JP2001287475A - Direct drawing type lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct drawing type lithographic printing original plate, in which no spotted scumming develops, not to mention even no scumming over the whole surface as an offset original plate and with which a large number of sheets of printed matters, which have clear images with neither its omission nor its deformation nor the like, can be printed. SOLUTION: This direct drawing type lithographic printing original plate is produced by providing an image receiving layer including at least a resin including a bond, in which a specified metal oxide particle and/or double oxide particle and a metal atom are connected through an oxygen atom with each other, and a binding resin including an organic polymer complex between a group, which can form a hydrogen bond with the above resin, and a polar functional group and having a hydrophilic surface, on a water resisting support.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct-drawing type lithographic printing plate precursor, and more particularly to a lithographic printing plate precursor for providing a lithographic printing plate capable of printing a large number of printed matters having clear images with no background stain. ..

[0002]

2. Description of the Related Art Currently, lithographic printing plates used mainly in the field of light printing include (1) a water-resistant support,
Direct drawing type original plate provided with a hydrophilic image receiving layer, (2) Direct drawing plate making on an original plate provided with an image receiving layer (lipophilic) containing zinc oxide on a water resistant support, and then a non-image area To obtain a printing plate by desensitizing treatment with a desensitizing solution, (3) An electrophotographic photosensitive material having a photoconductive layer containing photoconductive zinc oxide on a water-resistant support as an original plate , The non-image part after image formation,
Examples include a printing plate which is desensitized with a desensitizing solution, and (4) a silver salt photographic type original plate in which a silver halide emulsion layer is provided on a water-resistant support.

With the recent development of office equipment and the development of office automation, in the printing field, various methods such as electrophotographic printers, thermal transfer printers and ink jet printers can be applied to the direct drawing type lithographic printing plate precursor (1). There is a demand for an offset lithographic printing method in which plate making (that is, image formation) is performed, and a printing plate is directly created without performing a specific process for forming a printing plate.

A conventional direct drawing type lithographic printing plate precursor is provided with a surface layer serving as an image receiving layer on both sides of a support such as paper with a back layer and an intermediate layer interposed therebetween. PV or back layer
It is composed of a water-soluble resin such as A 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 pigments 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. Examples thereof include water-soluble resins such as polymers and styrene-maleic acid copolymers.

Further, glyoxal is used as a water-proofing agent,
Examples thereof include initial condensates of aminoplasts 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 for direct drawing, 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 when decomposed. , A resin containing a functional group that is cured by heat/light and having been previously cross-linked is used (Japanese Patent Laid-Open Nos. 1-226394 and 1-269593,
JP-A-1-288488), the functional group-containing resin and a thermosetting/photocurable resin are used in combination (JP-A-1-266546).
No. 1-275191, No. 1-309068), and the above-mentioned functional group-containing resin in combination with a crosslinking agent (JP-A 1-267093, 1-271292, 1-3).
No. 09067), improvement of hydrophilicity of non-image area, improvement of film strength of image receiving layer, and further improvement of printing durability have been investigated.

Further, in the image receiving layer, resin particles having a fine particle diameter of 1 μm or less containing hydrophilic groups such as carboxyl groups, sulfo groups and phosphono groups are contained together with an inorganic pigment and a binder (Japanese Patent Laid-Open No. Hei 10). 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.
No. 5,696984), it has been studied 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, while 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 was dissolved in the immersion water used for offset printing, and there were drawbacks such as deterioration of printing durability and occurrence of printing stains. Further, 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 original plate and the oil-based ink is not good, even in the non-image area Even if the above-mentioned hydrophilicity is sufficient and the above-mentioned printing stain does not occur, the problem that the oil-based ink in the image area is lost during printing, resulting in a decrease in printing durability, is still sufficiently solved. Not up to the point.

On the other hand, as the image receiving layer, a plate comprising a hydrophilic layer containing titanium oxide, polyvinyl alcohol and hydrolyzed tetramethoxysilane or tetraethoxysilane (Japanese Patent Laid-Open Nos. 3-42679 and 10-268583, etc.) can be mentioned. Be done. However, when the plate was actually made and printed as a printing plate, the printing durability of the image was insufficient.

[0011]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional direct drawing type lithographic printing plate precursor. It is an object of the present invention to provide an excellent direct drawing type lithographic printing original plate which does not generate 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 direct-drawing type lithographic printing plate precursor that provides a printing plate that is capable of printing a large number of clear image printed matter without background stains, distortions, etc. of the image. ..

[0012]

[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 trivalent to hexavalent metal, and z represents a metal M ⁰ . It represents a valence, and n represents 0, 1, 2, 3, or 4. However, z−n is 2 or more. ]

(3) The direct drawing type lithographic printing plate precursor as described in (1) or (2) above, wherein the surface of the image receiving layer has a Bekk smoothness of 30 (sec/10 cc) or more. (4) In the non-aqueous solvent having a specific electric resistance of 10 ⁹ Ω·cm or more and a dielectric constant of 3.5 or less, in the direct drawing type lithographic printing plate precursor as described in any one of (1) to (3) above, A method for producing a lithographic printing plate, comprising forming an image by an inkjet method by discharging an oily ink in which resin particles having a solid and hydrophobic charge are dispersed at least at room temperature by utilizing an electrostatic field.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention, on a water-resistant support, with a specific metal oxide particles and / or double oxide particles, a resin containing a bond in which metal atoms are connected via oxygen atoms (hereinafter, also referred to as a metal-containing resin) A direct drawing type lithographic plate provided with an image receiving layer of a hydrophilic surface containing at least a binder resin containing a complex of an organic polymer containing a group which forms a hydrogen bond with the resin and a polar functional group. It is a printing original plate.

In the present invention, specific metal oxide particles and/or
Or, in the dispersion of the composite oxide particles and the composite of the metal-containing resin and the organic polymer, the interaction between the two is high, and the dispersibility of the specific metal oxide particles and/or the composite oxide particles becomes good, and after film formation By the above interaction, a film having excellent printing durability can be obtained, and at the same time, excellent hydrophilicity and image adhesion can be exhibited.

