino Ethyl group, 2-bromoethyl group, 2- (2-methoxyethyl) oxyethyl group, 2-methoxycarbonylethyl group, 3-carboxypropyl group, benzyl group, etc.), -OCOR 'group, -COOR' group,- COR '
Group, -N (R ") (R") (R "represents a hydrogen atom or the same content as R'and may be the same or different), -NHCONHR 'group, -NHCOOR' group,-
Si (R ') ₃ group, -CONHR "group, -NHCOR'
Groups and the like. Multiple of these substituents may be substituted in the alkyl group)},

An optionally substituted linear or branched alkenyl group having 2 to 12 carbon atoms (for example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, etc. Examples of the group substituted with these groups include those having the same contents as the group substituted with the alkyl group, and a plurality of them may be substituted), or a group having 7 to 14 carbon atoms may be substituted. Good aralkyl group (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, etc.); the group substituted by these groups is the same as the group substituted by the alkyl group. The contents of
A plurality of them may be substituted), and an alicyclic group having 5 to 10 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, norbonyl group, adamantyl group) etc,
Examples of the group substituted with these groups include those having the same contents as the above-mentioned substituents of the alkyl group, and a plurality of them may be substituted), and an optionally substituted aryl group having 6 to 12 carbon atoms ( For example, a phenyl group and a naphthyl group, examples of the substituent include those having the same content as the group substituted by the alkyl group, and a plurality of them may be substituted),

Alternatively, a heterocyclic group which may be condensed with at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, as a hetero ring, a pyran ring, a furan ring, a thiophene ring, morpholine A ring, a pyrrole ring, a thiazole ring, an oxazole ring, a pyridine ring, a piperidine ring, a pyrrolidone ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a tetrahydrofuran ring and the like, which may have a substituent, may be contained. The same contents as the substituents in the alkyl group are mentioned, and a plurality of them may be substituted).

The reactive group Y is preferably a hydroxy group, a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a -OR ¹ group, a -OCOR ² group, a -OR group.
^{CH (COR 3) (COR 4} ) group, -CH (COR ³⁾ (CO
OR ⁴⁾ represents a group, or ^{-N (R 5) (R 6} ) group.

In the --OR ¹ group, R ¹ has 1 to 10 carbon atoms.
Optionally substituted aliphatic group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, propenyl group, butenyl group, heptenyl group) , Hexenyl group, octenyl group, decenyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2-methoxyethyl group, 2- (methoxyethyloxy) ethyl group, 2-
(N, N-diethylamino) ethyl group, 2-methoxypropyl group, 2-cyanoethyl group, 3-methyloxypropyl group, 2-chloroethyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, chlorocyclohexyl group, methoxycyclohexyl group , Benzyl group, phenethyl group, dimethoxybenzyl group, methylbenzyl group, bromobenzyl group and the like).

In the --OCOR ² group, R ² is an aliphatic group similar to R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (as the aromatic group, the aryl group in R ⁰ above). The same as those exemplified above can be mentioned). -CH
(COR ³⁾ (COR ⁴⁾ group and the -CH (COR ³⁾ (COO
In the R ⁴ ) group, R ³ is an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.)
Or an aryl group (eg, phenyl group, tolyl group, xylyl group, etc.), and R ⁴ is an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). Etc.), an aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, methoxybenzyl group, carboxybenzyl group, chlorobenzyl group, etc.) or aryl group (eg, phenyl group, (Tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, carboxyphenyl group, diethoxyphenyl group, etc.)
Represents Further, in the group —N (R ⁵ ) (R ⁶ ), R ⁵ and R ^5
6 may be the same as or different from each other, and preferably each is a hydrogen atom or an optionally substituted aliphatic group having 1 to 10 carbon atoms (for example, those having the same contents as R ^{1 of the} aforementioned —OR ¹ group). Is mentioned). More preferably, the total number of carbon atoms of R ⁵ and R ⁶ is 12 or less.

The (semi) metal M ⁰ is preferably a transition metal, a rare earth metal or a metal of Group III to V of the periodic table. More preferably Al, Si, Sn, Ge, Ti, Z
r, etc., and more preferably Al, Si, Sn, T
i, Zr and the like. Si is particularly preferable.

Specific examples of the (semi) metal compound represented by the general formula (I) include, but are not limited to, the following.

Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n
-Propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-
Hexyltri-t-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n
-Decyltriisopropoxysilane, n-decyltri-t
-Butoxysilane, n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane, phenyltrichloro Silane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane,

Tetrachlorsilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane,
Dimethyldibromosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane , Tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane , Trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, trifluoropropyl tri t- butoxysilane,

Γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltriisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane, γ-
Methacryloxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldiethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane, γ-mercaptopropylmethyldimethoxysilane ,
γ-mercaptopropylmethyldiethoxysilane, γ-
Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxinlan, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- ( 3,4
-Epoxycyclohexyl) ethyltriethoxysilane,

Ti (OR) ₄ (wherein R represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.)), TiC
l ₄ , Zn (OR) ₂ , Zn (CH ₃ COCHCOC
_{H 3) 2, Sn (OR} ) 4, Sn (CH 3 COCHCOCH 3)
₄ , Sn (OCOR) ₄ , SnCl ₄ , Zr (OR) ₄ , Zr
_{(CH 3 COCHCOCH 3) 4,} Al (OR) 3.

Next, in the present invention, the organic polymer forming a complex with the (semi) metal-containing resin will be described. The organic polymer has a group capable of forming a hydrogen bond with the (semi) metal-containing resin (hereinafter, also referred to as a specific bonding group). The specific bonding group preferably includes at least one bond selected from an amide bond (including a carboxylic acid amide bond and a sulfonamide bond), a urethane bond and a ureido bond, and a hydroxyl group.

Examples of the organic polymer include those containing, as a repeating unit component, the specific bonding group of the present invention in at least one polymer main chain and / or side chain. Preferably, as the repeating unit component, -N (R ¹¹ ) CO
^{-, - N (R 11)} SO 2 -, - NHCONH- and -N
A component in which at least one bond selected from HCOO- is present in the main chain and / or side chain of the polymer, and / or-
Examples include components containing an OH group. R ¹¹ in the amide bond represents a hydrogen atom or an organic residue, and examples of the organic residue include those having the same contents as the hydrocarbon group and the heterocyclic group for R ⁰ in the general formula (I). .

The polymer main chain contains the specific linking group of the present invention.
As the polymer having, -N (R ¹¹) CO-bonded
Is -N (R¹¹) SO₂-Amide resin having a bond, -N
Ureido resin having HCONH-bond, -NHCOO
-Examples include urethane resins containing a bond.

Examples of diamines and dicarboxylic acids or disulfonic acids used for the production of amide resins, diisocyanates used for ureido resins, and diols used for urethane resins include “Polymer Data Handbook-ed. Basic Edition- "Chapter I, Baifukan Co., Ltd. (1
986), Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" published by Taiseisha (1981) and the like can be used.

