JP2001232962A - Direct lithography type lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a direct lithography type lithographic printing original plate capable of printing many printed products of a clear image without lack, a strain or the like of the image without generating an overall uniform scum ming or a point-like scumming as an offset original plate. SOLUTION: The direct lithography type lithographic printing original plate comprises an image acceptive layer for forming a dispersed material containing a binding resin including metal oxide particles having a mean particle size of 0.01 to 5 μm (where metallic atom for constituting the metal oxide is at least one type selected from Mg, Ba, Ge, Sn, Zn, Pb, La, Zr, V, Cr, Mo, W, Mn, Co, Ni and Cu) for forming and a composite material of a resin having a bond connected with a metallic atom via an oxygen atom and an organic polymer having a group capable of forming a hydrogen bond with a resin and a silyl functional group represented by a -Si(R)n(OX)3-n [wherein R is a hydrogen atom or 1-12C hydrocarbon group, X is 1-12C aliphatic group, and n is 0, 1 or 2] 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 formula (I), R represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. X represents an aliphatic group having 1 to 12 carbon atoms. n represents 0, 1 or 2. ]

(2) The resin containing a bond in which the metal atom is connected via an oxygen atom is a polymer obtained by hydrolysis polycondensation of at least one metal compound represented by the following general formula (II). A lithographic printing plate precursor for direct drawing according to the above (1), characterized in that General formula (II) (R ⁰ ) _n M(Y) _zn [In the general formula (II), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M is 3 ~ Represents a hexavalent metal, z represents the valence of the metal M, n is 0, 1,
Represents 2, 3, or 4. However, z−n is 2 or more. ]

(3) The direct drawing 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 precursor, which comprises forming an image by an inkjet method by discharging an oil-based ink in which resin particles having a solid and hydrophobic charge are dispersed at least at room temperature by utilizing an electrostatic field.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention includes a resin containing a bond in which a metal atom is connected via an oxygen atom (hereinafter, referred to as a metal-oxide-containing particle having an average particle size of 0.01 to 5 μm of a metal oxide composed of a specific metal atom, on a water-resistant support. A dispersion containing at least a binder resin containing a complex of a metal-containing resin) and a group that forms a hydrogen bond with the resin and an organic polymer containing a silyl functional group is formed into a film. A lithographic printing plate precursor for direct drawing having an image-receiving layer having a hydrophilic surface.

In the present invention, in the dispersion of the metal oxide particles and the composite of the metal-containing resin and the organic polymer, the interaction between the two is high, the dispersibility of the metal oxide particles is good, and after the film formation, the above mutual interaction is achieved. By the action, a film having excellent printing durability is obtained, and at the same time, good hydrophilicity and image adhesion are 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
It is a metal oxide particle selected from a, Zr, V, Cr, Mo, W, Mn, Co, Ni and Cu. The metal oxide particles may be any as long as they have no problem in stability and material safety. Preferred metal atoms are Mg, Ge,
Sn, Zn, Pb, Zr, V, Cr, W, Ni or Cu
Is. The size of the particles is 0.0 in terms of average particle size.
It is 1-5 micrometers, and 0.02-3 micrometers is preferable. Within this range, preferable smoothness of the surface of the image receiving layer and image strength after image formation are obtained, and stains of printing ink in non-image areas do not occur.

These metal oxides are produced by a conventionally known method, for example, "Chemical Chemistry Lecture 9, Synthesis and Purification of Inorganic Compounds" edited by The Chemical Society of Japan, published by Maruzen Co., Ltd. (1958),
Chemistry Dictionary Edit Committee "Chemical Dictionary 3" 890-94
It is specifically described in page 9, 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 binder resin used in the image-receiving layer of the present invention is a resin containing a bond in which metal atoms are connected via oxygen atoms, that is, a metal-containing resin and a group capable of forming a hydrogen bond with this resin. And a resin composed of a complex with an organic polymer containing a specific silyl functional 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 is preferably a polymer obtained by hydrolytic polycondensation of a metal compound represented by the following general formula (II). General formula (II) (R ⁰ ) _n M(Y) _zn [In the general formula (II), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M is 3 ~ Represents a hexavalent metal, z represents the valence of the metal M, n is 0, 1,
Represents 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 are used singly or in combination of two or more kinds to produce a metal-containing resin.