The inorganic particles used in the image receiving layer of the present invention are
Metal atom is Mg, Ba, Ge, Sn, Zn, Pb, L
a, Zr, V, Cr, Mo, W, Mn, Co, Ni and Cu metal oxide and/or complex oxide particles (provided that at least one metal atom constituting the complex oxide is Mg, Al, Si, Ti, Zr, Cr, V, Mo,
Sn, W and Nb). The metal oxide particles and the double oxide particles may be any particles as long as they have no problem in stability and material safety. The metal oxide particles and the multiple oxide particles may be used alone or in combination of two or more kinds.

In the above metal oxide, the metal atoms are Mg, G
It is preferably e, Sn, Zn, Pb, Zr, V, Cr, W, Ni or Cu. The size of the particles is 0.01 to 5 μm in terms of average particle size, and 0.02 to 3
μm is preferred. The average particle size of the double oxide particles is 0.01
˜5 μm, preferably 0.02 to 3 μm. In these ranges, the preferable smoothness of the surface of the image receiving layer,
Image strength after image formation is obtained, and stains of printing ink in non-image areas do not occur.

The above metal oxide is produced by a conventionally known method, for example, "Chemical Chemistry Course 9, Synthesis and Purification of Inorganic Compounds", edited by The Chemical Society of Japan, published by Maruzen Co., Ltd. (1958), edited by the Chemical Dictionary. 890-949 “Chemical Encyclopedia 3” edited by the committee
Page, published by Kyoritsu Shuppan Co., Ltd. (1963) and the like. In addition, these compounds are also on the market as commercial products (for example, manufactured by Kanto Chemical Co., Inc., manufactured by Wako Pure Chemical Industries, Ltd.), and further, “Coloring Material Handbook” edited by the Coloring Materials Association, page 250, Asakura. Published by bookstores (1989), Akira Misono, "Paints and Pigments," page 184, published by Nikkan Kogyo Shimbun (196)
0 years) and the like.

The complex oxide used in the image-receiving layer of the present invention is a higher-order compound composed of two or more kinds of oxides, and a compound in which the presence of a basic ion as an oxygen acid is not recognized in its structure. (A complex oxide composed of three or more kinds of oxides may be particularly referred to as a complex oxide). This complex oxide is Mg, Al, Si, Ti, Zr, Cr, V, M
containing at least one metal atom selected from o, Sn, W and Nb, and other metal atoms in addition to the above atoms,
Li, Ca, Ba, Sr, Bi, Zn, Pb, Co, M
It is preferable to contain at least one metal atom selected from n, Cu, Ni, La, Ge and the like. Preferably, it is a double oxide composed of two kinds of metal atoms.

The double oxide is produced by a conventionally known method,
For example, “Metal Oxide” edited by Kozo Tabe, Tetsuro Kiyoyama, Kazuo Fueki
And complex oxides" Kodansha Co., Ltd. (1978), made into Japan
Academic Society "New Experimental Chemistry Lecture 8, Synthesis of Inorganic Compounds I" 31
Pages 2-322, published by Maruzen Co., Ltd. (1976), Nori Nakanishi
Hiko, Nao Bando, Ed., "Chemistry of Inorganic Fine Materials", p. 28, 3
It is described in Kyodo Shuppan Co., Ltd. (1988) and the like. Well
In addition, these compounds are, for example, “Metal
"Chemical General Catalog 10th Edition" (1998), etc.
It can be easily obtained as a sales item. Also, double acid
As the compound, specifically, metal aluminates [M¹A
l₂O_FourOr M¹O・Al₂O₃(Metal atom M¹As M
g, Co, Sr, Cu, Ni, Mn, etc.)], metal silicate
Class [eg M²SiO₃(Metal atom M²As Ca, B
a, Mg, Pb, Zn, Ti, etc.), cobalt silicate (C
o₂SiO_Four), bismuth silicate (Bi₂O₃・SiO₂),
Aluminum silicate (Al₂O₃・SiO₂) Etc.], titanium
Acid metals [eg M³TiO₃Or M³O・TiO₂(metal
Atom M³As Ca, Ba, Sr, Mg, Zn, C
o, Pb, Ni, Mn, etc.), zirconium titanate (Z
rO₂・TiO₂), aluminum titanate (Al₂TiO
_Five), lanthanum titanate (La₂Ti₂O₇) Etc.], zircon
Acid metals [eg M^FourZrO₃(Metal atom M^FourAs C
a, Ba, Sr, Mg, Cu, Pb, Ni, Co, Zn
Etc.), lithium zirconate (Li₂ZrO₃), zircon
Aluminum oxide (Al₂O₃・3ZrO₂), zirconate
Tan (TiO₂・ZrO₂) Etc.], metal stannates (eg
For example, M^FiveSnO ₃(Metal atom M^FiveAs Ca, Ba, S
r, Mg, Cu, Pb, Co, etc.), bismuth stannate (B
i₂O₃・SnO₃) Etc.], metal chromates [eg M⁶C
rO_Four(Metal atom M⁶As Sr, Pb, Co, etc.)
Etc.], metal tungstates [eg M⁷WO_Four(Metal original
Child M⁷As Ca, Ba, Sr, Co, Mg, Cu,
Pb, Ni, Mn, etc.), aluminum tungstate
(Al₂(WO_Four)₃Or Al₂O₃・3WO₃), Tung Ste
Zirconate (Zr(WO_Four)₂Or ZrO₂・2WO
₃), bismuth tungstate (Bi₂O₃・WO₃)etc〕,
Metal molybdates [eg M⁸MoO_Four(Metal atom M⁸
Sr, Co, Pb, Cu, Ba, Ni, etc.) and the like],
Metal vanadates [eg M⁹V₂O₆Or M⁹O・V₂O_Five
(Metal atom M⁹As, Ca, Mg, Mn, Sr, Cu,
Ni, Pb, etc.), lead zirconate titanate, titanic acid
Barium Strontium, Basic Lead Chromate (PbC
rO_Four-PbO) and the like.

The binder resin used in the image-receiving layer of the present invention is a bond-containing resin in which metal atoms are linked via oxygen atoms, that is, a metal-containing resin and a group capable of forming a hydrogen bond with this resin. And a resin comprising a complex with an organic polymer containing at least one polar functional group selected from a carboxyl group, a sulfo group and a phosphono group. The term "composite of metal-containing resin and organic polymer" is used to include a sol-like substance and a gel-like substance.