Examples of the other amide bond-containing polymer include a polymer containing a repeating unit represented by the following general formula (II), an N-acylated polyalkyleneimine, or polyvinylpyrrolidone and its derivative.

[0059]

[Chemical 1]

In the formula (II), Z ¹ represents -CO-, -SO ₂ -or -CS-. R ²⁰ has the same content as R ⁰ in formula (I). r ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.). r ¹ may be the same or different. p represents an integer of 2 or 3.

Among the polymers containing the repeating unit represented by the general formula (II), Z ¹ represents -CO- and p is 2
The polymer represented by is obtained by ring-opening polymerization of oxazoline which may have a substituent in the presence of a catalyst. Examples of the catalyst include sulfuric acid esters and sulfonic acid esters such as dimethyl sulfate and p-toluenesulfonic acid alkyl ester; alkyl halides such as alkyl iodide (for example, methyl iodide); metal fluorides of Friedel-Crafts catalysts; Acids such as sulfuric acid, hydrogen iodide and p-toluenesulfonic acid, and oxazolinium salts which are salts of these acids with oxazoline can be used. The polymer may be a homopolymer or a copolymer. Further, it may be a copolymer obtained by grafting this polymer on another polymer.

Specific examples of oxazoline include, for example:
2-oxazoline, 2-methyl-2-oxazoline, 2
-Ethyl-2-oxazoline, 2-propyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-
Butyl-2-oxazoline, 2-dichloromethyl-2-
Oxazoline, 2-trichloromethyl-2-oxazoline, 2-pentafluoroethyl-2-oxazoline, 2
-Phenyl-2-oxazoline, 2-methoxycarbonylethyl-2-oxazoline, 2- (4-methylphenyl) -2-oxazoline, 2- (4-chlorophenyl)
-2-oxazoline and the like. Preferred oxazolines include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline and the like. These oxazoline polymers can be used alone or in combination of two or more.

Regarding other polymers having the repeating unit represented by the general formula (II), thiazoline, 4,5-dihydro-1,3-oxazine or 4,5-dihydro-1,3-thiazine may be used instead of oxazoline. Can be similarly obtained by using.

As the N-acylated form of polyalkyleneimine, a carboxylic acid amide form containing -N (CO-R ²⁰ )-obtained by a polymer reaction with carboxylic acid halides, or a high-performance product with sulfonyl halides can be used. -N obtained by molecular reaction
A sulfonamide compound containing (SO ₂ —R ²⁰ ) — (wherein
R ²⁰ has the same meaning as R ²⁰ in formula (II)) can be mentioned.

Further, the polymer containing a specific bonding group of the present invention in the side chain of the polymer contains as a main component a component containing at least one bonding group selected from the specific bonding groups. There are things. Examples of such components include acrylamide, methacrylamide, crotonamide, vinylacetamide, and the following compounds. However, the present invention is not limited to these.

[0066]

[Chemical 2]

[0067]

[Chemical 3]

On the other hand, the hydroxyl group-containing organic polymer may be any of natural water-soluble polymers, semi-synthetic water-soluble polymers, and synthetic polymers. Polymer Compound I ”published by Asakura Shoten (196
0 years), "Development of Comprehensive Technical Data on Water-Soluble Polymers and Water-Dispersible Resins" edited by the Management Development Center, published by Management Development Center Publishing (1981), Shinji Nagatomo, "Applications and Markets of New Water-Soluble Polymers" ( Published by CMC Inc. (1988), "Development of Functional Cellulose" Published by CMC Inc. (1985)
Year)) and so on.

Examples of natural and semi-synthetic polymers include cellulose, cellulose derivatives (cellulose esters; cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose succinate, cellulose butyrate, cellulose acetate succinate, acetic acid). Cellulose butyrate, cellulose acetate phthalate, etc., cellulose ethers; methyl cellulose, ethyl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), starch, starch derivative ( Oxidized starch, esterified starches; nitric acid, sulfuric acid, phosphoric acid, acetic acid, propion , Esterified products of butyric acid, succinic acid, etc., etherified starches; methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethylated, etc.), alginic acid, pectin, carrageenan, tamarind gum, natural gums ( Gum arabic, guar gum, locust bean gum, tragacanth gum, xanthan gum, etc.), pullulan, dextran, casein, gelatin, chitin, chitosan and the like.

As the synthetic polymer, for example, polyvinyl alcohol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, (ethylene glycol / propylene glycol) copolymer, etc.), allyl alcohol copolymer, acryl containing at least one hydroxyl group are used. Polymer or copolymer of acid ester or methacrylic acid ester (for example, as an ester substituent, 2
-Hydroxyethyl group, 3-hydroxypropyl group,
2,3-dihydroxypropyl group, 3-hydroxy-2
-Hydroxymethyl-2-methylpropyl group, 3-hydroxy-2,2-di (hydroxymethyl) propyl group,
Polyoxyethylene group, polyoxypropylene group,
Etc.), a polymer or copolymer of N-substituted acrylamide or methacrylamide containing at least one hydroxyl group (as the N-substituent, for example, monomethylol group, 2-hydroxyethyl group, 3-hydroxypropyl group) , 1,1-bis (hydroxymethyl) ethyl group, 2,
3,4,5,6-pentahydroxypentyl group, etc.) and the like. However, the synthetic polymer is not particularly limited as long as it has at least one hydroxyl group in the side chain substituent of the repeating unit.

The organic polymers of the present invention may be used alone or in combination of two or more. The weight average molecular weight of the organic polymer is preferably 10 ³ to 10 ⁶ , and more preferably 5 × 10 ³ to 4 × 10 ⁵ .

In the composite of the (semi) metal-containing resin and the organic polymer, the ratio of the (semi) metal-containing resin and the organic polymer can be selected within a wide range, but the (semi) metal-containing resin / organic polymer mass is preferable. 10/90 to 90/1 in ratio
0, more preferably 20/80 to 80/20. Within this range, the strength of the image-receiving layer film and the water resistance to dampening water during printing will be good.

The binder resin containing the composite of the present invention comprises a hydroxyl group of a (semi) metal-containing resin produced by hydrolysis and polycondensation of the (semi) metal compound, and the specific bonding group in the organic polymer. Form a uniform organic-inorganic hybrid due to hydrogen bonding action and become microscopically homogeneous without phase separation. When a hydrocarbon group is present in the (semi) metal-containing resin, it is presumed that the affinity with the organic polymer is further improved due to the hydrocarbon group. Further, the composite of the present invention is excellent in film forming property.

The composite of the present invention is produced by hydrolytically polycondensing the (semi) metal compound and mixing it with an organic polymer, or by hydrolyzing the (semi) metal compound in the presence of the organic polymer. It is produced by polycondensation. Preferably, the organic-inorganic polymer composite of the present invention can be obtained by subjecting the (semi) metal compound to hydrolysis and polycondensation by a sol-gel method in the presence of an organic polymer. In the formed organic-inorganic polymer composite, the organic polymer is homogeneous in the gel matrix (that is, the three-dimensional fine network structure of the inorganic (semi) metal oxide) formed by the hydrolysis polycondensation of the (semi) metal compound. Are dispersed in.