Next, the metal compound represented by the general formula (II) will be described in detail. R ⁰ in the general formula (II) is preferably an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (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)},

An optionally substituted linear or branched alkenyl group having 2 to 12 carbon atoms (eg, 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 optionally substituted aromatic group having 6 to 12 carbon atoms (the aromatic group is the aryl group in R ⁰ described above). The same as those exemplified 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 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 (II) include, but are 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 represents an alkyl group (eg, 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 contains a group capable of forming a hydrogen bond with the metal-containing resin (hereinafter, also referred to as a specific bonding group) and a specific silyl functional group. In the organic polymer, the specific bonding group preferably includes at least one bond selected from an amide bond (including a carboxylic acid amide bond and a sulfonamide bond), a urethane bond and a ureido bond, and a hydroxyl group.

Examples of the organic polymer include those containing, as a repeating unit component, the specific bonding group of the present invention in 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 the organic residue is represented by the general formula (I
The same contents as the hydrocarbon group and heterocyclic group for R ⁰ in I) can be mentioned.

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

General formula (III)

[Chemical 1]

In the formula (III), Z ¹ is --CO-- or --SO ₂ --.
Or represents -CS-. R ²⁰ has the same content as R ⁰ in formula (II). r ¹ is 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 (III), Z ¹ represents a --CO-- bond,
The polymer in which p represents 2 can be obtained by ring-opening polymerization of oxazoline which may have a substituent in the presence of a catalyst. Examples of the catalyst include sulfuric acid esters and sulfonic acid esters such as dimethyl sulfate and p-toluenesulfonic acid alkyl ester; alkyl halides such as alkyl iodide (eg, methyl iodide); metal fluorides of Friedel-Crafts catalysts; Sulfuric acid, hydrogen iodide, p-
An acid such as toluene sulfonic acid or an oxazolinium salt which is a salt of these acids and oxazoline can be used. Incidentally, this polymer may be a homopolymer,
It may be 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.

Regarding other polymers having the repeating unit represented by the general formula (III), 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 (III)) can be mentioned.

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

[0046]

[Chemical 2]

[0047]

[Chemical 3]

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

Examples of natural and semi-synthetic polymers include cellulose, cellulose derivatives (cellulose esters; cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose succinate, cellulose butyrate, cellulose acetate succinate, acetic acid). Cellulose 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.

Examples of the synthetic polymer include polyvinyl alcohol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, (ethylene glycol/propylene glycol) copolymer, etc.), allyl alcohol copolymer, and acryl having at least one hydroxyl group. Polymers or copolymers of acid esters or methacrylic acid esters (as an ester substituent, 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 a silyl functional group represented by the above general formula (I).

The preferred hydrocarbon group represented by R in formula (I) is an optionally substituted alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). , Heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 3,6-dioxoheptyl group, 3- Sulfopropyl group, 2-carboxyethyl group,
2-methoxycarbonylethyl group, 3-chloropropyl group, 3-bromopropyl group, 2,3-dihydroxypropyl group, trifluoroethyl group, etc.), an alkenyl group having 3 to 12 carbon atoms which may be substituted (eg, propenyl). Group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, etc.), an aralkyl group having 7 to 12 carbon atoms which may be substituted (for example,
Benzyl group, phenethyl group, 3-phenylpropyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, carboxybenzyl group, etc.),

An alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or having 6 to 12 carbon atoms which may be substituted. Good aromatic groups (eg phenyl, naphthyl, tolyl, xylyl,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, carboxyphenyl group, sulfophenyl group, carboxymethylphenyl group, etc. ) And the like.