The metal-containing resin refers to a polymer mainly containing a bond composed of "oxygen atom-metal atom-oxygen atom".

The metal-containing resin of the present invention is preferably a polymer obtained by hydrolytic polycondensation of a metal compound represented by the following general formula (I). 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, z represents the valence of the metal M ⁰ , n represents 0,
Represents 1, 2, 3, or 4. However, z−n is 2 or more. Here, the hydrolysis polycondensation is a reaction in which a reactive group repeats hydrolysis and condensation under acidic or basic conditions to polymerize. The above metal compounds may be used alone or 2
Used in combination with one or more species for the production of metal-containing resin.

Next, the metal compound represented by the general formula (I) will be described in detail. R ⁰ in the general formula (I) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, 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. Group, cyano 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-dimethylaminoethyl 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), -NHCON
HR' group, -NHCOOR' group, -Si(R') ₃ group,
Examples thereof include -CONHR" group and -NHCOR' group.
Multiple of these substituents may be substituted in the alkyl group)},

A linear or branched alkenyl group having 2 to 12 carbon atoms which may be substituted (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, norbornyl 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 ( Examples of the substituent include a phenyl group and a naphthyl group, and examples of the substituent include those having the same content as the group substituted with the alkyl group, and a plurality of them may be substituted),

Alternatively, a heterocyclic group which may be condensed and contains at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom (for example, the heterocycle is a pyran ring, a furan ring, a thiophene ring or 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 or 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⁾
It represents a (COOR ⁴ ) group or a —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⁾ (C
In the OOR 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 aryl group (eg, phenyl group, tolyl group,
Represents a xylyl), R ⁴ represents an alkyl group (e.g. having 1 to 6 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.), an aralkyl group having 7 to 12 carbon atoms ( For example, 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 -N(R ⁵ )(R ⁶ ) group, R ⁵ and R
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 content 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 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 preferred are Al, Si, Sn, Ge, Ti, Zr and the like, and further more preferred are Al, Si, Sn, Ti, Zr and the like. Si is particularly preferable.

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

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,

Tetrachlorosilane, 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, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-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-butoxinlane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-( 3,4
-Epoxycyclohexyl)ethyltriethoxysilane,

Ti(OR) ₄ (R is an alkyl group (for example,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.), TiCl ₄ , Zn(OR)
_{2, Zn (CH 3 COCHCOCH 3} ) 2, Sn (OR) 4,
_{Sn (CH 3 COCHCOCH 3) 4} , Sn (OCOR) 4,
SnCl ₄ , Zr(OR) ₄ , Zr(CH ₃ COCHCOC
_{H 3) 4, Al (OR} ) 3.

Next, the organic polymer used in the present invention will be described. The organic polymer of the present invention contains a group capable of forming a hydrogen bond with a metal-containing resin (hereinafter also referred to as a specific bonding group) and a polar functional group selected from a carboxyl group, a sulfo group and a phosphono group. In the organic polymer of the present invention, 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. it can.

Examples of the organic polymer include those containing, as a repeating unit component, the specific bonding group of the present invention in the main chain and/or side chain of the polymer. Preferably, as the repeating unit component, —N(R ¹¹ )CO—, —N(R ¹¹ ).
Examples thereof include a component in which at least one bond selected from SO ₂ —, —NHCONH—, and —NHCOO— is present in the main chain and/or side chain of the polymer, and/or a component 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). ..

Examples of the polymer having a specific bonding group of the present invention in the polymer main chain include amide resins having -N(R ¹¹ )CO-bond or -N(R ¹¹ )SO ₂ -bond, -N
Ureido resin having HCONH-bond, -NHCOO
A urethane resin 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 (1)
986), Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" published by Taiseisha Co., Ltd. (1981) and the like can be used.

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

[0040]

[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), the polymer in which Z ¹ represents a —CO— bond and p represents 2 is catalyzed by an oxazoline which may have a substituent. It is obtained by ring-opening polymerization in the presence of 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 (eg, 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 etc. are mentioned. Preferred oxazolines include 2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline and the like. Such oxazoline polymers may be used alone or in combination of two or more.

For 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 obtained in a similar manner.

The N-acylated form of polyalkyleneimine is a carboxylic acid amide form containing -N(CO-R ²⁰ )- which is obtained by a polymer reaction with carboxylic acid halides, or a high-performance product with sulfonyl halides. -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 having 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.

[0047]

[Chemical 2]

[0048]

[Chemical 3]

On the other hand, the hydroxyl group-containing organic polymer of the present invention may be any of natural water-soluble polymers, semi-synthetic water-soluble polymers, and synthetic polymers. 19, Natural polymer compound I” published by Asakura Shoten
(1960), Management Development Center Publishing Division, "Water-soluble Polymer/Water-dispersible Resin Comprehensive Technical Data Book", Management Development Center Publishing Division (1981), Shinji Nagatomo, "Applications and Markets of New Water-Soluble Polymers" Published by CMC (1988),
"Development of Functional Cellulose" Published by CMC (1
985) and the like.

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 ethers such as cellulose butyrate, cellulose acetate phthalate, etc.; methylcellulose, ethylcellulose, cyanoethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylhydroxyethylcellulose, etc.), starch, starch derivatives ( Oxidized starch, esterified starches; esterified products of nitric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, butyric acid, succinic acid, etc., etherified starches; methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethyl And derivatives thereof, alginic acid, pectin, carrageenan, tamarind gum, natural gums (eg, gum arabic, guar gum, locust bean gum, tragacanth gum, xanthan gum), 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. Polymers or copolymers of acid esters or methacrylic acid esters (as ester substituents, for example, 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.), an N-substituted polymer or copolymer of acrylamide or methacrylamide containing at least one hydroxyl group (as the N-substituent, for example, a monomethylol group, a 2-hydroxyethyl group, a 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 polymer of the present invention further contains at least one polar functional group selected from a carboxyl group, a sulfo group, and a phosphono group (--PO ₃ H ₂ ). These polar functional groups may form salts. Since the organic polymer of the present invention contains a polar functional group, the hydrophilicity of the image-receiving layer using the same is further enhanced, and the scumming of the non-image area is prevented even under severe printing conditions. Have. The method for producing the organic polymer of the present invention is not particularly limited, and can be easily obtained, for example, by modifying the organic polymer having a hydroxyl group by a conventional method and introducing a polar functional group. The organic polymer having a hydroxyl group is not particularly limited as long as it has at least one hydroxyl group in the substituent of the repeating unit. In these production methods, adjustment can be made so that a desired amount of hydroxyl groups remain. Further, the organic polymer of the present invention can also be produced by a method using a monomer having a polar functional group as a starting material for synthesis.