The above-mentioned sol-gel method can be carried out by using a conventionally known sol-gel method. Specifically, "Sol-gel method for thin film coating" (Technical Information Association) (published) (1995), Sakubana Seo "Sol-gel method science" (agne Jofusha Co., Ltd.) ) (1988), S. Hirashima, "Technology for producing functional thin film by latest sol-gel method", Comprehensive Technology Center (published) (1992) and the like, according to the method described in detail.

The coating liquid for the image receiving layer is preferably an aqueous solvent, and further a water-soluble solvent is used together for the purpose of uniform liquefaction by suppressing precipitation during preparation of the coating liquid. As the water-soluble solvent, alcohols (methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.), ethers (tetrahydrofuran , Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, acetylacetone, etc.), esters (methyl acetate, ethylene glycol monoacetate, etc.), amides (formamide, N-methylformamide, pyrrolidone) , N-methylpyrrolidone, etc.) and the like, and one kind or a combination of two or more kinds. It may be.

Further, in order to accelerate the hydrolysis and co-condensation reaction of the (semi) metal compound represented by the general formula (I), it is preferable to use an acidic catalyst or a basic catalyst in combination.

As the catalyst, an acid or basic compound as it is or in a state of being dissolved in a solvent such as water or alcohol (hereinafter referred to as an acidic catalyst or a basic catalyst) is used. The concentration at that time is not particularly limited, but if the concentration is high, the hydrolysis and polycondensation rates tend to be high. However, if a basic catalyst with a high concentration is used, a precipitate may be generated in the sol solution,
The concentration of the basic catalyst is preferably 1N (converted to a concentration in an aqueous solution) or less.

The type of acidic catalyst or basic catalyst is not particularly limited, but when it is necessary to use a catalyst with a high concentration, a catalyst composed of elements that hardly remain in the catalyst crystal grains after sintering is used. Good. Specifically, as the acidic catalyst, hydrogen halide such as hydrochloric acid, nitric acid, sulfuric acid,
Sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, substituted carboxylic acids obtained by substituting R of structural formula RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, etc. Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia and amines such as ethylamine and aniline.

In addition, a cross-linking agent may be added to the image receiving layer in order to improve the film strength. Examples of the cross-linking agent include compounds usually used as cross-linking agents. Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook for Crosslinking Agents," published by Taiseisha (1981), "Polymer Data Handbook, Basic Edition," edited by the Society of Polymer Science, Baifukan (198)
6 years) and the like can be used.

For example, ammonium chloride, metal ions,
Organic peroxides, polyisocyanate compounds (for example, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene phenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate Nato, etc.), polyol compound (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyethylene glycol, 1,1,1
-Trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxies Resin (for example, "New Epoxy Resin" edited by Hiroshi Kakiuchi, Shokoido (1985), "Epoxy Resin" edited by Kuniyuki Hashimoto)
Compounds described in Nikkan Kogyo Shimbun (1969), etc.), melamine resin (for example, compounds described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbun (1969)) , Poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, "Oligomer" Kodanmori (Published in 1976), Eizo Omori "Functional Acrylic Resin" Techno System (1985)
And the like).

The image-receiving layer of the present invention is formed by coating the image-receiving layer coating liquid on a water-resistant support by any of the conventionally known coating methods and drying.

The thickness of the image receiving layer formed is 0.2 to 1
0 μm is preferable, and 0.5 to 8 μm is more preferable. Within this range, a film having a uniform thickness is formed, and the film has sufficient strength.

The surface smoothness of the image-receiving layer before the surface-grafted hydrophilic layer of the present invention is bonded is preferably 30 (sec / 10 ml) or more in terms of Beck's smoothness. Here, Beck's smoothness can be measured by a Beck's smoothness tester, and a test piece is placed on a highly smooth finished circular glass plate with a hole in the center at a constant pressure (1 kg / cm ² ). It measures the time required for a certain amount (10 ml) of air to pass between the glass surface and the test piece under pressure reduction under reduced pressure.

When plate making (image formation) is performed by an electrophotographic printer, the preferred range of the toner to be used is dry toner and liquid toner as follows.

In the electrophotographic printer using the dry toner, the Bekk smoothness of the surface of the image receiving layer of the original plate of the present invention is preferably 30 to 200 (sec / 10 ml), more preferably 50 to 150 (sec / 10 ml). Is. Within this range, in the process of transferring and fixing the toner image to the original plate, scattering toner is prevented from adhering to the non-image area (that is, scumming), and the toner adhesion in the image area is made uniform and sufficient. Good reproducibility of fine characters and uniformity of solid image area.

On the other hand, in the electrophotographic printer using the liquid toner, the Bekk smoothness of the surface of the image receiving layer is 30 (sec / 10 ml) or more, and the higher the better, the better 150-3000 (sec / sec).
10 ml), more preferably 200-2500 (sec / 10 ml)
Is.

In the case of an ink jet type printer or a thermal transfer type printer, the same range as in the case of the electrophotographic printer using the liquid toner is preferable. In this range, high-definition toner image areas such as fine lines / fine characters and halftone images are faithfully transferred / formed on the image receiving layer, and the surface of the image receiving layer and the toner image area are sufficiently adhered to each other, resulting in strong image area. Can be held.

More preferably, the shape of the surface of the image receiving layer before the surface-grafted hydrophilic layer of the present invention is bonded is such that unevenness is high and the intervals are close. Specifically, I
It is preferable that the surface center average roughness SRa defined by SO-468 is in the range of 1.3 to 3.5 μm, and the average wavelength Sλa indicating the density of the surface roughness is in the range of 50 μm or less. More preferably, SRa is 1.35 to 2.5
μm and Sλa are in the range of 45 μm or less. It is presumed that this suppresses the adhesion of the scattered toner to the non-image area after electrophotographic plate making and the thickening of the adhered toner during fixing.

Next, the water-resistant support used in the present invention will be described. As the water resistant support, an aluminum plate, a zinc plate, a copper-aluminum plate, a copper-stainless plate,
Trimetal plates such as bimetal plates such as chrome-copper plates, chrome-copper-aluminum plates, chrome-lead-iron plates, chrome-copper-stainless plates, etc., with a thickness of 0.1-3 mm, especially 0.1-1 mm The following are listed. Also, the thickness is 80μ
Examples of the paper include water-resistant paper having a thickness of m to 200 μm, a plastic film, or a paper or plastic film laminated with a metal foil.

The support used in the present invention preferably has a highly smooth surface. That is, the surface smoothness adjacent to the image receiving layer has a Beck's smoothness of 300 (sec / 10 m).
l) or more, more preferably 900 to 3000 (sec / 10 m)
It is preferably adjusted to 1), more preferably 1000 to 3000 (sec / 10 ml).

By controlling the smoothness of the surface of the support adjacent to the image receiving layer to be Beck smoothness of 300 (sec / 10 ml) or more, the image reproducibility and printing durability can be further improved. . Such an improving effect can be obtained even if the smoothness of the image receiving layer surface is the same,
It is considered that the increased smoothness of the surface of the support improved the adhesion between the image area and the image receiving layer.