X in the formula (I) represents an aliphatic group having 1 to 12 carbon atoms. Preferably an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-methoxyethyl group, 2-ethoxy group). Ethyl group, 3-methoxypropyl group, 3,6-dioxoheptyl group, 2-oxobutyl group, etc., and alkenyl groups having 3 to 8 carbon atoms which may be substituted (eg, propyl group, butenyl group, pentenyl group, hexenyl). Group, heptenyl group, octenyl group, etc.), C7-C12 optionally substituted aralkyl group (eg, benzyl group, phenethyl group,
3-phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted. Examples thereof include groups (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.). The more preferable aliphatic group for X includes an alkyl group having 1 to 4 carbon atoms which may be substituted.

N represents 0, 1 or 2. It is preferably 0 or 1.

The silyl functional group may be directly bonded to the side chain in the repeating unit of the polymer or the terminal of the polymer main chain, or may be bonded via a linking group. As the linking group, any linking group may be used, but specifically, for example, —O—, —CR ¹¹ R ¹² — [wherein R ¹¹ and R ¹² may be the same or different. , Hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), -OH
Group, cyano group, alkyl group (methyl group, ethyl group, 2-
Chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.], —S—, —NR
^13- [wherein R ¹³ is a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, 2 -Methoxyethyl group, 2-chloroethyl group, 2-
Cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group,
A methoxyphenyl group etc.)], -C
O -, - COO -, - OCO -, - CONR 13 -, - S
^{_{O 2 NR 13 -, - SO}} 2 -, - NHCONH -, - NHC
_{OO -, - NHSO 2 -,} - CONHCOO -, - CO
NHCONH-, and the like, and a linking group composed of a single bonding group such as NHCONH- or a combination of two or more thereof.

The method for producing the organic polymer of the present invention is not particularly limited, and for example, it can be easily obtained by modifying an organic polymer having a hydroxyl group by a conventional method and introducing a silyl 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. For example, there is a method in which a silylating agent having a silyl functional group of the general formula (I) is used to react with the hydroxyl group of the above organic polymer to modify. Specifically, it can be easily carried out according to the method described in “Synthesis and Application of Reactive Polymer” published by CMC (1989), JP-B-46-30711, JP-A-5-32931 and the like. However, it is not limited to these. In these production methods, adjustment can be made so that a desired amount of hydroxyl groups remain.

The hydroxyl group-containing resin may be a natural polymer, a semi-synthetic polymer, or a synthetic polymer, and specifically, "Water-soluble polymer/water-dispersible resin comprehensive technical data collection" edited by the Management Development Center Published by Management Development Center Publishing Department (1981
), Shinji Nagatomo "Applications and Markets of New Water-Soluble Polymers"
Published by CMC Co., Ltd. (1988), “Development of Functional Cellulose” Published by CMC Co., Ltd. (1985), supervised by Mitsuo Kotake “Large Organic Chemistry Vol. 19: Natural Polymer Compound I” Asakura Shoten (1960) 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 Derivatives, alginic acid, pectin, carrageenan, tamarind gum, natural gums (eg gum arabic, guar gum, locust bean gum, transgant gum, xanthan gum), pullulan, dextran, casein, gelatin, chitin, chitosan Be done.

Examples of the synthetic polymer include polyvinyl alcohol, polyalkylene glycol [polyethylene glycol, polypropylene glycol, (ethylene glycol/propylene glycol) copolymer, etc.], allyl alcohol copolymer, and acryl containing at least one hydroxyl group. Acid copolymers or methacrylic acid copolymers, acrylic acid ester or methacrylic acid ester polymers or copolymers containing at least one hydroxyl group [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, polyoxy Propylene group etc.], N-substituted polymer or copolymer of acrylamide or methacrylamide containing at least one hydroxyl group [as N-substituent, for example, monomethylol group, 2-hydroxyethyl group, 3-hydroxypropyl group] Group, 1,1-bis(hydroxymethyl)ethyl group, 2,3,4,5,6-pentahydroxypentyl group, etc.] and the like. However, as a synthetic polymer,
The side chain substituent of the repeating unit is not particularly limited as long as it has at least one hydroxyl group. Further, the organic polymer of the present invention can also be produced by a method using a monomer having a silyl functional group as a starting material for synthesis.