The content of the polar functional group in the organic polymer of the present invention is usually 0.1 to 90 mol %, preferably 0.5 to 50 m as the unit component having the polar functional group.
ol%, more preferably 1.0 to 45 mol%. When the organic polymer is a polysaccharide or a protein, the unit component refers to its constituent monosaccharide or amino acid. However, these unit components may have a plurality of polar functional groups. The weight average molecular weight of the organic polymer of the present invention is preferably 10
^{It is from 3} to 10 ⁶ , more preferably from 5×10 ³ to 4×10 ⁵ .

In the composite of the metal-containing resin and the organic polymer of the present invention, the ratio of the metal-containing resin and the organic polymer can be selected in a wide range, but the metal-containing resin/organic polymer mass ratio is preferably 10/90 to 90. /10, more preferably 20/80 to 80/20. Within this range, the film strength of the image receiving layer, the water resistance to dampening water during printing, and the affinity with inks, toners and the like will be good.

In the binder resin containing the composite of the present invention, the hydroxyl group of the metal-containing resin produced by the hydrolytic polycondensation of the metal compound and the specific bonding group and polar functional group in the organic polymer are combined. A hydrogen-bonding action forms a uniform organic-inorganic hybrid, and becomes microscopically homogeneous without phase separation. When a hydrocarbon group is present in the metal-containing resin, it is presumed that the affinity with the organic polymer is further improved due to the hydrocarbon group. The composite of the present invention is excellent in film forming property.

The composite of the metal-containing resin of the present invention and the organic polymer is produced by hydrolyzing and polycondensing the metal compound and mixing it with the organic polymer, or in the presence of the organic polymer, the metal compound is added. It is produced by hydrolysis polycondensation. Preferably, the organic/inorganic polymer composite of the present invention can be obtained by hydrolytic polycondensation of the metal compound by a sol-gel method in the presence of an organic polymer. In the produced organic-inorganic polymer composite, the organic polymer is uniformly dispersed in the gel matrix (that is, the three-dimensional fine network structure of the inorganic metal oxide) produced by the hydrolysis polycondensation of the metal compound.

The sol-gel method as the above preferable method can be carried out by using a conventionally known sol-gel method. Specifically, "Thin-gel thin film coating technology" (Technical Information Association) (published) (1995), Sakubana Sio "Sol-gel method of science" (Agne Jofusha) (published) ) (1988), S. Hirashima, "Technology for functional thin film formation by latest sol-gel method", Comprehensive Technology Center (Published) (19
1992) and the like, and can be carried out according to the method described in detail in the textbook.

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) and the like, and may be used alone or in combination of two or more.

Further, in order to accelerate the hydrolysis and polycondensation reaction of the 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 a 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 having a high concentration is used, a precipitate may be formed in the sol solution, so the concentration of the basic catalyst is preferably 1 N (mol/L) (concentration in 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 having a high concentration, a catalyst composed of an element that hardly remains 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.

The image-receiving layer of the present invention may contain other components in addition to the above components. Inorganic pigment particles other than the inorganic particles of the present invention may be contained as other components. For example, silica, alumina, kaolin, clay,
Examples thereof include calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate, hydrous titanium oxide and titanium oxide. These other inorganic pigments are used within the range of not more than 40% by mass with respect to the inorganic particles of the present invention. It is preferably within 20% by mass.

The ratio of pigment/binder resin in the image receiving layer is
Generally, the binder resin is 8 to 50 with respect to 100 parts by mass of the pigment.
It is a ratio of parts by mass, preferably 10 to 30 parts by mass. Here, the term "pigment" means the total sum of the inorganic particles used in the present invention and inorganic pigments other than those.
Within this range, the effects of the present invention are effectively exhibited, the film strength during printing is maintained, and the high hydrophilicity of the non-image area is maintained. Further, the image portion is sufficiently adhered to the image receiving layer, and sufficient printing durability can be obtained without causing image defects even when the number of printed sheets increases.

In addition, a crosslinking agent may be added to the image receiving layer in order to further 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 of Crosslinking Agents", Taiseisha (1981), Polymer Society of Japan, "Polymer Data Handbook, Basic Edition", 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 (Published in 1969), etc.), melamine resins (for example, compounds described in "Yulia 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 preferably 0.2 to 10 μm, more preferably 0.5 to 8 μm. Within this range, a film having a uniform thickness is formed, and the film has sufficient strength.

The image receiving layer of the present invention preferably has a surface smoothness of 30 (sec/10 cc) or more in terms of Bekk smoothness. Here, the Beck's smoothness can be measured by a Beck's smoothness tester. Beck's smoothness tester is a high-smoothly finished circular glass plate with a hole in the center, where the test piece is pressed at a constant pressure of 1 kg/cm ² (about 98 kPa) and a fixed amount (10 cc) under reduced pressure. ), the time required for the air to pass between the glass surface and the test piece is measured.

When plate making (image formation) is carried out by an electrophotographic printer, the toner used is preferably dry toner or liquid toner in the following ranges.

