JP2000289361A - Direct lithographic printing original plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a direct lithographic printing original plate, with which a large number of sheets of printed matter having clear images having no omission, nor distortion or the like without scumming can be printed and which is especially suitable for an electrostatic discharging model ink jet type plate- making using an oily ink. SOLUTION: The printing plate has an image accepting layer at least including a binder resin having an average particle diameter of 0.01-5 μm and including a composite between a siloxane bond-including resin, which is formed by chaining at least one kind of particle selected from the group consisting of water-containing metal oxides made of metal atoms such as Mg, Al, Zn, Ge, Ti, Co, Zr, Sn, Fe, Cu, Ni, Pb, Pd, Cd, Mo, Cr, Ga, Mn, V, Ce or La with Si through an oxygen atom, and an organic polymer including a group, which forms a hydrogen bond with the siloxane bond-including resin, on a water resistant support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing original plate for direct drawing, and more particularly to a lithographic printing original plate for providing a lithographic printing plate capable of printing a large number of clear printed images without background contamination. .

[0002]

2. Description of the Related Art Lithographic printing plates currently used mainly in the field of light printing include (1) a water-resistant support,
(2) A direct-printing type master provided with a hydrophilic image-receiving layer, (2) a non-image area after directly making a plate on a water-resistant support provided with an image-receiving layer (lipophilic) containing zinc oxide Is subjected to a desensitizing treatment with a desensitizing solution to form a printing plate. (3) An electrophotographic light-sensitive material having a photoconductive layer containing photoconductive zinc oxide on a water-resistant support is used as an original plate. , The non-image part after image formation,
A printing plate is prepared by desensitizing with a desensitizing solution, and (4) a silver salt photographic 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 OA, in the printing field, various methods such as an electrophotographic printer, a thermal transfer printer, and an ink jet printer have been applied to the above-mentioned (1) original plate for direct drawing type lithographic printing. There is a demand for an offset lithographic printing method in which a printing plate is directly prepared without performing a specific process for making a printing plate (that is, image formation) and making a printing plate.

[0004] 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 via a back layer and an intermediate layer. Back layer or intermediate layer is PV
It is composed of a water-soluble resin such as A or 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.

[0005] Examples of 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 derivatives thereof, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, and vinyl acetate-crotonic acid. Water-soluble resins such as a polymer and a styrene-maleic acid copolymer combination are exemplified.

Glyoxal is used as a waterproofing agent,
Examples 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. 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 direct drawing type lithographic printing plate precursor, the binder has a functional group which generates a carboxyl group, a hydroxyl group, a thiol group, an amino group, a sulfo group or a phosphono group by decomposition. A resin which contains a functional group which is cured by heat / light and is crosslinked in advance (JP-A-1-226395, JP-A-1-269593,
JP-A-1-288488, and JP-A-1-266546, in which the above functional group-containing resin and a heat / photocurable resin are used in combination.
, JP-A-1-275191 and JP-A-1-309068), and the above-mentioned functional group-containing resin and a crosslinking agent are used in combination (Japanese Patent Application Laid-Open Nos. 1-267093, 1-271292 and 1-3).
09067), improvement of the hydrophilicity of the non-image area, improvement of the film strength of the image receiving layer, and improvement of the printing durability are being studied.

The image receiving layer contains resin particles having a fine particle diameter of 1 μm or less containing hydrophilic groups such as a carboxyl group, a sulfo group, and a phosphono group, together with an inorganic pigment and a binder (Japanese Patent Application Laid-open No. No. 4-201387, 4-2
No. 23196) or fine resin particles containing a functional group capable of generating a hydrophilic group as described above by decomposition (Japanese Patent Application Laid-Open Nos. 4-319492 and 4-353).
No. 495, No. 5-119545, No. 5-58071
To improve the hydrophilicity of the non-image area.

However, the conventional printing plate thus obtained increases the hydrophobicity by increasing the amount of a water-proofing agent or using a hydrophobic resin in order to improve the printing durability. In this case, the printing durability is improved, but the hydrophilicity is reduced to cause printing stains. On the other hand, if the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is reduced. In particular, in a use environment at a high temperature of 30 ° C. or more, the surface layer is dissolved in immersion water used for offset printing, and there are drawbacks such as a decrease in printing durability and generation of printing stains. Furthermore, in the case of a direct drawing type lithographic printing plate, an oil-based ink or the like is drawn on the image receiving layer as an image portion. If the adhesiveness between the receiving layer of the printing plate and the oil-based ink is not good, the non-image portion is used. However, even if the above-mentioned printing stains are not generated as described above, the problem that the oily ink in the image area is lost at the time of printing and the printing durability is reduced as a result is still sufficiently solved. Has not been reached.

On the other hand, a plate comprising a hydrophilic layer containing titanium oxide, polyvinyl alcohol and hydrolyzed tetramethoxysilane (or tetraalkoxysilane) as an image receiving layer (for example, JP-A-3-42679,
No. 0-268583). However, when actually making a plate and printing it as a printing plate, the printing durability of the image was insufficient.

[0011]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of the conventional direct drawing type lithographic printing plate precursor. SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent direct drawing type lithographic printing plate precursor that does not generate not only uniform background stains but also point-like background stains 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 capable of printing a large number of clear images without any background stains and without any missing or distorted images. .

[0012]

The above object is achieved by the following constitution. (1) On a water-resistant support, an average particle size of 0.01 to 5 μm
m, Mg, Al, Zn, Ge, Ti, Co, Zr, S
n, Fe, Cu, Ni, Pb, Pd, Cd, Mo, C
at least one particle selected from a hydrated metal oxide comprising a metal atom consisting of r, Ga, Mn, V, Ce, or La; a siloxane bond-containing resin in which Si is connected via an oxygen atom; A direct-printing lithographic printing plate precursor comprising an image receiving layer containing at least a binder resin comprising a complex of a bond-containing resin and an organic polymer having a group capable of forming a hydrogen bond.

(2) The resin according to (1), wherein the resin containing a siloxane bond in the image receiving layer is a polymer obtained by hydrolytic polycondensation of at least one silane compound represented by the following general formula (I). ) The direct-printing type lithographic printing plate described in (1).