The highly smooth surface of the water-resistant support regulated in this way refers to the surface on which the image-receiving layer is directly coated. For example, a conductive layer, an under layer, an over layer, which will be described later, are formed on the support. When a coat layer is provided, its conductive layer,
It means the surface of the under layer and the overcoat layer. As a result, the image receiving layer whose surface state has been adjusted as described above is sufficiently retained without being affected by the irregularities on the surface of the support, and the image quality can be further improved.

As a method of setting the smoothness range, various conventionally known methods can be used. Specifically, a method of melting and adhering the surface of the substrate with a resin, a method of adjusting the Bekk smoothness of the surface of the support by a method such as a calender strengthening method using a highly smooth heat roller, and the like can be mentioned.

The lithographic printing plate precursor according to the present invention is an electrostatic latent image-forming layer formed on a water-resistant support by forming a toner image by an electrophotographic recording method or discharging an oil-based ink by utilizing an electrostatic field. It can also be preferably used as a lithographic printing plate precursor used for forming an image by a discharge type inkjet method, and a lithographic printing plate obtained by image formation can print a large number of clear images.

The image formation by the electrophotographic recording method is usually an electrophotographic process, and the transfer of the toner image onto the transfer material is performed by electrostatic transfer. The water-resistant support as the printing plate precursor is preferably electrically conductive, and particularly has a volume specific resistance value of 10 ⁴ to 10 ¹³ Ω · cm, and more preferably 10 ⁷ to 10 ¹² Ω · cm. As a result, bleeding / distortion of the transferred image, toner adhesion stains on the non-image area, and the like are suppressed to a level where there is no practical problem, and a good image is obtained.

Also in the image formation by the electrostatic discharge type ink jet recording system, it is preferable that the water resistant support has conductivity, and at least the portion immediately below the image receiving layer is 10 ¹⁰ Ω · cm. It preferably has the following specific electric resistance value, and more preferably 10 ¹⁰ Ω · cm or less for the entire water resistant support. The above-mentioned specific electric resistance value is more preferably 10 ⁸ Ω · cm or less, and the value may be infinitely zero. When the conductivity is within the above range, when the charged ink droplets adhere to the image receiving layer, the charge of the ink droplets quickly disappears through the ground plane, so that a clear image without disturbance is formed. .

The specific electric resistance value (also called the volume specific electric resistance value or the specific electric resistance value) is measured by JIS.
It was carried out by a three-terminal method in which a guard electrode was provided according to K-6911.

In order to give the above-mentioned conductivity to the portion of the support directly below the image-receiving layer, a layer comprising a conductive filler such as carbon black and a binder is provided on a substrate such as paper or film. Examples of the method include coating, attaching a metal foil, and depositing a metal.

On the other hand, examples of the conductive material of the whole support include conductive paper impregnated with sodium chloride, a plastic film mixed with a conductive filler such as carbon black, a metal plate such as aluminum, etc. Can be mentioned.

For example, it can be obtained by using a conductive base paper in which a substrate is impregnated with sodium chloride or the like and providing a conductive layer having water resistance on both surfaces thereof. Examples of the base paper used as the substrate include wood pulp paper, synthetic pulp paper,
A mixed paper of wood pulp paper and synthetic pulp paper can be used as it is. The thickness of the base paper is 80 μm to 2
00 μm is preferable.

The conductive layer is formed by applying a layer containing a conductive filler and a binder to both sides of the conductive paper. The thickness of the conductive layer applied is 5 μm to 2 μm.
0 μm is preferable.

As the conductive filler, particulate carbon black, graphite such as silver, copper, nickel,
Metal powders such as brass, aluminum, steel and stainless steel, tin oxide powders, flaky aluminum or nickel, fibrous carbon and the like can be mentioned.

As the resin used as the binder, various resins are appropriately selected and used. Specifically, as the hydrophobic resin, for example, acrylic resin, vinyl chloride resin, styrene resin, styrene-butadiene resin,
Examples of the hydrophilic resin include styrene-acrylic resin, urethane resin, vinylidene chloride resin, vinyl acetate resin, and the like. Examples of the hydrophilic resin include polyvinyl alcohol resin, cellulose derivative, starch and its derivative, polyacrylamide resin, and styrene. Examples thereof include maleic anhydride-based copolymers.

Another method for forming a conductive layer is to laminate a conductive thin film. As the conductive thin film, for example, a metal foil, a conductive plastic film or the like can be used. More specifically, examples of the metal foil laminate include aluminum foil, and examples of the laminate of the conductive plastic film include polyethylene resin mixed with carbon black. The aluminum foil may be either hard or soft, and the thickness is 5μ.
m to 20 μm is preferable.

The extrusion laminating method is preferred for laminating polyethylene resin mixed with carbon black. The extrusion laminating method is a method in which polyethylene is heat-melted to form a film, which is immediately pressed onto a base paper and then cooled and laminated, and various apparatuses are known. The thickness of the laminate layer is preferably 10 μm to 30 μm. When a plastic film or a metal plate having conductivity is used as the substrate, assuming that the entire support has conductivity, it can be used as it is if the water resistance is satisfied.

As the conductive plastic film, for example, polypropylene or polyester film mixed with a conductive filler such as carbon fiber or carbon black can be used, and as the metal plate, aluminum or the like can be used. The thickness of the substrate is preferably 80 μm to 200 μm. If it is less than 80 μm, the strength of the printing plate is insufficient,
When it exceeds 200 μm, the handling property such as the transportability in the drawing device is deteriorated.

Next, the structure in which the conductive layer is provided will be described. As a water resistant substrate, the thickness is 80 μm to 2
Paper having a water resistance of 00 μm, a plastic film, a paper laminated with a metal foil, a plastic film, or the like can be used.

As the method for forming the conductive layer on the substrate, the method described in the case where the whole support has conductivity can be used. That is, a layer containing a conductive filler and a binder is applied to one surface of the substrate in a thickness of 5 μm to 20 μm. Alternatively, it can be obtained by laminating a metal foil or a conductive plastic film.

As a method other than the above, for example, a metal vapor deposition film of aluminum, tin, palladium, gold or the like may be provided on a plastic film. As described above, a water resistant support having conductivity can be obtained.

In the present invention, as described above, a back coat layer (back surface layer) can be provided on the side of the support opposite to the image receiving layer for the purpose of preventing curling. However, the back coat layer has a smoothness. It is preferably in the range of 150 to 700 (sec / 10 ml). As a result, when the printing plate is supplied to the offset printing machine, the printing plate is accurately set in the printing machine without causing misalignment or slippage.

The thickness of the water resistant support provided with the under layer or the back coat layer is in the range of 90 to 130 μm, preferably 100 to 120 μm.

The lithographic printing original plate of the present invention can be preferably used as a direct drawing type lithographic printing original plate, and a lithographic printing plate can be prepared by forming an image by a thermal transfer recording system, an electrophotographic recording system or an inkjet recording system. It can be carried out.