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 cc), more preferably 50 to 150 (sec/10 cc). 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, background stain), 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 (seconds/10 cc) or more, and the higher the better, the better 150-3000 (seconds/second).
10cc), more preferably 200 to 2500 (seconds/10cc)
Is. In the case of an inkjet printer or a thermal transfer printer, the same range as that of the electrophotographic printer using the liquid toner is preferable. Within 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 of the present invention is such that unevenness is high and the intervals are close.
Specifically, the surface center average roughness SRa defined by ISO-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. preferable. More preferably, SRa is 1.
35 to 2.5 μm, and Sλa is in the range of 45 μm or less. It is presumed that this suppresses the adhesion of 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., whose thickness is 0.1-3 mm, especially 0.1-1 mm. The ones 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 on the side adjacent to the image receiving layer has a Beck's smoothness of 300 (sec/10).
cc) or more, preferably 900 to 3000 (seconds/10 cc), and more preferably 100.
It is preferably 0 to 3000 (seconds/10 cc). By controlling the smoothness of the surface of the support on the side adjacent to the image receiving layer to be Beck smoothness of 300 (sec/10 cc) or more, image reproducibility and printing durability can be further improved. Such an improving effect can be obtained even if the surface of the image receiving layer has the same smoothness, and the increase in the smoothness of the surface of the support improves the adhesion between the image portion and the image receiving layer. Conceivable.

Here, the Beck's smoothness can be measured in the same manner as described above.

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 applied. 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 is adjusted as described above is sufficiently retained without being affected by the unevenness of 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. Specific examples thereof include a method of melt-bonding the surface of the substrate with a resin and 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.

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

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 original plate is preferably electrically conductive, and its volume resistivity value is particularly preferably 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 drops adhere to the image receiving layer, the charge of the ink drops immediately disappears through the ground plane, so that a clear image without disturbance is formed. To be done. The measurement of the specific electric resistance value (also referred to as the volume specific electric resistance value or the specific electric resistance value) was performed by a three-terminal method in which a guard electrode was provided based on JIS 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 vapor-depositing a metal.

On the other hand, examples of the substrate having conductivity as a whole include conductive paper impregnated with sodium chloride, a plastic film mixed with a conductive filler such as carbon black, and a metal plate such as aluminum. Be done.

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 on both sides of the conductive paper. The thickness of the conductive layer applied is 5 μm to 2
0 μm is preferable. As the conductive filler, particulate carbon black, graphite, for example, metal powder such as silver, copper, nickel, brass, aluminum, steel, stainless steel, tin oxide powder, flaky aluminum or nickel, fibrous carbon, etc. can give.

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. As the hydrophilic resin, for example, polyvinyl alcohol resin, cellulose derivative, starch and its derivative, polyacrylamide resin, 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 material include aluminum foil, and examples of the laminate material 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 preferable 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 plastic film having conductivity, for example, polypropylene or polyester film mixed with 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 as a printing plate is insufficient,
If it exceeds 200 μm, the handling property such as the transportability in the drawing device is deteriorated.

A structure in which a conductive layer is provided will be described. As a water resistant substrate, the thickness is 80 μm to 200 μm
m, water-resistant treated paper, plastic film, or metal foil laminated paper or plastic film 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 formed on one surface of the substrate to a thickness of 5 μm to 2 μm.
Apply at 0 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 surface 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 (seconds/10 cc). 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.

Plate-making is carried out by forming an image on the lithographic printing plate precursor of the present invention by a thermal transfer recording system, an electrophotographic recording system or an ink jet recording system.

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), or the like, or a commercially available PPC copying machine.
A combination of a scanning exposure method using laser light that is exposed based on digital information and a development method that uses 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 fixed by suction from the back surface by air suction. 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 detecting means of the photosensitive material. Thereafter, for example, scanning exposure is performed by a laser light source 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 the light-sensitive material and the wet development method described on page 275 and after of the above-mentioned reference can be used. The exposure mode at this time is performed corresponding to the toner image development mode. For example, in the case of reversal development, the negative image, that is, the 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 an excessive 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. Next, the toner image formed as described above on the photoconductor is transferred and fixed on the lithographic printing original plate which is the material to be transferred, or is transferred and fixed on the lithographic printing original plate via the intermediate transfer member. To do.

The ink jet recording method may be any of the conventionally known recording methods.
An oil-based ink is preferable from the viewpoint of fixing property and difficulty in clogging of the ink, and an electrostatic discharge type inkjet method is preferable because it hardly causes image bleeding. A solid jet method using hot melt ink is also preferably used.

As an on-demand type inkjet 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, etc.

This is because ink is supplied 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 a high voltage is selectively applied to these electrodes. The ink near the electrodes is ejected onto the recording paper that is close to and facing the slits for recording.

As another method not using a slit-shaped recording head, Japanese Patent Laid-Open No. 61-211048 discloses that a hole is formed in a film-shaped ink support having a plurality of fine holes, and ink is filled in the multi-needle. A means for selectively applying a voltage by electrodes to move the ink in the premises to the recording paper is disclosed.

The oil-based ink used is preferably a solid and hydrophobic resin at least at room temperature (15° C. to 35° C.) using a non-aqueous solvent having a specific electric resistance of 10 ⁹ Ω·cm or more and a dielectric constant of 3.5 or less as a dispersion medium. The particles are dispersed. By using such a dispersion medium, the specific electric resistance of the oil-based ink is appropriately controlled, the ink is appropriately ejected by the electric field, and the image quality is improved. Further, by using the resin particles as described above, the affinity with the image receiving layer is increased, a good image quality is obtained and the printing durability is improved. Specifically, JP-A-10-203039 and 10-2502.
The oil-based inks described in No. 54 and the like are mentioned.

As the solid jet method, So
lid Inkjet Platemaker SJ02A (manufactured by Hitachi Koki Co., Ltd.),
A commercially available printing system such as MP-1200Pro (manufactured by Dynic Corporation) can be used.

The plate making method using the ink jet recording method will be described more specifically with reference to FIGS. 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. Through the means, the ink is supplied to the inkjet recording apparatus 1 using the 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 (master plate for plate-making printing).

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 has a slit sandwiched between them, the tip of which is an ejection slit 10a, the ejection electrode 10b is arranged in the slit, and the oil ink 11 is filled in the slit. Is becoming

In the head 10, a voltage is applied to the ejection electrode 10b according to the digital signal of the 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 ejection 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, on the lithographic printing plate precursor,
An image is formed by an inkjet method using an oil-based ink to obtain a plate making master.