Formula (I) (R ⁰ ) _n Si (Y) _4-n [In the formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. Y is a hydrogen atom, a halogen atom, -O
R ¹ , —OCOR ² or —N (R ³ ) (R ⁴ ) (R ¹ and R ² each represent a hydrocarbon group; R ³ and R ⁴ may be the same or different; Represents a hydrogen group). n represents 0, 1 or 2. However, the number of Si atoms is 3
Excludes cases where more than one hydrogen atom is bonded. ]

(3) The original plate for direct drawing type lithographic printing as described in (1) or (2) above, wherein the smoothness of the surface of the image receiving layer is 30 (sec / 10 cc) or more in Beck smoothness. .

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention provides a water-resistant support, which has an average particle diameter of 0.01 to 5 μm of a hydrated metal oxide comprising a specific metal atom.
Image receiving containing at least a binder resin containing at least a composite of a siloxane bond-containing resin in which Si is connected via an oxygen atom and an organic polymer containing a group having a hydrogen bonding property, together with the particles of This is a direct drawing type lithographic printing plate precursor provided with a layer.

The inorganic particles used in the image receiving layer of the present invention include:
Metal atoms are Mg, Al, Zn, Ge, Ti, Co, Z
r, Sn, Fe, Cu, Ni, Pb, Pd, Cd, M
It is a hydrated metal oxide selected from o, Cr, Ga, Mn, V, Ce and La. The hydrated metal oxide may be any hydrated oxide particle having no problem in stability and material safety, but is preferably a hydrated metal oxide selected from Ti, Mg, Al, Fe or Zn. The size of the particles is 0.01 to 5 μm in average particle size,
It is preferably from 0.02 to 3 μm, more preferably from 0.05 to 2 μm. Within this range, favorable smoothness of the surface of the image receiving layer and strength of the image portion after image formation are obtained, and adhesion of the printing ink to the non-image portion does not occur.

The hydrated metal oxide used in the image receiving layer of the present invention refers to the hydrated oxide of each of the above metal atoms, and is represented by M (O) (O
H) _n or a compound represented by M _x O _y · yH ₂ O (where M in the above general formula represents a metal atom, and n, x,
y and χ each represent an integer). Specifically, edited by The Chemical Society of Japan, “Experimental Chemistry Course 9, Synthesis and Purification of Inorganic Compounds”, published by Maruzen Co., Ltd. (1958), “Inorganic Compound and Complex Dictionary”
Published by Kodansha Co., Ltd. (1979), “Coloring Material Handbook” edited by The Coloring Material Association, 250 pages, published by Asakura Shoten (1989)
), "Paints and Pigments", written by Akira Misono, p. 184, published by Nikkan Kogyo Shimbun (1960).

The binder resin provided for the image receiving layer of the present invention includes a siloxane bond-containing resin in which Si is connected via an oxygen atom (hereinafter abbreviated as a siloxane polymer).
It is a resin comprising a complex of the siloxane bond-containing resin and an organic polymer having a group capable of forming a hydrogen bond. The “composite of a siloxane polymer and an organic polymer” is used to include a sol-like substance and a gel-like substance.

The siloxane polymer refers to a polymer mainly containing a bond composed of "oxygen atom-silicon atom-oxygen atom". Preferably, the polymer has a substituent in the main chain and / or a hydroxyl group at a terminal of the main chain. Further, it contains a hydrocarbon group as required. Thereby, according to the combination with the inorganic particles and the organic polymer used together,
The formation of a uniform film, the close contact of the image area, and the like can be adjusted.

The siloxane polymer of the present invention is preferably a polymer obtained by hydrolytic polycondensation of the silane compound represented by the above general formula (I). here,
Hydrolytic polycondensation is a reaction in which a hydrolyzable group repeatedly undergoes hydrolysis and condensation under acidic or basic conditions to polymerize, thereby generating a hydroxyl group. The above silane compounds can be used alone or in combination of two or more.

Next, the silane compound represented by formula (I) will be described in detail. R ⁰ in the general formula (I) is
Preferably, a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
A hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and the like; groups that can be substituted with these groups include a halogen atom (a chlorine atom, a fluorine atom, a bromine atom), a hydroxy group, a thiol group, and a carboxy group. Group, sulfo 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 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, -C OR 'group, -COR'
A group, -N (R ") (R") (R "represents the same content as a hydrogen atom or the aforementioned R 'and may be the same or different), a -NHCONHR' group, a -NHCOOR 'group,-
Si (R ′) ₃ group, —CONHR ″ group, —NHCOR ′ group, etc. These substituents may be substituted plurally in the alkyl group.

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

Alternatively, a condensed heterocyclic group containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom (for example, as a hetero ring, a pyran ring, a furan ring, a thiophene ring, a morpholine Ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc., and may contain a substituent. The same contents as the substituents in the alkyl group are mentioned, and plural substituents may be used).

Y is preferably a halogen atom (representing a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), --O
R ¹ , —OCOR ² or —N (R ³ ) (R ⁴ ).

In the —OR ¹ group, R ¹ has 1 to 10 carbon atoms.
Which may be substituted (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, propenyl, butenyl, heptenyl) Hexenyl, octenyl, decenyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-methoxyethyl, 2- (methoxyethyloxy) ethyl, 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, phenethyl, dimethoxybenzyl, methylbenzyl, bromobenzyl, etc.).

In the --OCOR ² group, R ² is an aliphatic group having the same contents as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (an aromatic group in the R ⁰ is And the same as those exemplified for the aryl group). −
In the N (R ³ ) (R ⁴ ) group, R ³ and R ⁴ may be the same or different from each other, and are each a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
0 optionally substituted aliphatic group (for example, the above-mentioned -OR
It represents an the like) the same contents as ¹ group R ¹ in. More preferably, the total number of carbon atoms of R ³ and R ⁴ is 16 or less.

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

Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-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-octadecyltri-t-butoxysilane, phenyltrichlor 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, vinyltri-t-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysila , Trifluoropropyl triethoxysilane, trifluoropropyl triisopropoxysilane, trifluoropropyl tri t- butoxysilane,

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

General formula (I) for use in the image receiving layer of the present invention
Together with the silane compound represented by Ti, Zn, Sn,
A metal compound that can be formed into a film by a sol-gel method, such as Zr or Al, can be used in combination. As the metal compound used,
For example, Ti (OR ⁵ ) ₄ (R ⁵ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc .; the same applies hereinafter), TiCl ₄ , Zn (OR ⁵ ) ₂ , Zn (CH ₃ CO ₃ )
CHCOCH ₃ ) ₂ , Sn (OR ⁵ ) ₄ , Sn (CH ₃ COC)
HCOCH ₃ ) ₄ , Sn (OCOR ⁵ ) ₄ , SnCl ₄ , Zr
(OR ⁵ ) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , Al
(OR ⁵ ) _{3 and the} like.