The content of the silyl functional group in the organic polymer is usually 0.01 to 50 mol %, preferably 0.1 to 20 as the unit component having the silyl functional group.
mol%, more preferably 0.2 to 15 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 silyl functional groups.
The organic polymers may be used alone or in combination of two or more. The organic polymer of the present invention, which contains a silyl functional group, has the effect of further increasing the film strength of the image receiving layer using the same and improving the printing durability of the printing plate obtained.

The organic polymer can be easily reacted by the condensation reaction of the [—Si(R) _n (OX) _{3 -n} ] group in the step of heating and drying after forming the coating film.

[0063]

[Chemical 4]

A siloxane bond represented by the formula (3) is formed to cause bridging between the polymers, and the film is cured to sufficiently maintain the film strength of the image receiving layer. Although the details are unknown, the surface of the image receiving layer of the present invention is sufficiently hydrophilic, and at the same time, the image adhesion is extremely good, and the printing durability as a printing plate is dramatically improved.

The weight average molecular weight of the organic polymer of the present invention is preferably 10 ³ to 10 ⁶ , more preferably 5×10 ⁶ .
^{It is 3} to 4×10 ⁵ .

In the composite of the metal-containing resin and the organic polymer, 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 2
It is 0/80 to 80/20. Within this range, the strength of the film of the image receiving layer and the affinity with the water-proof ink, toner, etc. for the dampening water during printing become good.

The binder resin containing the composite of the present invention has a hydroxyl group of the metal-containing resin produced by the hydrolytic polycondensation of the metal compound, the specific bonding group in the organic polymer and the silyl functional group. A uniform organic-inorganic hybrid is formed by the action of hydrogen bonding, etc., and it 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. Further, the composite of the present invention is excellent in film forming property.

The composite of the present invention is produced by subjecting the metal compound to hydrolysis polycondensation and mixing with an organic polymer, or by subjecting the metal compound to hydrolysis polycondensation in the presence of an organic polymer. To be done.

Preferably, the organic-inorganic polymer composite of the present invention can be obtained by subjecting the metal compound to hydrolysis and polycondensation 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 synthesized 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 (II), 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 metal oxide particles of the present invention may be contained as other components. Examples thereof include silica, alumina, kaolin, clay, titanium oxide, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate and magnesium carbonate. These other inorganic pigments are used within the range of not more than 40 mass% with respect to the metal oxide 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 pigment means the sum total including the metal oxide used in the present invention and an inorganic pigment 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 cross-linking agent may be added to the image receiving layer in order to improve the film strength. Examples of the cross-linking agent include compounds usually used as cross-linking agents. Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook 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 preferable range of toner to be used is dry toner and liquid toner as follows.

In an electrophotographic printer using a 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 irregularities are highly formed 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 coated. For example, a conductive layer, an under layer, or an over layer described later 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 for 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 type lithographic printing plate precursor of the present invention comprises an oil-based ink which forms a toner image on an image-receiving layer provided on a water-resistant support by an electrophotographic recording method or utilizes 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 droplets adhere to the image receiving layer, the charge of the ink droplets quickly disappears through the ground plane, so that a clear image without disturbance is formed. 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 impart 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 formation of the conductive layer is achieved by applying a layer containing a conductive filler and a binder to both sides of the conductive paper. The thickness of the conductive layer applied is 5 μm to 2
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.

An 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 conductive plastic film, for example, polypropylene or polyester film mixed with a conductive filler such as carbon fiber or carbon black can be used, and as the metal plate, aluminum or the like can be used. The thickness of the substrate is preferably 80 μm to 200 μm. If it is less than 80 μm, the strength 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 side of the support opposite to the image receiving layer for the purpose of preventing curling. However, the back coat layer has a smoothness. It is preferably in the range of 150 to 700 (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 film thickness of the water resistant support provided with the under layer or back coat layer is in the range of 90 to 130 μm, preferably in the range of 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 the excess developing solution, squeeze such as rubber roller, gap roller, reverse roller, etc., corona squeeze, air squeeze, etc. as shown on page 283 of the same document are performed. It is also preferable to rinse only with the carrier liquid of the developer before squeezing. 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,
A method called an electrostatic acceleration type ink jet or a slit jet described in Journal of Image Electronics Engineers, vol. 10, (No. 3), p157 (1981) and the like is known, and a specific embodiment thereof is, for example, JP-A-56- 170, 56-4467, 57-151
No. 374 and the like.