[0110]

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 1 100 g of zinc oxide (FINEX-50, manufactured by Sakai Chemical Industry Co., Ltd.; average particle size: 40 nm), polyvinyl alcohol modified with sulfonic acid (SK-5102, manufactured by Kuraray Co., Ltd.); modification amount = 25 mol% 10% by weight aqueous solution of 90 g and water 2
40 g of the mixture was dispersed in a paint shaker (Toyo Seiki Co., Ltd.) for 30 minutes, and 107 g of a previously hydrolyzed 20% by mass tetramethoxysilane water/ethanol (1:1) solution and a 20% colloidal silica aqueous solution (Snow Tech C and 182 g of Nissan Chemical Industries Ltd. were mixed to obtain an image receiving layer composition. The above image was formed on a support (Beck smoothness on the under side: 2000 (sec/10 cc)) of an ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing original plate for light printing. The receiving layer composition was applied using a wire bar and dried in an oven at 100° C. for 10 minutes to give a dry coating amount of 5 g/
An m ² image-receiving layer was prepared and used as a lithographic printing original plate.

The surface smoothness (second/10 cc) of this lithographic printing plate precursor was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air capacity of 10 cc.
It was 0 (second/10cc). 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
Surface contact angle meter (CA-D, manufactured by Kyowa Interface Science Co., Ltd.)
It was 5 degrees or less when measured using.

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 the unevenness of toner transfer is not recognized at all. However, the background fog caused by the toner scattering was also slight, and there was no problem in practical use.

Next, after making the lithographic printing plate precursor by the same operation as described above, it was treated with a fully automatic printing machine (AM-2850 (manufactured by AM Co.) as fountain solution for PS plate treatment). Agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) with distilled water 5
The 0-fold diluted solution was placed in a fountain solution tray and printing was performed by using a black ink for offset printing through a plate-making product in a printing machine (standard condition). The printed image (ground fog, solid uniformity of image area) of the 10th printed matter was visually evaluated using a 20 times magnifying glass, and it was extremely good. Further, 5,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas and had no practical problems with ink stains on non-image areas. Further, printing was carried out by reducing the supply amount of the immersion water by 30% as compared with the case of the standard printing conditions described above, but 5000 or more good prints which were the same as the prints under the standard conditions were obtained. The original plate of the present invention can produce a large number of excellent printed matter even under severe printing conditions.

Comparative Example 1 Sulfonic acid-modified polyvinyl alcohol (SK-5102) of the image receiving layer composition was replaced with polyvinyl alcohol (PVA).
-117, manufactured by Kuraray Co., Ltd., except that the original plate for lithographic printing was prepared in the same manner as in Example 1. The surface of the obtained plate had a Bekk smoothness of 140 (sec/10 cc) and a contact angle with water of 5 degrees or less.

The above plate was made in the same manner as in Example 1. The image quality of the plate made was almost the same as that of Example 1 and the amount of scattered toner in the non-image area was small and the image was good. However, when printing was performed under the same conditions as in Example 1, a printed matter similar to that in Example 1 was obtained under standard conditions, but when printing was performed by reducing the supply amount of immersion water by 30%, the printed matter was From the printout, dust-like stains with a slight amount of printing ink adhering to the non-image area were observed. Further, when the image was printed as it was, and the image portion was missing, about 1000 sheets were printed.

Example 2 Barium titanate (BaTiO ₃ : average particle size 0.6 μm)
m) 100 g of sulfonic acid modified polyvinyl alcohol (SK-5102, manufactured by Kuraray Co., Ltd.; modification amount=25)
90% of a 10% by weight aqueous solution (mol%) and 240 g of water are mixed, and the mixture is mixed with a paint shaker (Toyo Seiki Co., Ltd.) to 30
Preliminarily hydrolyzed to the liquid dispersed for 20 minutes by mass.
Tetramethoxysilane water/ethanol (1:1) solution 1
An image receiving layer composition was obtained by mixing 07 g and 182 g of a 20% colloidal silica aqueous solution (Snowtex C, Nissan Chemical Industries, Ltd.). The above image-receiving layer composition was applied to a support of ELP-2X type master using a wire bar and dried in an oven at 100° C. for 10 minutes to prepare an image-receiving layer having a dry coating amount of 5 g/m ^2. The planographic printing plate was used.

The surface smoothness (second/10 cc) of this lithographic printing plate precursor was measured using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under an air volume of 10 cc.
It was 0 (second/10cc). 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
Surface contact angle meter (CA-D, manufactured by Kyowa Interface Science Co., Ltd.)
It was 5 degrees or less when measured using.

The lithographic printing plate precursor described above was replaced with "AM-Straig
"HT Imaging System" commercially available laser printer using dry toner AMSIS 1200-
The plate was made through J Plate Setter (trade name).

The copy image of the obtained plate-making product was visually evaluated using a 20-fold loupe, and 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 the unevenness of toner transfer is not recognized at all. However, the background fog caused by the toner scattering was also slight, and there was no problem in practical use.

Next, the lithographic printing plate precursor was subjected to plate making by the same operation as described above, and then treated as a fountain solution with a fully automatic printing machine (AM-2850 (manufactured by AM Co., Ltd.)) for PS plate treatment. Agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) with distilled water 5
The 0-fold diluted solution was placed in a fountain solution tray and printing was performed by using a black ink for offset printing through a plate-making product in a printing machine (standard condition). The printed image (ground fog, solid uniformity of image area) of the 10th printed matter was visually evaluated using a 20 times magnifying glass, and it was extremely good. Further, 5,000 or more good prints were obtained which had an image without fine lines, missing fine characters and uneven solid areas and had no practical problems with ink stains on non-image areas. Further, printing was carried out by reducing the supply amount of the immersion water by 30% as compared with the case of the standard printing conditions described above, but 5000 or more good prints which were the same as the prints under the standard conditions were obtained. The original plate of the present invention can produce a large number of excellent printed matter even under severe printing conditions.

Example 3 <Preparation of direct-drawing type lithographic printing plate precursor> The following composition was used together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.).
After being dispersed at room temperature for 20 minutes, the glass beads were filtered to obtain a dispersion.