Next, the organic polymer used in the present invention will be described. The organic polymer used in the present invention,
It has a “group capable of forming a hydrogen bond with a siloxane bond-containing resin”. Such a group preferably includes at least one bond selected from an amide bond (including a carboxamide bond and a sulfonamide bond), a urethane bond and a ureido bond, and a hydroxyl group.

The organic polymer has, as a repeating unit component, at least one group capable of forming a hydrogen bond with the siloxane bond-containing resin (hereinafter, also simply referred to as a specific bonding group of the present invention) in the main chain of the polymer and / or And those contained in the side chain. Preferably, as a repeating unit ^{component, -N (R 11) CO -} , - N (R 11) SO 2 -, - N
Examples include a component in which at least one type of bond selected from HCONH- and -NHCOO- is present in the main chain and / or side chain of the polymer, and / or a component containing an -OH group. R ¹¹ in the amide bond represents a hydrogen atom or an organic residue, and examples of the organic residue include those having the same contents as the hydrocarbon group and the heterocyclic group in R ⁰ in Formula (I). .

The polymer main chain contains the specific bonding group of the present invention.
The polymer having -N (R ¹¹) CO-bond or
Is -N (R¹¹) SO_TwoAmide resin having a bond, -N
Ureido resin having HCON-bond, -NHCOO-
A urethane resin containing a bond is exemplified.

Examples of the diamines and dicarboxylic acids or disulfonic acids used in the production of the amide resin, the diisocyanates used for the ureide resin, and the diols used for the urethane resin include, for example, "Polymer Data Handbook-"Basics-"Chapter I (published by Baifukan) (1
986), Shinzo Yamashita, Tosuke Kaneko, "Crosslinking Agent Handbook", Taiseisha, 1981, and the like.

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

[0038]

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

In the polymer containing a repeating unit represented by the general formula (II), Z ¹ represents —CO—, and p represents 2
Is obtained by subjecting an optionally substituted oxazoline to ring-opening polymerization in the presence of a catalyst. Examples of the catalyst include sulfates and sulfonates such as dimethyl sulfate and alkyl p-toluenesulfonate; alkyl halides such as alkyl iodide (eg, methyl iodide); metal fluorides among Friedel-Crafts catalysts; Acids such as sulfuric acid, hydrogen iodide and p-toluenesulfonic acid, and oxazolinium salts which are salts of these acids with oxazoline can be used. This polymer may be a homopolymer or a copolymer. Further, a copolymer in which this polymer is grafted to another polymer may be used.

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

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

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

The polymer containing the 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 group. Things. Examples of such components include acrylamide, methacrylamide, crotonamide, vinylacetamide, and the following compounds. However, the present invention is not limited to these.

[0045]

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[0046]

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On the other hand, the hydroxyl group-containing organic polymer may be any of a natural water-soluble polymer, a semi-synthetic water-soluble polymer, and a synthetic polymer. Polymer Compound I ", published by Asakura Shoten (196
0), Business Development Center Publishing Division, “Water-Soluble Polymer / Water-Dispersible Resin Comprehensive Technical Documents”, Business Development Center Publishing Division (1981), Nagatomo Shinji, “Applications and Markets of New Water-Soluble Polymers” ( Published by CMC Corporation (1988), "Development of Functional Cellulose" Published by CMC Corporation (1985)
Year)).

For example, 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, acetate acetate). Cellulose ethers such as cellulose butyrate and cellulose acetate phthalate; methyl cellulose, ethyl cellulose, cyanoethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), starch, starch derivatives ( Oxidized starch, esterified starches; nitric acid, sulfuric acid, phosphoric acid, acetic acid, propion , Butyric acid, esterified products such as succinic acid, etherified starches; derivatives such as methylated, ethylated, cyanoethylated, hydroxyalkylated, carboxymethylated), alginic acid, pectin, carrageenan, tamarind gum, natural gums ( Gum arabic, guar gum, locust bean gum, gum tragacanth, 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 containing at least one hydroxyl group. Polymers or copolymers of acid esters or methacrylic esters (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.), N-substituted polymers or copolymers of acrylamide or methacrylamide (for example, monomethylol group, 2-hydroxyethyl group, 3-
Hydroxypropyl group, 1,1-bis (hydroxymethyl) ethyl group, 2,3,4,5,6-pentahydroxypentyl group, etc.). 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 weight average molecular weight of the organic polymer used in the image receiving layer of the present invention is preferably from 10 ³ to 10 ⁶ , more preferably from 5 × 10 ³ to 4 × 10 ⁵ .

In the composite of the siloxane polymer and the organic polymer of the present invention, the ratio of the siloxane polymer to the organic polymer can be selected in a wide range, but preferably, the polymerization ratio of siloxane polymer / organic polymer is from 10/90 to 9/9.
0/10, more preferably 20/80 to 80/20. Within this range, the strength of the film of the image receiving layer and the water resistance to fountain solution during printing will be good.

The binder resin containing the composite of the present invention is characterized in that the hydroxyl group present in the siloxane polymer, for example, the hydroxyl group of the siloxane polymer formed by hydrolytic polycondensation of the silane compound, and the “ The `` specific bonding group '' forms a uniform organic-inorganic hybrid by hydrogen bonding, becomes microscopically homogeneous without phase separation, and maintains the affinity between the siloxane polymer and the organic polymer used in the present invention. It is estimated that Further, when a hydrocarbon group is present in the siloxane polymer, it is presumed that the affinity with the organic polymer is further improved due to the hydrocarbon group. The composite of the present invention has excellent film-forming properties.

Such an organic / inorganic polymer composite resin is produced by hydrolytic polycondensation of the silane compound and mixing with the organic polymer, or hydrolyzing the silane compound in the presence of the organic polymer. It is easily produced by polycondensation.