As the electrophotographic recording method, any conventionally known recording method can be used. For example, "Basics and Applications of Electrophotographic Technology" edited by The Electrophotographic Society of Japan, published by Corona Publishing Co., Ltd. (1988), Kenichi Eda, Journal of the Electrophotographic Society 27 ,
113 (1988), Akio Kawamoto, 33 , 149 (19)
94), Akio Kawamoto, 32 , 196 (1993), etc., or a commercially available PPC copying machine.

The combination of the scanning exposure method using laser light which is exposed based on digital information and the developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below.

First, the photosensitive material is positioned on the flat bed by the register pin method, and then sucked and fixed by air suction from the back surface. Next, for example, the photosensitive material is charged by the charging device described in "Basics and Applications of Electrophotographic Technology", page 212 et seq. The corotron or scotron system is common. At this time, it is also preferable to control the charging condition by giving feedback so that the surface potential is always within a predetermined range based on the information from the charging potential detection means of the photosensitive material. Then, for example, scanning exposure with a laser light source is performed using the method described on page 254 and the like of the above cited material.

Next, a toner image is formed using the liquid developer. The light-sensitive material charged and exposed on a flat bed can be removed from it, and the wet development method shown on page 275 and after of the above-mentioned reference can be used. The exposure mode at this time corresponds to the toner image development mode. For example, in the case of reversal development, a negative image, that is, an image portion is irradiated with laser light to charge the photosensitive material with the same charge polarity. The toner having the toner is used and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. The details of the principle are described on page 157 and after of the above cited material.

After the development, in order to remove the excess developing solution, squeeze such as rubber roller, gap roller, reverse roller, etc., corona squeeze, air squeeze, etc. as shown on page 283 of the same document are performed. It is also preferable to rinse only with the carrier liquid of the developer before squeezing.

Then, the toner image formed as described above on the photoconductor is transferred onto a lithographic printing plate precursor which is a transfer target material.
It is fixed, or transferred and fixed on the lithographic printing original plate via an intermediate transfer member.

The ink jet recording method may be any of the conventionally known recording methods.
An oil-based ink is preferred because of its fixability, difficulty in clogging of ink, and the like, and an electrostatic discharge type inkjet method is preferred because it does not easily cause image bleeding. A solid jet method using hot melt ink is also preferably used.

On-demand ink jet system using electrostatic force Susumu Ichinose, Yuji Ohba, IEICE Transactions Vol.J66-C (No.1), p47 (1983), Tadayoshi Ohno, Mamoru Mizuguchi, IEICE A method called an electrostatic acceleration type ink jet or a slit jet described in magazines vol.10, (No.3), p157 (1981) and the like is known, and a specific mode is, for example, JP-A-56-170, No. 56-4467, No. 57-
No. 151374 and the like.

This is achieved by supplying ink from the ink tank to the slit-shaped ink chamber in which a large number of electrodes are arranged on the inner surface of the slit-shaped ink holding portion, and by selectively applying a high voltage to these electrodes. The ink near the electrodes is ejected onto the recording paper that is in close proximity to the slit for recording.

As another method which does not use a slit-shaped recording head, Japanese Patent Laid-Open No. 61-211048 discloses that a hole is formed in a film-like ink support having a plurality of fine holes and ink is filled therein to form a multi-needle. A means for selectively applying a voltage by electrodes to move the ink in the holes to the recording paper is disclosed. In addition, as a solid jet method, Solid
Inkjet Platemaker SJ02A (manufactured by Hitachi Koki Co., Ltd.), MP
A commercially available printing system such as -1200Pro (manufactured by Dynic Co., Ltd.) can be used.

A plate making method using the ink jet recording method will be described more specifically with reference to the drawings. The apparatus system shown in FIG. 1 has an inkjet recording apparatus 1 that uses oil-based ink.

As shown in FIG. 1, first, pattern information of an image (graphic or text) to be formed on the master (lithographic printing original plate) 2 is transmitted from an information supply source such as the computer 3 via the bus 4. Then, the ink is supplied to the inkjet recording apparatus 1 using the oil-based ink. The ink jet recording head 10 of the recording apparatus 1 stores oil-based ink therein, and when the master 2 passes through the recording apparatus 1, minute droplets of ink are sprayed onto the master 2 according to the above information. As a result, the ink adheres to the master 2 in the above pattern. In this way, an image is formed on the master 2 to obtain a plate-making master (plate-making printing original plate).

An example of an ink jet recording apparatus used in the apparatus system of FIG. 1 is shown in FIGS. 2 and 3. 2 and 3
In FIG. 1, members common to those in FIG. 1 are designated by common reference numerals. FIG. 2 is a schematic configuration diagram showing a main part of such an ink jet recording apparatus, and FIG. 3 is a partial sectional view of a head.

The head 10 provided in the ink jet recording apparatus is, as shown in FIG.
01 and the lower unit 102 have a slit sandwiched between them, the tip of which is an ejection slit 10a, the ejection electrode 10b is disposed in the slit, and the oil ink 11 is filled in the slit. Has become.

In the head 10, a voltage is applied to the ejection electrode 10b according to a digital signal of image pattern information. As shown in FIG. 2, the counter electrode 10c is installed so as to face the ejection electrode 10b.
The master 2 is provided above. By applying a voltage, a circuit is formed between the ejection electrode 10b and the counter electrode 10c, the oil-based ink 11 is ejected from the ejection slit 10a of the head 10, and an image is formed on the master 2 provided on the counter electrode 10c. It is formed.

The width of the discharge electrode 10b is preferably as narrow as possible in order to form a high quality image. For example, the head 10 of FIG. 3 is filled with oil-based ink, and the tip of the ejection electrode 10b having a width of 20 μm is used.
The distance between b and the counter electrode 10c is set to 1.5 mm, and a voltage of 3 kV is applied for 0.1 msec between the electrodes to obtain 40 μm.
Printing of m dots can be formed on the master 2. As described above, a plate making master is obtained by forming an image on the lithographic printing plate precursor by an inkjet method using an oil-based ink.

[0130]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 <Preparation of lithographic printing plate precursor> The following composition 1A was dispersed with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 10 minutes, and then Composition 1B was added 33 times.
g was added and dispersed for 1 minute at room temperature with a paint shaker (Toyo Seiki Co., Ltd.), and then glass beads were filtered out to obtain a dispersion.

(Composition 1A) Porous filler; Alumina RK30 (manufactured by Iwatani Chemical Co., Ltd., average particle size 0.6 μm, average pore size 50 Å, average specific surface area 300 m ² / g 31 g, PVA 117 (Kuraray ( Co., Ltd.) 5 wt% aqueous solution 70 g Colloidal silica 20% aqueous solution (Snowtex C (Nissan Chemical Co., Ltd.) 60 g

[0133] (Composition 1B) ・ Tetraethoxysilane 92g ・ Ethanol 163g ・ Water 163g ・ Nitric acid 0.1g

Support of ELP-1X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing (Beck smoothness on the under side: 1
000 (sec / 10 cc)), the above image-receiving layer composition was applied using a wire bar so that the applied amount after drying was 5 g / m ² , and dried in an oven at 100 ° C. for 10 minutes. Then, a hydrophilic surface graft layer was formed by the following method.