Zinc oxide (FINEX-50, manufactured by Sakai Chemical Industry Co., Ltd.) 100 g 10% aqueous solution of carboxylic acid-modified polyvinyl alcohol (KL-118, manufactured by Kuraray Co., Ltd.; change amount=25 mol%) 250 g Tetraethoxysilane 4.2 g Ethanol 8.6 g Colloidal silica 20% aqueous solution (Snowtex C) 182 g Fluorinated alkyl ester (FC-430, 3M product) 0.25 g Curing agent CH ₂ =CHSO ₂ CH ₂ CONH(CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH=CH ₂ 1.0 g 1N (mol/L) hydrochloric acid 4 g water 150 g

Using the ELP-2X type master support,
The above composition was coated thereon with a wire bar so that the coating amount after drying was 6 g/m ² , dried by touch and then heated at 110° C. for 30 minutes to form an image receiving layer to form a lithographic plate. The original plate for printing. The surface of the obtained original plate had a Bekk smoothness of 750 (seconds/10 cc) and a contact angle with water of 5 degrees or less.

<Production 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 together with glass beads in a 500 ml glass container, dispersed for 60 minutes with a paint shaker (Toyo Seiki Co., Ltd.), and then the glass beads were separated by filtration to obtain a photosensitive layer. It was a dispersion liquid.

[0127]

[Chemical 4]

Next, this 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 a dark place to have a surface potential of +450 V, and then the original was read in advance by a color scanner and color-separated. After making corrections related to the color reproduction of the image, based on the information stored in the hard disk in the system as digital image data, using a semiconductor laser drawing device as an exposure device, a beam spot of 788 nm Exposure was performed at a diameter of 15 μm and a pitch of 10 μm and a scanning 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 (mJ/m ² ).

Subsequently, the liquid developer having the following contents is used for development, followed by rinsing in a bath of Isopar G to remove stains on the non-image area. Then, the surface temperature of the photoconductor is adjusted to 50° C. with warm air. It was dried so that the remaining amount of Isopar G was (10 mg/toner 1 g). Further, subsequently, a precharge of -6 KV was applied to the photoconductor by a corona charger, the image surface of the photoconductor was overlapped with the lithographic printing original plate, and a negative corona discharge was applied from the electrophotographic photoconductor side to transfer. ..

<Liquid Developer> The components having the following compositions 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 toner solid content 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.

(Composition for kneading) Ethylene/methacrylic acid copolymer 4 parts by mass (Mitsui DuPont, Nucrel N-699) Carbon black #30 (manufactured by Mitsubishi Kasei) 1 part by mass Isopar L (manufactured by Exxon) ) 15 parts by mass

The lithographic printing plate precursor with the image formed thereon was heated at a temperature of 10
The toner image area was completely fixed by heating at 0° C. for 30 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, using the printing plate prepared as described above, Oliver 94 type (manufactured by Sakurai Mfg. Co., Ltd.) was used as a printing machine, and SLM-OD (Mitsubishi Paper Mills Co., Ltd.) was used as fountain solution.
A solution prepared by diluting 100% by volume with distilled water was placed in a dampening water tray part, and printing was performed by passing a plate-making product through a printing paper using a black ink for offset printing. When the printed image of the 10th printed sheet was visually evaluated using a 20 times magnifying glass, no background stain was found due to the adhesion of printing ink to the non-image area, and the uniformity of the solid image area was good. Further, under observation with an optical microscope at a magnification of 200 times, fine lines, thinning of fine characters, loss, etc. were not observed, and the image quality was good. 10,000 or more prints with the same print quality as this were obtained.

Example 4 <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 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 processing was performed so that it would be about (second/10cc).

(Paint for back 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

Next, an under layer coating material 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 processing was performed so that it would be about (second/10cc).

(Coating 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

By mixing the above-mentioned components, the total solid content becomes 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 was measured as follows. The under layer coating material was applied onto a stainless steel plate that had been thoroughly degreased and washed to obtain a coating film having a dry coating amount of 10 g/m ² . The specific electrical resistance value of the obtained sample was measured by the three-terminal method with a guard electrode according to JIS K-6911, and a value of 4×10 ⁹ Ω·cm was obtained.

<Preparation of direct-drawing lithographic printing plate precursor> The following composition was dispersed together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 20 minutes, and then the glass beads were separated by filtration to obtain a dispersion. Obtained.

Barium titanate (BaTiO ₃ : average particle size 0.6 μm) 100 g Phosphono group-modified polyvinyl alcohol (modification amount=7 mol %) 10% aqueous solution 270 g tetraethoxysilane 30 g methyltrimethoxysilane 3 g Snowtex C 20% aqueous solution 91 g ethanol 10g 1N (mol/L) hydrochloric acid 5g water 150g

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, and dried in an oven at 100° C. for 20 minutes to prepare a planographic printing plate. The original edition was created. Bekk smoothness of the surface of the original plate is 500
(Sec/10 cc), the contact angle with water was 5 degrees or less.

<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. Further, 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. ．
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, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion 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 put 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
As a solid content, 5 g (solid content) of the above blue dispersion and 0.08 g of octadecene-half-maleic acid octadecylamide copolymer were diluted to 1 liter of Isopar G to prepare a blue oil-based ink (IK-1). Created.

[0145] The original plate obtained above can be used to draw personal computer output.
8400 was modified, the ink ejection head shown in FIG. 2 was attached to the pen plotter, and the oil-based ink (IK-1) was added to the lithographic printing plate precursor installed on the counter electrode with a gap of 1.5 mm. ) Was used for printing to make a plate. At the time of plate making, the under layer provided directly under the image receiving layer of the printing plate and the counter electrode were electrically connected using a silver paste. The plate-prepared plate was adjusted so that the plate surface temperature was 70° C., and the ink image was fixed with a Ricoh fuser (manufactured by Ricoh Co., Ltd.) for 10 seconds. The drawn image of the obtained plate-making product was observed and evaluated by 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 (manufactured 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 pan, and black ink for offset printing was used.
Printing was carried out by passing the plate-making product on printing paper. When the printed image of the 10th printed matter was visually evaluated using a magnifying glass of 20 times, no background stain was found due to the adherence of the printing ink in the non-image area, and the uniformity of the solid image area was good. .. 20 more
Observation with a 0× optical microscope showed no fine lines, thinning of fine characters, missing, etc., and good image quality. More than 5,000 prints with print quality equivalent to this were obtained.