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 which does not use a slit-shaped recording head, Japanese Patent Laid-Open No. 61-211048 discloses that a hole is formed in a film-shaped ink support having a plurality of fine holes and ink is filled therein, and a multi-needle is used. A means for selectively applying a voltage by electrodes to move the ink in the holes 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 JP-A-10-25
Examples thereof include oil-based inks described in No. 0254.

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 the 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.

[0122]

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), trialkoxysilyl group-modified polyvinyl alcohol R-1130 (manufactured by Kuraray Co., Ltd.; modification amount=0) 10% by mass aqueous solution 11 of 0.3 mol%)
3 g and 240 g of water were dispersed together with glass beads for 30 minutes with a paint shaker (manufactured by Toyo Seiki Co., Ltd.). Further, there is 20 of tetraethoxysilane previously hydrolyzed.
Mass% (water/ethanol (1/1) mass ratio) solution 110
g and colloidal silica (Snowtec C (20 mass% aqueous dispersion), manufactured by Nissan Chemical Industries, Ltd.; average particle size: 20n
m) 200 g was added and dispersed for 3 minutes, and then the glass beads were filtered out to obtain an image receiving layer composition.

A support of an ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light printing [Beck smoothness on the under side: 20]
00 (sec/10 cc)], and apply the above-mentioned image-receiving layer composition using a wire bar.
After drying for 1 minute, an image-receiving layer having a dry coating amount of 8 g/m ² was prepared and used as a lithographic printing original plate.

Comparative Example A A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that titanium oxide (TiO ₂ : average particle diameter 0.3 μm) was used in place of zinc oxide. ..

The performance evaluation results of each original plate obtained as described above are shown in Table-A.

[0127]

[Table 1]

Each item shown in Table-A was evaluated according to the following contents.

Note 1) Smoothness of the surface of the image receiving layer The original plate for lithographic printing was changed to a Beck smoothness tester (Kumagaya Riko Co., Ltd.).
Manufactured by K.K., and its smoothness (second/10 cc) is measured under the condition of an air capacity of 10 cc.

Note 2) Contact angle with water 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 at room temperature was measured with a surface contact angle meter (C
It is measured using A-D, Kyowa Interface Science Co., Ltd.

Note 3) Image reproducibility Using the lithographic printing plate precursor prepared as described above, the servo plotter DA8400 manufactured by Graphtec Co., which can draw the output of a personal computer, was modified and shown in FIG. 2 in the Ben plotter section. An ink discharge head was attached, and printing was carried out by using an oil-based ink (IK-1) having the following content on a lithographic printing plate precursor set on a counter electrode with a gap of 1.5 mm. Continuously, RICOH FUSER model 592
(Manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 80° C. and heated for 1 minute to sufficiently fix the image area. A copy image of the obtained plate-making product (that is, a printing plate) was visually observed with an optical microscope at a magnification of 200 times.

<Preparation of Oil-based Ink (IK-1)> 12 g of dispersion stabilizing resin (PS-1) having the following structure, 1 part of vinyl acetate
A mixed solution of 00 g and Isopar G321 g was heated to a temperature of 75° C. with stirring under a nitrogen stream. As a polymerization initiator, 1.5 g of 2,2'-azobis(isovaleronitrile) (abbreviation AIVN) was added and reacted for 3 hours. Further, 1.0 g of this initiator was added, and after reacting for 3 hours, the temperature was raised to 100° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, it was passed through a nylon cloth of 200 mesh, and the white dispersion obtained had a polymerization rate of 93% and an average particle size of 0.1.
The latex had a good monodispersity of 38 μm. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.).