(Method for forming surface graft layer) Oxygen glow treatment was performed under the following conditions by using a planographic magnetron sputtering device (CFS-10-EP70 manufactured by Shibaura Eletech) as a glow treatment for the surface of the image receiving layer.

(Oxygen glow processing conditions) -Initial vacuum: 1.2 × 10 ^-3 Pa-Argon pressure: 0.9 Pa-RF glow: 1.5 KW-Processing time: 60 sec

Next, the glow-treated film was immersed in a nitrogen-bubbled acrylic acid aqueous solution (20 Wt%) at 60 ° C. for 4 hours. The immersed membrane was washed with running water for 10 minutes to obtain a hydrophilic lithographic printing plate precursor having acrylic acid graft-polymerized on the surface. The weight (graft amount) of the hydrophilic surface graft layer was measured by a gravimetric method and found to be 1.3 g / m ²
Met. The original plate for lithographic printing was measured for its smoothness using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air capacity of 10 cc, and was 205 (sec / 10 cc). Further, 2 μl of distilled water was placed on the surface of the lithographic printing plate precursor, and the surface contact angle (degree) after 30 seconds was measured using a surface contact angle meter (trade name CA-D, manufactured by Kyowa Interface Science Co., Ltd.). It was 5 degrees or less.

The lithographic printing plate precursor described above was converted into "AM-Straig
"HT Imaging System" commercially available laser printer using dry toner AMSIS 1200-
The plate was made through J Plate Setter (trade name). When the copied image of the obtained plate-making product was visually evaluated using a 20-fold loupe, the plate-making image quality was good. That is, the plate-making product of the present invention obtained by dry-type toner transfer from a laser printer has no thin lines or fine characters, the solid part is uniform, and no unevenness in toner transfer is observed at all. Also, the background fog caused by the toner scattering was slight and it was a good one with no practical problems.

Next, after making the above lithographic printing plate precursor by the same operation as described above, using a fully automatic printing machine AM-2850 (trade name, manufactured by AM Co.) as a fountain solution, P
A solution prepared by diluting the S plate processing agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) with distilled water 50 times is put in a dampening water tray part, and printing is performed using a red ink containing a varnish for offset printing. Natsuta. The printed image (ground fog, solid uniformity in the image area) of the 10th printed matter was visually evaluated using a 20-fold magnifying glass, and it was extremely good. In addition, it has an image with fine lines, missing thin characters, and even solid areas,
10,000 or more good prints were obtained in which ink stains on the non-image area did not cause any practical problems. The original plate of the present invention can produce a large number of good printed matter.

Comparative Example 1 In Example 1, a lithographic printing plate precursor was prepared without forming a hydrophilic graft surface layer. The surface of the obtained original plate had a Bekk smoothness of 160 degrees (sec / 10 cc) and a contact angle with water of 5 degrees or less. This original plate was prepared and printed in the same manner as in Example 1. The image quality of the plate made is
It was almost the same as in Example 1, and the amount of scattered toner in the non-image area was small and the image was good. However, the printed matter had stains on the non-image area when printed.

Example 2 <Preparation of lithographic printing plate precursor> The following composition 2A was dispersed together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 10 minutes, and then the composition 2B was added 33 times.
g was added and dispersed for 1 minute at room temperature with a paint shaker (Toyo Seiki Co., Ltd.), and then glass beads were filtered out to obtain a dispersion.

(Composition 2A) Porous filler; aluminum hydroxide RH30 (manufactured by Iwatani Chemical Co., Ltd., average particle size 1.5 μm, average pore size 100 Å, average specific surface area 50 m ² / g 31 g, rutile type oxidation) Titanium (manufactured by Wako Pure Chemical Industries, Ltd.) 11 g-PVA 117 (Kuraray Co., Ltd.) 5 wt% aqueous solution 70 g-Colloidal silica 20% aqueous solution (Snowtex C (Nissan Chemical Industry Co., Ltd.) 60 g

[0143] (Composition 2B) ・ Tetraethoxysilane 92g ・ Ethanol 163g ・ Water 163g ・ Nitric acid 0.1g

Support for ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing (Beck smoothness on one side of under side:
2000 (sec / 10 cc or more), and the above composition is coated thereon with a wire bar to give a coating amount of 6 g / m ²
So that it is coated and dried by touch, then at 110 ℃, 3
A lithographic printing plate precursor was prepared by heating for 0 minutes.

(Method for forming surface graft layer) Oxygen glow treatment was performed under the following conditions by using a planographic magnetron sputtering device (CFS-10-EP70 manufactured by Shibaura Eletech) for glow treatment on the surface of the image receiving layer.

(Oxygen glow treatment conditions) Initial vacuum: 1.2 × 10 ^-3 Pa Argon pressure: 0.9 Pa RF glow: 1.5 KW Treatment time: 60 sec

Next, the glow-treated film was immersed in a nitrogen-bubbled acrylamide aqueous solution (20% by mass) at 60 ° C. for 4 hours.
Soak for a time. The immersed membrane was washed with running water for 10 minutes to obtain a hydrophilic lithographic printing plate precursor having acrylamide graft-polymerized on the surface. When the mass (graft amount) of the hydrophilic surface graft layer was measured by a gravimetric method,
It was 1.3 g / m ² . The Beck smoothness of the surface of the obtained original plate was 1000 (sec / 10 cc), and the contact angle with water was 5 degrees or less.

<Preparation of Electrophotographic Photosensitive Member> 2 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 14.4 g of the following binder resin (P-1), and the following binder resin (P-2) 3 ．
A mixture of 6 g, 0.15 g of the following compound (A) and 80 g of cyclohexanone was put in a 500 ml glass container together with glass beads and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and then the glass beads were separated by filtration to disperse the photosensitive layer. It was a liquid.

[0149]

[Chemical 4]

Next, the dispersion was degreased to a density of 0.
Apply on a 2mm thick aluminum plate with a wire bar,
After being dried by touch, it was heated in a circulating oven at 110 ° C. for 20 seconds. The film thickness of the obtained photosensitive layer was 8 μm.

The electrophotographic photosensitive member prepared as described above was corona-charged in the dark to have a surface potential of +450 V, which was then read from a manuscript in advance with a color scanner and color-separated. After making corrections related to color reproduction, using a semiconductor laser drawing device as an exposure device, a beam of 788 mm was obtained based on the information stored in the hard disk in the system as digital image data. Exposure was performed with a spot diameter of 15 μm and a pitch of 10 μm and a scan speed of 300 cm / sec (that is, 2500 dpi). Exposure was performed so that the exposure amount on the photoconductor at this time was 25 erg / cm ² .