Examples 5 to 11 In place of the sulfonic acid-modified polyvinyl alcohol (SK-5102) and tetramethoxysilane in the image-receiving layer coating solution in Example 1, the organic polymer 2 shown in Table 1 below was used.
Example 1 except that 4 g and 24 g of the metal compound were used respectively.
An original plate for a lithographic printing plate was prepared in the same manner as in.

[0148]

[Table 1]

The Bekk smoothness of the surface of each of the obtained original plates was in the range of 100 to 170 (sec/10 cc), and the contact angle of the surface with water was 5 degrees or less. When a plate was made and a printing plate was prepared in the same manner as in Example 1, and printing was carried out, the obtained printed products all had clear image quality with no stains on the non-image areas, as in the printing plate of Example 1. The printing durability was as good as 4,000 sheets or more.

Examples 12 to 18 In place of the sulfonic acid-modified polyvinyl alcohol (SK-5102) and tetramethoxysilane in the image-receiving layer coating solution in Example 2, the organic polymer 2 shown in Table 2 below was used.
Example 2 except that 4 g and 24 g of the metal compound were used respectively.
An original plate for a lithographic printing plate was prepared in the same manner as in.

[0151]

[Table 2]

The Bekk smoothness of the surface of each of the obtained original plates was in the range of 110 to 160 (sec/10 cc), and the contact angle of the surface with water was 5 degrees or less. When printing was carried out as a plate making and printing plate in the same manner as in Example 2, all of the obtained prints had clear image quality with no stains on the non-image areas, like the printing plate of Example 2. The printing durability was as good as 4,000 sheets or more.

Examples 19 to 35 In Example 1, instead of zinc oxide FINEX-50, which is a component of the image receiving layer composition, particles of metal oxides shown in Table 3 (the average particle size of each particle is 0. A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the lithographic printing plate precursor was used. The Bekk smoothness of the surface of each obtained original plate is 1
In the range of 50 to 200 (sec/10 cc), the contact angle of water on the surface was 5 degrees or less. Plate making in the same manner as in Example 1,
When printing was performed as a printing plate, all of the obtained prints had a clear image quality with no stains on the non-image areas, like the printing plate of Example 1, and had a printing durability of 4,000 sheets or more. It was good.

[0154]

[Table 3]

Examples 36 to 53 In Example 2, instead of barium titanate which is a component of the image receiving layer composition, the particles of the complex oxide shown in Table 4 (the average particle size of each particle is 0.03 to 2 μm). ) Was used to prepare a lithographic printing plate precursor in the same manner as in Example 2. The Bekk smoothness of the surface of each obtained original plate is 160 to 220 in all cases.
In the range of (sec/10cc), the contact angle of the surface with water was 5 degrees or less. When printing was carried out as a plate making and printing plate in the same manner as in Example 2, all of the obtained prints had clear image quality with no stains on the non-image areas, like the printing plate of Example 2. The printing durability was as good as 4000 sheets or more.

[0156]

[Table 4]

Example 54 In Example 4, instead of 100 g of barium titanate, which is a component of the composition used for preparing the lithographic printing plate precursor for direct drawing, 70 g of barium titanate was used, and oxidation with an average particle size of 0.6 μm was performed. A lithographic printing plate precursor was prepared in the same manner as in Example 4 except that 30 g of magnesium was used. The Bekk smoothness of the surface of each of the obtained original plates was in the range of 530 (sec/10 cc), and the contact angle of the surface with water was 5 degrees or less. When printing was carried out as a plate making and printing plate in the same manner as in Example 4, all of the obtained prints had clear image quality with no stains on the non-image areas, like the printing plate of Example 4. , Printing durability 7.0
It was a good one with more than 1,000 sheets.

By using the direct drawing type lithographic printing plate precursor of the present invention, it is possible to obtain an excellent image in which not only spot-like background stains but also spot-like background stains are not generated. 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 image formation 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 original plate of the present 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]

DESCRIPTION OF SYMBOLS 1 Ink jet recording apparatus 2 Master (lithographic printing original plate) 3 Computer 4 Bath 10 Head 10a Ejection slit 10b Ejection electrode 10c Counter electrode 11 Oil-based ink 101 Upper unit 102 Lower unit

Claims (4)

[Claims] 1. An average particle size of 0.01 to 0.5 on a water resistant support.
5 μm metal oxide particles (however, the metal atoms constituting the metal oxide are Mg, Ba, Ge, Sn, Zn, Pb, L
a, Zr, V, Cr, Mo, W, Mn, Co, Ni and/or Cu) and/or double oxide particles having an average particle diameter of 0.01 to 5 μm (however, double oxide). At least one kind of metal atom constituting
1, Si, Ti, Zr, Cr, V, Mo, Sn, W and Nb) and a resin containing a bond in which a metal atom is connected via an oxygen atom and a group capable of forming a hydrogen bond with the resin. And an image receiving layer containing at least a binder resin containing a complex with an organic polymer containing at least one polar functional group selected from a carboxyl group, a sulfo group and a phosphono group. Original plate for drawing type planographic printing. 2. The resin containing a bond in which metal atoms are connected via an oxygen atom is a polymer obtained by hydrolysis polycondensation of at least one metal compound represented by the following general formula (I). The lithographic printing plate precursor for direct drawing according to claim 1. 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, z represents the valence of the metal M ⁰ , n represents 0,
Represents 1, 2, 3, or 4. However, z−n is 2 or more. ] 3. The direct drawing type lithographic printing plate precursor as claimed in claim 1, wherein the surface of the image receiving layer has a Bekk smoothness of 30 (sec/10 cc) or more. 4. The direct drawing type lithographic printing plate precursor according to claim 1, wherein at least a nonaqueous solvent having a specific electric resistance of 10 ⁹ Ω·cm or more and a dielectric constant of 3.5 or less is used. A method for producing a lithographic printing plate, comprising forming an image by an inkjet method by ejecting an oil-based ink in which resin particles having a solid and hydrophobic charge at room temperature are dispersed by using an electrostatic field.