Preferably, an organic / inorganic polymer composite can be obtained by hydrolytic polycondensation of the silane compound by a sol-gel method in the presence of an organic polymer. In the formed organic-inorganic polymer composite, the organic polymer is uniformly dispersed in a matrix of a gel (ie, a three-dimensional fine network structure of an inorganic metal oxide) formed by hydrolytic polycondensation of a silane compound.

The sol-gel method as a preferred method can be carried out using a conventionally known sol-gel method. Specifically, "Thin-film coating technology by sol-gel method" (Technical Information Association) (published) (1995), Saio Sakuhana "Science of sol-gel method" (Agne Shofusha) (published) (1988), Takashi Hirashima, "Technology for preparing functional thin films by the latest sol-gel method," General Technology Center (published) (19)
1992) according to a method described in detail in a written document.

The coating liquid for the image receiving layer is preferably an aqueous solvent, and furthermore, a water-soluble solvent is used in combination for uniform liquefaction by suppressing precipitation during preparation of the coating liquid. Examples of the water-soluble solvent include 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.) and ethers (tetrahydrofuran , Ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc.), ketones (acetone, methyl ethyl ketone, acetylacetone, etc.), esters (methyl acetate, ethylene glycol monomethyl monoacetate, etc.), amides (formamide, N-methylformamide, Pyrrolidone, N-methylpyrrolidone, etc.) It may be used in combination with the above.

Further, in order to promote the hydrolysis and polycondensation reaction of the silane compound represented by the general formula (I),
It is preferable to use an acidic catalyst or a basic catalyst together. As the catalyst, an acid or basic compound used 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, respectively) is used. The concentration at that time is not particularly limited, but when the concentration is high, the rate of hydrolysis and polycondensation tends to increase. However, when a highly concentrated basic catalyst is used, a precipitate may be formed in the sol solution. Therefore, the concentration of the basic catalyst is preferably 1 N (concentration conversion in an aqueous solution) or less.

The type of the acidic catalyst or the 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 such that the catalyst hardly remains in the crystal grains after sintering. Is good. Specifically, examples of the acidic catalyst include hydrogen halides 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 in which R of the structural formula RCOOH is substituted by another element or a substituent,
Examples of the basic catalyst such as sulfonic acid such as benzenesulfonic acid include ammoniacal base 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 components described above. As other components, inorganic pigment particles other than the specific hydrated metal oxide particles of the present invention may be contained. Examples include silica, alumina, kaolin, clay, titanium oxide, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate and the like. These other inorganic pigments are used in an amount not exceeding 40 parts by weight based on the hydrated metal oxide particles of the present invention. Preferably, it is within 20 parts by weight.

Pigment in image receiving layer (hydrous metal oxide particles of the present invention and other inorganic pigment particles optionally used)
The ratio of the binder resin is generally from 8 to 50 parts by weight, preferably from 10 to 30 parts by weight, based on 100 parts by weight of the pigment. In this range,
The effect of the present invention is effectively exhibited, the film strength during printing is maintained, and the high hydrophilicity of the non-image portion is maintained. Further, the image portion is sufficiently adhered to the image receiving layer, and sufficient printing durability can be obtained without causing image defects even when the number of printed sheets increases.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. Examples of the crosslinking agent include compounds that are usually used as a crosslinking agent. Specifically, Shinzo Yamashita and Tosuke Kaneko, “Crosslinking Agent Handbook” Taiseisha (1981), edited by The Society of Polymer Science, “Polymer Data Handbook, Basic Edition” Baifukan (198)
6 years) can be used.

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

The image-receiving layer of the present invention is formed by applying the above-mentioned coating solution on a water-resistant support by any of the conventionally known coating methods and drying. The thickness of the formed image receiving layer is preferably from 0.2 to 10 μm, more preferably from 0.5 to 8 μm. In 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 Beck smoothness. Further, when plate making is performed by an electrophotographic printer, the preferred range of the toner used is a dry toner or a liquid toner as follows.

In an electrophotographic printer using a dry toner, the surface of the image receiving layer of the original plate of the present invention has a thickness of 30 to 200.
(Second / 10 cc), more preferably 50 to 150
(Second / 10 cc). Within this range, in the process of transferring the toner image to the master and fixing it, the scattering toner is prevented from adhering to the non-image area (that is, background contamination), and the toner adhesion of the image area is uniform and sufficient, and the fine line The reproducibility of fine characters and the uniformity of solid image portions are improved.

On the other hand, in an electrophotographic printer using a liquid toner, the surface of the image receiving layer is preferably 30 (sec / 10 cc) or more, and the higher, the better, the better, 150 to 3000 (sec / 10 cc), more preferably 200 to 2500 (sec / cc). 10cc). In the case of an ink jet printer or a thermal transfer printer, the same range as in the case of the electrophotographic printer using the liquid toner is preferable. Within this range, a high-definition toner image portion such as a fine line, a thin character, or a halftone image is faithfully transferred and formed on the image receiving layer, and the surface of the image receiving layer and the toner image portion are sufficiently adhered to each other. Can be held.

Here, the Beck smoothness can be measured by a Beck smoothness tester. A test piece is placed on a highly smooth finished circular glass plate having a hole in the center at a constant pressure (1 kg / cm). ^It measures the time required for a fixed amount (10 cc) of air to pass between the glass surface and the test piece under reduced pressure.

More preferably, the shape of the surface of the image receiving layer of the present invention is set to a state in which irregularities are formed at high intervals.
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 surface roughness density is in the range of 50 μm or less. preferable. More preferably, SRa is 1.
35 to 2.5 μm, and Sλa is within a range of 45 μm or less. It is presumed that this suppresses the adhesion of the scattered toner to the non-image portion after the electrophotographic plate making and the fatness at the time of fixing the adhered toner.

Next, the water-resistant support provided 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, chromium-copper-aluminum plates, chromium-lead-iron plates, chromium-copper-stainless steel plates, and the thickness is 0.1 to 3 mm, particularly 0.1 to 1 mm. One. In addition, thickness 80μ
Paper, plastic film or metal film-laminated paper or plastic film which has been subjected to a water resistance treatment of m to 200 μm, and the like can be given.

The support provided in the present invention preferably has a highly smooth surface. That is, the smoothness of the surface on the side adjacent to the image receiving layer is 300 (sec / 10 c
c) or more, more preferably 900 to 3000 (sec / 10c
It is preferably prepared in c), more preferably from 1000 to 3000 (sec / 10 cc). By regulating the smoothness of the surface of the support on the side adjacent to the image receiving layer to a Beck smoothness of 300 (sec / 10 cc) or more, image reproducibility and printing durability can be further improved. Such an improvement effect can be obtained even if the smoothness of the image receiving layer surface is the same, and the adhesion between the image portion and the image receiving layer is improved by increasing the smoothness of the support surface. Conceivable.