[0133]

[Chemical 5]

A part of the white dispersion was subjected to a centrifuge (rotation speed 1×10 ⁴ rpm, rotation time 60 minutes) to collect and dry the precipitated resin particle component. The weight average molecular weight (Mw; polystyrene equivalent GPC value) of the resin particles is 2
×10 ⁵ , glass transition point (Tg) was 38° C. (referred to as resin particles (PL-1)).

On the other hand, 10 g of dodecyl methacrylate/acrylic acid copolymer (copolymerization ratio: 95/5 mass ratio), 10 g of nigrosine and 30 g of Isopar G were put in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) together with glass beads for 4 hours. Dispersion gave a fine dispersion of nigrosine.
60 g (as solid content) of the resin particles (PL-1),
A black oil-based ink (IK-1) was prepared by diluting 7.5 g of the above nigrosine dispersion and 0.06 g of dodecene-half-maleic acid octadecylamide copolymer into 1 liter of Isopar E.

Note 4) Printing durability A printing plate was prepared by performing image formation and fixing of the image area on the lithographic printing plate precursor in the same manner as in Note 3) above. Using this printing plate, a solution obtained by diluting PS-3 treatment agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) with water 50 times as immersion water was used as a printing machine, and Oliver 94 type (Sakurai Co., Ltd.) was used as a printing machine. (Manufactured by Seisakusho Co., Ltd.) was used to print with black ink for offset printing. The printing durability is defined as the number of printed sheets with a clear image that is free of background stains and fine lines and characters.

From the results in Table-A, Example 1 and Comparative Example A
The surface smoothness of the image receiving layer was almost the same, and the contact angle with water was 0°, and the surface hydrophilicity was good. In Example 1, the plate that was actually made had no blurring or distortion of fine lines, fine characters, etc., the density of the solid portion was sufficient, and the dot image on the plate was perfectly circular and good. On the other hand, in Comparative Example A, the dot shape, the thin line, the thin character, and the like were the same as those in Example 1, but the density of the solid portion was low.
When the obtained printing plate was actually printed, in Example 1, 15,000 sheets of a printed matter having a clear image without printing ink adhesion stain on the non-image portion were obtained, while in Comparative Example A, Although the image area did not become dirty, the missing image area was 1500.
It happened about once.

Examples 2 to 18 In place of 100 g of zinc oxide in Example 1, each compound shown in Table B below (the average particle size of each particle is 0.03 to
Each lithographic printing plate precursor was prepared in the same manner as in Example 1 except that 100 g of 2 μm) was used. The Bekk smoothness of the surface of each obtained original plate was 260 to 320 (second/10 cc), and the contact angle with water was 0 degree. For each original plate, a plate was made and printed in the same manner as in Example 1. The resulting printed matter had a clear image with no background stains on the non-image area and no blurring or distortion of fine lines and characters. The results of printing durability of each of these plates are shown in Table-B. Each plate showed good printing durability of 6,000 sheets or more.

[0139]

[Table 2]

Example 19 <Preparation of direct-drawing lithographic printing plate precursor> The following composition was used together with glass beads in a paint shaker (Toyo Seiyaku Co., Ltd.).
After being dispersed at room temperature for 30 minutes, the glass beads were filtered to obtain a dispersion.

Cobalt oxide (average particle size; 1.7 μm) 45 g 10% by weight aqueous solution of gelatin 70 g Triethoxysilyl group-modified starch (PENON Amycol No. 3L, manufactured by Nitto Kagaku Co., Ltd.; modification amount=2 mol) %) 30 g Colloidal silica 20% by mass dispersion (Snowtec C) 25 g Tetraethoxysilane 30 g Fluorinated alkyl ester (FC-430, 3M) 0.2 g Curing agent CH ₂ =CHSO ₂ CH ₂ CONH(CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH=CH ₂ 0.5 g 1 N (mol/L) hydrochloric acid 2 g Water/ethanol (1/1) mass ratio mixed solvent 200 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 400 (sec/10 cc) and a contact angle with water of 0 degree.