Subsequently, the liquid developer having the following contents is used for development, and then rinsed in a bath of Isopar G alone to remove stains on the non-image area, and then the surface temperature of the photoconductor is kept at 50 ° C. with warm air. It was dried so that the remaining amount of Isopar G was 10 mg / g of toner. Subsequently, this photoreceptor was precharged with a corona charger at -6 KV, the image surface of this photoreceptor was superposed on the above-mentioned lithographic printing plate precursor, and negative corona discharge was applied from the electrophotographic photoreceptor side to transfer.

<Liquid developer> The components having the following composition were mixed in a kneader and kneaded at 95 ° C for 2 hours to obtain a mixture. The mixture was cooled in a kneader and then ground in the same kneader. 1 part by mass of this pulverized product and 4 parts by mass of Isopar H were dispersed for 6 hours with a paint shaker to obtain a dispersion. This dispersion is diluted with Isopar G so that the solid content of the toner is 1 g per liter, and at the same time 1 barium petrone is used as a charge control agent that imparts negative chargeability.
A liquid developer was prepared so as to contain 0.1 g per liter.

[0154] (Composition for kneading) ・ Ethylene / methacrylic acid copolymer 4 mass group     (Nucrel N-699 manufactured by Mitsui DuPont) ・ Carbon black # 30 (manufactured by Mitsubishi Kasei Co., Ltd.) 1 part by mass ・ Isoper L (manufactured by Exxon) 15 parts by mass

The image-forming lithographic printing plate precursor was heated at a temperature of 10
The toner image area was completely fixed by heating at 0 ° C. for 30 seconds. The drawn image of the obtained plate-making product was observed and evaluated with an optical microscope at a magnification of 200 times. It was a clear image with no blurring or loss of fine lines or characters.

Next, the printing plate prepared as described above is
As a printing machine, Oliver 94 type (made by Sakurai Manufacturing Co., Ltd.)
SLM-OD (Mitsubishi Paper Mills, Ltd.)
Solution) was diluted 100 times with distilled water, placed in a dampening water pan, and printing was performed using a red ink containing a varnish for offset printing. When the printed image of the 10th printed matter was visually evaluated using a magnifying glass of 20 times, no background stain was observed due to the adhesion of printing ink to the non-image area, and the uniformity of the solid image area was good. Further, even when observed with an optical microscope at a magnification of 200 times, fine lines, thinning of fine characters, missing, etc. were not recognized, and the image quality was good. 10,000 or more prints having a print quality equivalent to this and having no background stain were obtained.

Example 3 <Preparation of Water-Resistant Support> A high-quality paper weighing 100 g / m ² was used as a substrate, and one surface of the substrate was coated with a back layer coating composition having the following composition by using a wire bar. Dry coating amount 12g /
After providing the back layer of m ^2, the back layer has a smoothness of 100.
The calendar process was performed so that it was about (sec / 10 ml).

[0158] (Paint for back coat layer)   ・ Kaolin (50% aqueous dispersion) 200 parts   ・ Polyvinyl alcohol aqueous solution (10%) 60 parts   ・ SBR latex (solid content 50%, Tg: 0 ° C.) 100 parts   ・ Melamine resin (solid content 80%, Sumirez resin SR-613) 5 parts

Then, an under layer coating composition having the following composition was applied to the other surface of the substrate using a wire bar to form an under layer having a dry coating amount of 10 g / m ² , and then the under layer had a smoothness of 1500. The calendar process was performed so that it was about (sec / 10 ml).

[0160] (Paint for under layer)   ・ Carbon black (30% aqueous dispersion) 5.4 parts   ・ Clay (50% aqueous dispersion) 54.6 parts   ・ SBR latex (solid content 50%, Tg: 25 ° C.) 36 parts   ・ Melamine resin (solid content 80%, Sumirez resin SR-613) 4 parts

The above components were mixed to give a total solid content of 2
Water was added so as to be 5% to obtain an under layer coating material.

The specific electric resistance value of the obtained under layer is
It measured as follows. The under layer coating is applied to a stainless steel plate that has been thoroughly degreased and washed, and the dry coating amount is 10 g /
The coating film was m ² . The specific electrical resistance of the obtained sample was measured by the three-terminal method with a guard electrode according to JIS K-6911 to obtain a value of 4 × 10 ⁹ Ω · cm.

The following composition 3A was mixed with glass beads at 10 at room temperature in a paint shaker (Toyo Seiki Co., Ltd.).
After dispersing for 3 minutes, 33 g of Composition 3B was further added, and the mixture was dispersed for 1 minute at room temperature with a paint shaker (Toyo Seiki Co., Ltd.), and then glass beads were filtered out to obtain a dispersion.

(Composition 3A) Porous filler; magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., average particle size 0.6 μm, average pore size 200 Å, average specific surface area 100 m ² / g 31 g PVA 117 (Kuraray Co., Ltd. 5 wt% aqueous solution 70 g Colloidal silica 20% aqueous solution; Snowtex C (Nissan Chemical Co., Ltd.) 60 g

[0165] (Composition 3B) ・ Tetramethoxysilane 92g ・ Ethanol 163g ・ Water 163g ・ Nitric acid 0.1g

This dispersion was coated on the above water-resistant support with a wire bar so that the coating amount after drying was 6 g / m ² , dried in an oven at 100 ° C. for 20 minutes, and then subjected to lithographic printing. The original version was created.

(Method for forming surface graft layer) Oxygen glow treatment was performed under the following conditions using a planographic magnetron sputtering device (CFS-10-EP70 manufactured by Shibaura Eletech) as a glow treatment for the surface of the image receiving layer.

(Oxygen glow treatment conditions) Initial vacuum: 1.2 × 10 ^-3 Pa Argon pressure: 0.9 Pa RF glow: 1.5 KW Treatment time: 60 sec

Next, the glow-treated film was immersed in a nitrogen-bubbled methacrylamide aqueous solution (20% by mass) at 60 ° C. for 4 hours. The immersed membrane was washed with running water for 10 minutes to obtain a hydrophilic lithographic printing plate precursor having methacrylamide graft-polymerized on its surface. The weight (graft amount) of the hydrophilic surface graft layer was measured by a gravimetric method and found to be 1.3 g / m ² .

<Preparation of Oil Ink (IK-1)> (Production of Resin Particles) Poly (dodecyl methacrylate) 1
A mixed solution of 4 g, 100 g of vinyl acetate, 4.0 g of octadecyl methacrylate and 286 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, 1.5 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added and reacted for 4 hours. Furthermore, 0.8 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was added, and then the mixture was heated to a temperature of 80 ° C. and reacted for 2 hours, and then A ．
I. B. N. 0.6 g was added and reacted for 2 hours. Then, the temperature was raised to 100 ° C. and the mixture was stirred as it was for 1 hour to distill off unreacted monomers. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having a polymerization rate of 93% and an average particle size of 0.35 μm. Particle size is CAP
It was measured with A-500 (manufactured by Horiba, Ltd.).