The highly smooth surface of the water-resistant support thus regulated refers to the surface on which the image-receiving layer is directly applied. For example, a conductive layer, an underlayer, and an overlayer described below are formed on the support. When providing a coat layer, the conductive layer,
Refers to the surface of the underlayer or overcoat layer. As a result, the image receiving layer in which the surface shape is adjusted as described above is sufficiently retained without being affected by the unevenness of the surface of the support, and the image quality can be further improved.

As a method of setting the smoothness within the above range, various conventionally known methods can be used. Specifically, a method of adjusting the Beck smoothness of the surface of the support by a method such as a method of melting and bonding the substrate surface with a resin, a method of strengthening a calendar with a highly smooth heat roller, and the like can be used.

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

The image formation by the electrophotographic recording system is usually performed by an electrophotographic process, and the transfer of the toner image onto the material to be transferred is performed by electrostatic transfer. The water-resistant support as a printing original plate is preferably conductive, and particularly preferably has a volume resistivity of 10 ⁴ to 10 ¹³ Ω · cm, more preferably 10 ⁷ to 10 ¹² Ω · cm. As a result, bleeding / distortion of the transferred image, toner adhesion to the non-image portion, and the like are suppressed to such an extent that there is no practical problem, and a good image can be obtained.

Also in the image formation by the electrostatic discharge type ink jet recording method, it is preferable that the water-resistant support has conductivity, and at least a portion immediately below the image receiving layer is 10 ¹⁰ Ω · cm. It is preferable that the material has the following specific electric resistance value, and it is more preferable that the entire water-resistant support has a resistivity of 10 ¹⁰ Ω · cm or less. 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 droplet adheres to the image receiving layer, the charge of the ink droplet quickly disappears through the ground plane, so that a clear image without disturbance is formed. . The measurement of the specific electric resistance (also called the specific electric resistance of the volume or the specific electric resistance) is performed according to JIS.
The test was performed by a three-terminal method provided with a guard electrode based on K-6911.

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

On the other hand, examples of the substrate having conductivity as a whole include conductive paper impregnated with sodium chloride or the like, plastic films mixed with a conductive filler such as carbon black, and metal plates such as aluminum. No.

The water-resistant support having conductivity which can be preferably used in the present invention will be described in detail. A substrate having conductivity as a whole can be obtained, for example, by using a conductive base paper impregnated with sodium chloride or the like on a substrate and providing a water-resistant conductive layer on both surfaces thereof. As the base paper used as the base, for example, wood pulp paper, synthetic pulp paper, or a mixed paper of wood pulp paper and synthetic pulp paper can be used as it is. Further, the thickness of the base paper is preferably from 80 μm to 200 μm.

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 applied conductive layer is 5 μm to 2 μm.
0 μm is preferred. 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, flaked aluminum or nickel, fibrous carbon, etc. No.

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

Another method for forming the 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, an aluminum foil is used as a metal foil laminate, and a polyethylene resin mixed with carbon black is used as a laminate of a conductive plastic film. The aluminum foil may be either hard or soft and has a thickness of 5μ.
m to 20 μm are preferred.

Extrusion lamination is preferred for laminating polyethylene resin mixed with carbon black. Extrusion lamination method is to heat-melt polyolefin, turn it into a film, and immediately press-bond it to base paper.
This is a method of cooling and laminating, and various devices are known. The thickness of the laminate layer is 10 μm to 30 μm
Is preferred. As the whole support has conductivity,
When a conductive plastic film or metal plate is used as the substrate, it can be used as it is as long as it has sufficient water resistance.

As a plastic film having conductivity, for example, polypropylene or polyester film mixed with a conductive filler such as carbon fiber or carbon black can be used. As a 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, handling properties such as transportability in the drawing apparatus will be reduced.

Next, a structure in which a layer having conductivity is provided will be described. 80 μm to 20 μm thick as a water-resistant substrate
Paper, a plastic film or a paper laminated with a metal foil, a plastic film or the like which has been subjected to a water resistance treatment of 0 μm can be used. As a method for forming a conductive layer on a substrate, the method described above in the case where the entire 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 with a thickness of 5 μm or more.
Apply at 20 μm. Alternatively, it can be obtained by laminating a metal foil or a plastic film having conductivity.

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

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

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

An image is formed on the lithographic printing original plate of the present invention by a thermal transfer recording system, an electrophotographic recording system, an ink jet recording system or the like, and plate making is performed.

As the electrophotographic recording method, any of the conventionally known recording methods can be used. For example, Electrophotography Society of Japan, "Basics and Application of Electrophotography Technology" (Corona Co., Ltd., 1988), Kenichi Eda, Journal of Electrophotography Society 27 ,
113 (1988); Kawamoto Akio; 33 , 149 (19)
94), Akira Kawamoto, 32 , 196 (1993), or a commercially available PPC copying machine.
A combination of a scanning exposure method using a laser beam for exposing based on digital information and a developing method using a liquid developer is an effective process because a high-definition image can be formed. An example is shown below.

First, the photosensitive material is positioned on the flatbed by the register pin method, and then suction-fixed from the back surface by air suction and fixed. Next, the photosensitive material is charged by the charging device described in, for example, the above-mentioned “Basics and Application 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 conditions by applying feedback so that the surface potential always falls within a predetermined range based on the information from the charged potential detecting means of the photosensitive material. Thereafter, for example, scanning exposure using a laser light source is performed using the method described on page 254 and thereafter of the above-cited reference material.

Next, a toner image is formed using a liquid developer. The photosensitive material charged and exposed on the flatbed can be removed therefrom, and the wet developing method described on page 275 et seq. The exposure mode at this time is performed in correspondence with the toner image development mode. For example, in the case of reversal development, the negative image, that is, the same charge polarity as that when the photosensitive material is charged by irradiating the image portion with laser light and charging the photosensitive material Is applied, and a developing bias voltage is applied so that the toner is electrodeposited on the exposed portion. Details of the principle are described on page 157 et seq.