<Preparation of Electrophotographic Photosensitive Member> 2 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 14.4 g of the following binder resin (P-1), and the following binder resin (P-2) 3 ．
A mixture of 6 g, 0.15 g of the following compound (A) and 80 g of cyclohexanone was put 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. Next, this dispersion was applied onto a degreased 0.2 mm-thick amylnium plate with a wire bar, dried by touch with a finger, and then heated in a circulating oven at 110° C. for 20 seconds. The film thickness of the obtained photosensitive layer was 8 μm.

[0144]

[Chemical 6]

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 by a color scanner in advance and color-separated. After the correction related to the color reproduction of the image was recorded, the beam spot diameter was measured with the light of 788 nm using the semiconductor laser drawing device as the exposure device based on the information stored in the hard disk in the system as the digital image data. The exposure was performed at a pitch of 10 μm and a scanning speed of 300 cm/sec as 15 μm (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, it is developed with a liquid developer having the following content, and then rinsed in a bath of Isopar G alone to remove stains on the non-image area. It was dried so that the remaining amount 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. ..

<Preparation of 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 weight of this crushed product and Isopar H4
A mass part was dispersed for 6 hours with a paint shaker to obtain a dispersion. This dispersion has a toner solid content of 1 g per liter.
Thus, a liquid developer was prepared by diluting with Isopar G, and at the same time containing 0.1 g of basic barium petrone as a charge control agent imparting a negative charge property per liter.

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

The image-forming lithographic printing plate precursor was heated at a temperature of 10
The toner image area was completely fixed by heating at 0° C. for 30 seconds. The drawn image of the obtained plate-making product was observed and evaluated 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, using the printing plate prepared as described above, Oliver 94 type (manufactured by Sakurai Manufacturing 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 matter was visually evaluated using a 20 times magnifier,
No background stains due to the adhesion of printing ink to the non-image area were observed, 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. Furthermore, 13,000 or more prints having the same print quality as the above were obtained.

Example 20 <Preparation of Water-Resistant Support> As a substrate, basis weight 100 g/m
^{In step 2} , polyethylene was laminated on both sides of a water resistant base paper having a thickness of 115 μm to prepare a WP paper having 15 μm on one side and 20 μm on the other side. Then, a coating for an under layer having the following composition is applied to the surface of the polyethylene laminate layer having a thickness of 15 μm using a wire bar, and a dry coating amount of 10 g/
After providing an under layer of m ² , the smoothness of the under layer is 1
Calendar processing was performed so that the time would be about 500 (seconds/10 cc).

<Under layer coating material> The following components were mixed and water was added so that the total solid content concentration was 25% to give an under layer coating material. -Carbon black (30% aqueous dispersion) 7.2 parts-Clay (50% aqueous dispersion) 52.8 parts-SBR latex (solid content 50%, Tg: 25°C) 36 parts-Melamine resin (solid content 80) %, Sumirez Resin SR-613) 4 parts

The specific electric resistance value of the obtained under layer is
It measured as follows. The under layer coating material is applied to a stainless steel plate that has been thoroughly degreased and washed, and the dry coating amount is 10 g.
/M ² of the coating film. 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 1×10 ⁸ Ωcm was obtained.

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

Manganese dioxide (average particle size: 0.3 μm) 80 g Trialkoxysilyl group-modified polyvinyl alcohol (R-2130, manufactured by Claret Co., Ltd.; modification amount=2.5 mol %) 10% by mass aqueous solution 270 g Clay 10 g Tetra Propoxysilane 40g Methyltrimethoxysilane 3g Alumina sol (Alumina sol 520, Nissan Chemical Industries, Ltd., average particle size: 20 nm) 10g Ethanol 110g 1N (mol/L) hydrochloric acid 5g Water 150g

This dispersion was coated on the above water-resistant support using a wire bar so that the coating amount of the dryer would be 6 g/m ^2, and dried in an oven at 100° C. for 20 minutes to obtain a lithographic plate. An original plate for printing was prepared. The surface of the obtained original plate had a Bekk smoothness of 120 (sec/10 cc) and a contact angle with water of 0 degree.