(Preparation of Ink) Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 mass ratio) 1
0 g, 10 g of alkali blue and Shersol 71,
30 g together with glass beads was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine blue dispersion of alkali blue. 50 g of the above resin particles
A blue oil-based ink (IK-1) was prepared by diluting 5 g (solid content) of the above-mentioned blue dispersion and 0.06 g of zirconium naphthenate into 1 liter of Isopar G (as solid content).

[0172] The original plate obtained above can be used to draw the output of a personal computer by Graphtec Servo Proter DA
8400 is modified, the ink discharge head shown in FIG. 2 is attached to the pen plotter, and the above oil-based ink (IK-1) is applied to the lithographic printing plate precursor that is installed on the counter electrode with a gap of 1.5 mm. Was used to make a plate. At the time of plate making, the under layer provided directly below the image receiving layer of the printing original plate and the counter electrode were electrically connected using a silver paste.

The plate made by the Ricoh fuser (manufactured by Ricoh Co., Ltd.) adjusted to a plate surface temperature of 70 ° C.
The ink image was fixed by heating for 2 seconds. The image of the obtained plate-making product was observed and evaluated with an optical microscope at a magnification of 200 times. It was a clear image with no blurring or loss of fine lines or characters.

Next, the printing plate prepared as described above is
As a printing machine, Oliver 94 type (made by Sakurai Manufacturing Co., Ltd.)
As a dampening water, a solution prepared by diluting EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 100 times with distilled water was placed in a dampening water saucer part, and a red ink containing a varnish for offset printing was used. Printing was done. When the printed image of the 10th printed sheet was visually evaluated using a magnifying glass of 20 times, no background stain was found due to the adhesion of the printing ink in the non-image area, and the uniformity of the solid image area was good. . Further, even when observed with an optical microscope at a magnification of 200 times, fine lines, thin characters, thinning, and the like were not observed, and the image quality was good. 10,000 or more prints having a print quality equivalent to this and having no background stain were obtained.

Examples 4 to 7 A lithographic printing plate precursor was prepared in the same manner as in Example 3 except that the compounds shown in Table 1 below were used in place of the methacrylamide used as the hydrophilic monomer in Example 3. did.

[0176]

[Table 1]

The Beck's smoothness of the surface of each obtained original plate is 8
Within the range of 00 to 1200 (sec / 10cc), the contact angle with water was 5 degrees or less. When a printing plate was prepared by making a plate in the same manner as in Example 3, and printing was performed, all of the obtained prints had clear image quality with no stains on the non-image areas, as with the prints of Example 3. The printing durability was as good as 10,000 sheets or more.

Example 8 Using the lithographic printing plate precursor prepared in Example 3, an ink jet plate making machine using solid ink, which is commercially available as “SJ120 (Hitachi Koki Co., Ltd.)”, is used. I made a plate.

When the copy image of the obtained plate-making product was visually evaluated using a 20-fold loupe, the plate-making image quality was good.
That is, the plate-making product of the present invention obtained from the solid inkjet plate-making machine is a fine line, there is no loss of fine characters, the solid part is uniform, and the non-image part is good without background fog due to ink scattering. there were.

Next, after making the lithographic printing plate precursor by the same operation as described above, a fully automatic printing machine AM-2850 (manufactured by AM Co.) was used as fountain solution to prepare a PS plate treating agent. EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 50 with distilled water
The double-diluted solution was placed in a fountain solution tray, and printing was performed using a red ink containing a varnish for offset printing. The printed image (ground fog, solid uniformity in the image area) of the 10th printed matter was visually evaluated using a 20-fold magnifying glass, and it was extremely good. Further, 10000 or more good printed matters were obtained which had an image without fine lines, missing fine characters and uneven solid areas, and had no ink stains on non-image areas. The original plate of the present invention can produce a large number of good printed matter.

[0181]

By using the lithographic printing plate precursor of the present invention, it is possible to obtain an excellent image that does not cause spot stains as well as uniform stains on the entire surface. Furthermore, it is possible to print a large number of printed matter with clear images without image loss or distortion.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system used for forming an image on a lithographic printing plate precursor according to the invention.

FIG. 2 is a schematic configuration diagram showing a main part of an inkjet recording apparatus used for forming an image on a lithographic printing plate precursor according to the invention.

FIG. 3 is a partial cross-sectional view of a head of an inkjet recording apparatus used for forming an image on a lithographic printing plate precursor according to the invention.

[Explanation of symbols]

1 Inkjet recording device 2 Master plate for lithographic printing 3 computer 4 bus 10 heads 10a discharge slit 10b Discharge electrode 10c counter electrode 11 oil-based ink 101 Upper unit 102 Lower unit

Continued front page    F-term (reference) 2C056 EA24 FB01                 2H114 AA04 AA22 AA27 BA10 DA41                       DA64 DA71 DA75 EA01 EA03                       EA05 EA08 FA00 FA11 GA01                       GA34                 4J002 CP002 CP171 CQ031 DA016                       DA026 DA036 DB016 DE076                       DE086 DE096 DE106 DE136                       DE186 DF016 DG026 DG046                       DH046 DJ006 DJ016 DK006                       DL006 FA092 FA096 FD012                       FD016 GF00                 4J031 AA55 AA56 AA59 AB04 AD01                       AD03 AF10 AF28

Claims (6)

[Claims] 1. In a lithographic printing plate precursor having an image-receiving layer on a water-resistant support, the image-receiving layer has porous filler particles and metal atoms and / or metalloid atoms connected through oxygen atoms. A binder resin comprising a complex of a resin containing a bond and an organic polymer containing a group capable of forming a hydrogen bond with the resin, and at least one hydrophilic functional group in the image receiving layer. A lithographic printing plate precursor having a surface-grafted hydrophilic layer to which the polymer compound is chemically bound. 2. A polymer compound having at least one hydrophilic functional group, wherein the polymer chain end is attached to the image-receiving layer directly or through a trunk polymer compound chemically bound to the image-receiving layer. The lithographic printing plate precursor as claimed in claim 1, wherein the lithographic printing plate precursor is a straight-chain polymer compound chemically bound to the above. 3. The lithographic printing plate precursor as claimed in claim 1, wherein the average pore size distribution of the porous filler particles is 1Å to 1 μm. 4. A lithographic printing plate precursor according to claim 1, average specific surface area of the porous filler particles is characterized by a 0.05m ² / g~5000m ² / g. 5. The mixing ratio of the binder resin and the total filler in the image receiving layer is such that the binder resin / the total filler = 80/20 to 5/9.
It is 5 (mass ratio), The lithographic printing plate precursor in any one of Claims 1-4 characterized by the above-mentioned. 6. A resin containing a bond in which a metal atom and / or a semimetal atom are connected via an oxygen atom is obtained by hydrolysis co-condensation of at least one compound represented by the following general formula (I). A lithographic printing plate precursor as claimed in any one of claims 1 to 5, which is a polymer. General formula (I) (R ⁰ ) _n M ⁰ (Y) _zn [In the general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M ⁰ Is 3-6
Represents a valent metal or metalloid, z represents the valence of M ⁰ , and n
Represents 0, 1, 2, 3 or 4. However, z−n is 2 or more. ]