After development, in order to remove excess developer, squeeze such as rubber roller, gap roller, reverse roller, corona squeeze, air squeeze and the like are performed as shown on page 283 of the same document. It is also preferable to rinse only the carrier liquid of the developer before squeezing. Next, the toner image formed on the photoreceptor as described above is transferred and fixed on a lithographic printing original plate as a transfer material, or transferred and fixed on a lithographic printing original plate via an intermediate transfer member. Things.

The ink-jet recording method may be any of the conventionally known recording methods, and includes a method of drying an ink image.
An oil-based ink is preferable from the viewpoint of fixability, difficulty of clogging of the ink, and the like, and an electrostatic discharge type ink jet system which does not easily cause image bleeding is preferable. A solid jet system using hot melt ink is also preferably used.

For electrostatic discharge type ink jet recording, a recording apparatus described in International Patent Publication Nos. WO93 / 11866, 97/27058, and 97/27060 is used.
The oil-based ink used is preferably a non-aqueous solvent having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less, in which solid and hydrophobic resin particles are dispersed at least at room temperature (15 ° C. to 35 ° C.). It is a thing. By using such a dispersion medium, the electric resistance of the oil-based ink is properly controlled, and the ink is appropriately ejected by the electric field, thereby improving the image quality. Further, by using the resin particles as described above, the affinity with the image receiving layer is increased, and good image quality is obtained and printing durability is improved. Specifically, Japanese Patent Application 9-14
Nos. 8624, 9-154509, 9-35156
Nos. 3, 9-21011, 9-21017, 9
Oil-based inks described in US Pat.

Further, the solid jet method includes So
lid Inkjet Platemaker SJ02A (Hitachi Koki Co., Ltd.),
Commercially available printing systems 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 the drawings. The apparatus system shown in FIG. 1 has an ink jet recording apparatus 1 using oil-based ink.

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

FIGS. 2 and 3 show examples of the ink jet recording apparatus used in the apparatus shown in FIG. 2 and 3
In FIG. 1, members common to those in FIG. 1 are denoted 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.

As shown in FIG. 3, the head 10 provided in the ink jet recording apparatus includes the upper unit 1.
01 and a lower unit 102, the tip of which is a discharge slit 10a, a discharge electrode 10b is arranged in the slit, and the oil ink 11 is filled in the slit. Has become.

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

The width of the discharge electrode 10b is preferably as narrow as possible to form a high quality image. For example, the head 10 of FIG. 3 is filled with oil-based ink, and the ejection electrode 10 b having a tip of 20 μm width is used.
b and the counter electrode 10c are set to 1.5 mm, and a voltage of 3 KV is applied between the electrodes for 0.1 millisecond to obtain 40 μm.
An m dot print can be formed on the master 2.

FIGS. 4 and 5 show examples of the construction of another ink jet recording apparatus. FIG. 4 is a schematic diagram showing only a part of the head for explanation. As shown in FIG. 4, the ink jet recording head 13 includes a head body 14 made of an insulating material such as plastic, ceramic, and glass, and meniscus regulating plates 15 and 16. In the figure, 1
Reference numeral 7 denotes an ejection electrode for applying a voltage to form an electrostatic field in the ejection section.

Further, the head main body will be described in detail with reference to FIG. 5 in which the regulating plates 15 and 16 have been removed from the head. The head main body 14 is provided with a plurality of ink grooves 18 for circulating ink perpendicular to the edge of the head main body. The shape of the ink groove 18 may be set to a range in which capillary force acts so that a uniform ink flow can be formed, and particularly preferably, the width is 10 to 200 μm and the depth is 10 to 30 μm.
0 μm. An ejection electrode 17 is provided inside the ink groove 18. The ejection electrode 17 is formed on the head body 14 made of an insulating material by a known method using a conductive material such as aluminum, nickel, chromium, gold, and platinum. Alternatively, it may be formed only on a part. The discharge electrodes are electrically independent.

The two adjacent ink grooves form one cell, and the leading end of the partition wall 19 at the center of the cell forms the ejection portion 2.
0 and 20 'are provided. In the discharge portions 20 and 20 ′, the partition walls are thinner than the other partition portions 19 and are sharpened. The tip of the discharge section may be slightly chamfered as in 20 '. Such a head body is manufactured by a known method such as machining, etching, or molding of an insulating material block. The thickness of the partition wall at the discharge portion is preferably 5 to 100 μm, and the radius of curvature of the sharpened tip is preferably 5 to 50 μm. Although only two cells are shown in the figure, the cells are separated by a partition 21 and the tip 22 thereof is connected to the discharge unit 2.
It is chamfered so as to be retracted from 0, 20 '.

The ink is supplied to the head from the direction I by ink supply means (not shown) through the ink groove, and the ink is supplied to the discharge section. Excess ink is collected in the O direction by an ink collecting means (not shown).
As a result, fresh ink is always supplied to the ejection unit. In a state in which the ink near the ejection unit is irradiated with light as shown in L, the ink is provided on the ejection electrode with respect to a counter electrode (not shown) which is provided so as to face the ejection unit and holds a lithographic printing original plate on its surface. By applying a signal voltage corresponding to the data, the ink is ejected from the ejection unit and an image is formed on the lithographic printing original plate.

As described above, on the lithographic printing original plate,
An image is formed by an ink-jet method using an oil-based ink to obtain a plate-making master.

[0107]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1a Hydrous titanium oxide (PC-101, manufactured by Titanium Industry Co., Ltd.)
100 g, 113 g of a 10 wt% aqueous solution of polyvinyl alcohol (PVA203, manufactured by Kuraray Co., Ltd.) and 240 g of water
And mix with a paint shaker (Toyo Seiki Co., Ltd.)
20 wt% hydrolyzed in advance in the liquid dispersed for 0 minutes
Tetramethoxysilane water / ethanol (1: 1) solution 1
07g and 20% aqueous colloidal silica Snowtec C
(Nissan Chemical Industry Co., Ltd.) 182 g to obtain an image receiving layer composition. ELP-1X type master used as electrophotographic lithographic printing original plate for light printing (trade name,
The above image-receiving layer composition was applied to a support (underside Beck smoothness: 1000 (second / 10 cc)) of a Fuji Photo Film Co., Ltd. using a wire bar, and the mixture was heated in an oven.
After drying at 00 ° C for 10 minutes, the coating amount after drying is 5 g / m
An image receiving layer of No. ² was prepared and used as a lithographic printing original plate.