The above lithographic printing plate precursor was prepared by using AM-Straight.
Laser printer using dry toner commercially available as Imaging System (AMSIS 1200-J Pl
The plate was made through ateSetter-trade name-).

The copy image of the obtained plate-making product was visually evaluated with 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 toner transfer from a laser printer has no thin lines or fine characters, the solid part is uniform, no unevenness in toner transfer is observed, and the non-image part is also not present. However, the background fog caused by the toner scattering was also slight and it was good without any practical problems.

Next, after making the lithographic printing plate precursor by the same operation as described above, PS was used as fountain solution using a fully automatic printing machine (AM-2850, trade name of AM Co., Ltd.).
A solution obtained by diluting the plate treating agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water was placed in the dampening water pan.
Using black ink for offset printing, printing was performed by passing the plate through a printing machine. 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. In addition, 12,000 good prints were obtained.

Examples 21 to 25 In Example 1, instead of the trialkoxysilyl group-modified polyvinyl alcohol R-1130 and tetraethoxysilane in the coating liquid for the image receiving layer, the organic polymers and metal compounds shown in Table C below were used. A lithographic printing original plate was prepared in the same manner as in Example 1 except that the above was used.

[0160]

[Table 3]

The Bekk smoothness of the surface of each of the obtained original plates was in the range of 250 to 300 (sec/10 cc), and the contact angle of the surface with water was 0 degree. When a printing plate was prepared by making in the same manner as in Example 1, and printing was carried out, all of the obtained prints had a clear image quality with no stain in the non-image area, as in the printing plate of Example 1. The printing durability was as good as 13,000 sheets or more.

Example 26 A composition having the following content was dispersed in a paint shaker for 20 minutes to give a dispersion, which was dried on a support for ELP-2X so that the coating amount after drying was 6 g/m ^2. Was applied, dried by touch to the touch, and then heated at 100° C. for 30 minutes to prepare a lithographic printing original plate.

<Image Receiving Layer Composition> Zinc oxide (FINEX-50) 45 g Silica (Sylysia 310, manufactured by Fuji Silysia Chemical Ltd.; average particle size: 1.8 μm) 5 g Trialkoxysilyl group-modified dextrin (CRF-) M2, manufactured by Nippon Starch Chemical Co., Ltd.; modification amount=2 mol%) 30 g tetraethoxysilane 28 g benzyltrimethoxysilane 2 g 1 N (mol/L) hydrochloric acid 2 g water 300 g

Then, it was heated at 100° C. for 30 minutes to prepare a lithographic printing original plate. The Beck smoothness of the obtained image receiving layer was 250 (sec/10 cc), and the contact angle with water on the surface was 5 degrees or less.

Plate making was carried out using the same inkjet recording device and oil-based ink as in Example 1. The image quality of the obtained plate-making product was clear with no distortion or bleeding in a fine image such as fine lines and fine characters. Next, when printing was performed in the same manner as in Example 1, the obtained printed matter had a clear image quality with no stain in the non-image area, as in the case of the printed matter of Example 1.
The printing durability was as good as 14,000 sheets or more.

[0166]

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 Cu) and a bond-containing resin in which metal atoms are connected via an oxygen atom and a hydrogen bond with the resin. An image-receiving layer formed by forming a dispersion containing at least a binder resin containing a complex with an organic polymer containing a silyl functional group represented by the following general formula (I) A direct-drawing lithographic printing plate precursor characterized by having: General formula (I)-Si(R) _n (OX) _3-n [In formula (I), R represents a hydrogen atom or a C1-C12 hydrocarbon group. X represents an aliphatic group having 1 to 12 carbon atoms.
n represents 0, 1 or 2. ] 2. The resin containing a bond in which metal atoms are connected via an oxygen atom is a polymer obtained by hydrolytic polycondensation of at least one metal compound represented by the following general formula (II). The lithographic printing plate precursor for direct drawing according to claim 1. General formula (II) (R ⁰ ) _n M(Y) _zn [In the general formula (II), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group, Y represents a reactive group, and M is 3 ~ 6
Represents a valent metal, z represents the valence of the metal M, 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.