The surface smoothness (sec / 10 cc) of this lithographic printing original plate was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air capacity of 10 cc.
5 (sec / 10 cc). In addition, 2 μl of distilled water was placed on the surface of the lithographic printing plate precursor, and the surface contact angle (degree) after 30 seconds.
Was measured using a surface contact angle meter (trade name CA-D, manufactured by Kyowa Interface Science Co., Ltd.) and found to be 5 degrees or less.

The lithographic printing original plate described above is referred to as “AM-Straig
ht Imaging System ”, a laser printer using dry toner AMSIS 1200-
Plates were made through J Plate Setter (trade name).

When the copied image of the plate-making product obtained was visually evaluated using a 20-power loupe, the plate-making quality was good.
In other words, the plate-making product of the present invention obtained by dry toner transfer from a laser printer has no thin lines and no missing fine characters, the solid portion is uniform, no unevenness in toner transfer is observed at all, and the non-image portion In addition, the ground fogging due to toner scattering was fine and good without practical problems.

Next, after making a lithographic printing original plate by the same operation as described above, a fully automatic printing machine AM-2850 (trade name,
Using a solution prepared by diluting a PS plate treating agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water as a dampening solution using a dampening solution receiving portion using a dampening solution. And printing was performed through a plate-making product on a printing machine using black ink for offset printing. The printed image (ground fog, solid uniformity of the image area) of the tenth print was visually evaluated using a 20-fold loupe, and was found to be extremely good. Further, 3,000 or more good printed materials having an image free of fine lines, missing fine characters and uneven solid portions and having no practical problem with ink stains in non-image portions were obtained. The original plate of the present invention can obtain many good printed materials.

Comparative Example 1 A lithographic printing plate precursor was prepared in the same manner as in Example 1a, except that the hydrated titanium oxide in the image receiving layer composition was changed to titanium oxide (manufactured by Ishihara Sangyo Co., Ltd.). The surface of the obtained plate had a Beck smoothness of 160 (sec / 10 cc) and a contact angle with water of 5
Degrees.

The above plate was made in the same manner as in Example 1a. The image quality of the plate thus produced was almost the same as that of Example 1a, the amount of scattered toner in the non-image area was small, and the image was good. However, when printing was performed in the same manner as in Example 1a, the printed matter was found to have dust-like stains in which the printing ink slightly adhered to the non-image area from the start of printing. Further, printing was performed as it was, and a missing image portion occurred at a place where about 1,000 sheets were printed.

Example 1b The hydrous titanium oxide of the image receiving layer composition was replaced with hydrous magnesium hydroxide (Starbrand 200, Kamijima Chemical Co., Ltd.)
Lithographic printing plate precursor was prepared in the same manner as in Example 1a, except that the lithographic printing plate precursor was changed to Example 1a. The surface of the obtained lithographic printing plate precursor had a Beck smoothness of 130 (sec / 10 cc) and a contact angle with water of 5 ° or less.

The lithographic printing plate precursor was made in the same manner as in Example 1a. The plate-making product obtained was free of fine lines and fine characters, the solid portion was uniform, no unevenness in toner transfer was observed, the non-image portion, and the background fogging due to toner scattering were slight and practically problematic. There was no good thing.

Next, printing was performed in the same manner as in Example 1a. The printed image (ground fog, solid uniformity of the image area) of the tenth print was visually evaluated using a 20-fold loupe, and was found to be extremely good. Furthermore, a good printed material having an image free from thin lines, missing fine characters and uneven solid portions, and having no practical problem with ink stains on non-image portions is 3,000.
More than one sheet was obtained. The original plate of the present invention can obtain many good printed materials.

Example 2a <Preparation of Direct-Drawing Lithographic Printing Plate> The following composition was used together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.)
) For 20 minutes at room temperature, and then the glass beads were separated by filtration to obtain a dispersion.

Hydrous titanium oxide (PC-101A, Titanium Industry Co., Ltd.) 100 g Gelatin (Wako Pure Chemical Industries, Ltd.) 10 wt% aqueous solution 300 g Tetraethoxysilane 4.2 g Ethanol 8.6 g Colloidal silica 20% aqueous solution ( Snowtech C, Nissan Chemical Industries, Ltd.) 182 g Fluoroalkyl ester (FC-430, manufactured by 3M) 0.25 g Hardener CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂ 1.0g 1N hydrochloric acid 4g Water 150g

A support of ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing plate for light printing (under one side Beck smoothness:
2000 (sec / 10 cc) or more), and the above composition was applied thereon by using a wire bar so as to have a coating weight of 6 g / m ² after drying, and then dried by touch, and then further dried at 110 ° C. and 30 ° C.
After heating for 1 minute, an image receiving layer was formed to obtain a lithographic printing original plate. The Beck smoothness of the surface of the obtained plate was 800 (sec / 10
cc), the contact angle with water was 5 degrees or less.

<Preparation of Electrophotographic Photoreceptor> 2 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink Co., Ltd.), 14.4 g of the following binder resin (P-1), and the following binder resin (P-2) 3 .
6 g, a mixture of 0.15 g of the following compound (A) and 80 g of cyclohexanone were put together with glass beads in a 500 ml glass container, and the mixture was placed on a paint shaker (Toyo Seiki Co., Ltd.)
), And the glass beads were filtered off to obtain a photosensitive layer dispersion.

[0122]

Embedded image

Next, this dispersion was subjected to a degreasing treatment.
Apply on a 2mm thick aluminum plate with a wire bar,
After drying to the touch, it was heated in a circulation oven at 110 ° C. for 20 seconds. The thickness of the obtained photosensitive layer was 8 μm.

The electrophotographic photoreceptor prepared as described above is corona-charged in a dark place to charge the surface potential to +450 V, then read in advance from a document by a color scanner, color-separated, and subjected to some system-specific. After the correction relating to the color reproduction of the image was made, based on the information stored in the hard disk in the system as digital image data, the beam spot was irradiated with 788 nm light using a semiconductor laser drawing apparatus as an exposure apparatus. Exposure was performed at a diameter of 15 μm, a pitch of 10 μm, and a scan speed of 300 cm / sec (that is, 2500 dpi). Exposure was performed so that the exposure amount on the photoconductor at this time was 25 erg / cm ² .

Subsequently, development was carried out using a liquid developer having the following contents, followed by rinsing in a single bath of Isopar G to remove stains on the non-image area, and then using hot air having a photoconductor surface temperature of 50 ° C. It was dried so that the remaining amount of Isopar G was (10 mg / g of toner weight). Subsequently, the photosensitive member was precharged at −6 KV with a corona charger, the image surface of the photosensitive member was overlapped with the lithographic printing plate precursor, and transferred by applying a negative corona discharge from the electrophotographic photosensitive member side. .

<Liquid developer> The following components 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. One part by weight of the ground product and 4 parts by weight of Isopar H were dispersed with a paint shaker for 6 hours to obtain a dispersion. This dispersion is diluted with Isopar G so that the toner solid content is 1 g per liter, and at the same time, basic barium petrone is used as a charge control agent for imparting negative charge.
A liquid developer was prepared so as to contain 0.1 g per liter.

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

The lithographic printing original plate on which the image was formed was placed at a temperature of 10
By heating at 0 ° C. for 30 seconds, the toner image area was completely fixed. The obtained image of the plate was observed and evaluated at a magnification of 200 times with an optical microscope. The image was clear with no bleeding or missing of fine lines and characters.

Next, the printing plate prepared as described above was used as a printing machine with an Oliver 94 type (manufactured by Sakurai Seisakusho Co., Ltd.), and as a dampening solution, SLM-OD (Mitsubishi Paper Mills, Ltd.).
Was diluted 100 times with distilled water, placed in a fountain solution tray, and printed using a black ink for offset printing on a printing paper through a plate. When the printed image of the tenth printed material was visually evaluated using a 20-fold magnification, no background stain due to the adhesion of the printing ink to the non-image portion was observed, and the uniformity of the solid image portion was good. Further, when observed with an optical microscope at a magnification of 200 times, no fine lines or fine characters were found to be thin or missing. More than 10,000 prints of the same print quality were obtained.

Example 2b Hydrous titanium oxide of the image receiving layer composition was replaced with hydrous aluminum hydroxide (Alumina White A, manufactured by Daimei Chemical Co., Ltd.).
A lithographic printing original plate was prepared in the same manner as in Example 2a, except that this was changed to. The surface of the obtained master had a Beck smoothness of 1050 (sec / 10 cc) and a contact angle with water of 5 ° or less.

The lithographic printing plate precursor was made in the same manner as in Example 2a. The obtained image of the plate was observed and evaluated at a magnification of 200 times with an optical microscope. The image was clear with no bleeding or missing of fine lines and characters.

Next, printing was performed in the same manner as in Example 2a. When the printed image of the tenth printed material was visually evaluated using a 20-fold magnification, no background stain due to the adhesion of the printing ink to the non-image portion was observed, and the uniformity of the solid image portion was good. Further, when observed with an optical microscope at a magnification of 200 times, no fine lines or fine characters were found to be thin or missing. More than 10,000 prints of the same print quality were obtained.

Example 3b <Preparation of Water-Resistant Support> A high-grade paper weighing 100 g / m ² was used as a substrate, and a coating for a back layer having the following composition was applied to one surface of the substrate using a wire bar. Dry application amount 12g /
After the m ² back layer is provided, the smoothness of the back layer is 100
(Second / 10 cc) Calendar processing was performed.

(Coating for Back Layer) ・ Kaolin (50% aqueous dispersion) 200 parts ・ Polyvinyl alcohol aqueous solution (10%) 60 parts ・ SBR latex (solid content 50%, Tg 0 ° C.) 100 parts ・ Melamine resin (solid content) 80%, Sumiretz Resin SR-613) 5 parts

Next, a coating for an under layer having the following composition was applied to the other surface of the substrate by using a wire bar, and an under layer having a dry coating amount of 10 g / m ² was provided. (Second / 10 cc) Calendar processing was performed.

(Coating for under layer)-Carbon black (30% aqueous dispersion) 5.4 parts-Clay (50% aqueous dispersion) 54.6 parts-SBR latex (solid content 50%, Tg 25 ° C) 36 parts・ 4 parts of melamine resin (solid content 80%, Sumiretz Resin SR-613)

The above components were mixed, and the total solid content was 2
Water was added so as to be 5% to obtain a paint for the under layer.
The specific electric resistance of the obtained under layer was measured as follows. The under layer coating was applied on a sufficiently degreased and washed stainless steel plate to form a coating having a dry coating amount of 10 g / m ² . The specific electrical resistance of the obtained sample was measured by a three-terminal method provided with a guard electrode based on JIS K-6911, and a value of 4 × 10 ⁹ Ω · cm was obtained.

<Preparation of a master plate for direct drawing type lithographic printing> The following composition was dispersed together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) at room temperature for 20 minutes, and the glass beads were separated by filtration. I got

Hydrous titanium oxide (made by Ishihara Sangyo) 100 g Starch (PENON ZP-2, manufactured by Nisseki Chemical Co., Ltd.) 10% aqueous solution 300 g tetraethoxysilane 30 g methyltrimethoxysilane 3 g Snowtec C 20% aqueous solution 91 g ethanol 10 g 1N hydrochloric acid 5g 150g water

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

<Preparation of Oil-Based Ink (IK-1)> (Production Example of Resin Particles) Poly (dodecyl methacrylate)
A mixed solution of 14 g, 100 g of vinyl acetate, 4.0 g of octadecyl methacrylate and 286 g of Isopar H was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isovaleronitrile) (abbreviated as AIVN) was added as a polymerization initiator and reacted for 4 hours. Further, after adding 0.8 g of 2,2'-azobis (isobutyronitrile) (abbreviated as AIBN), the mixture was heated to a temperature of 80 ° C and reacted for 2 hours. .
I. B. N. Was added and reacted for 2 hours. Thereafter, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour to remove unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 93% and an average particle size of 0.35 μm. Particle size is CAP
A-500 (manufactured by Horiba, Ltd.) was used.

(Preparation of Ink) Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 weight ratio) 1
0 g, alkali blue 10 g and Shellsol 71,
30 g together with glass beads was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine alkali blue dispersion. 50 g of the above resin particles
By diluting 5 g (solid content) of the above blue dispersion and 0.08 g of octadecene-half-maleic acid octadecylamide copolymer into 1 liter of Isopar G (as solid content), a blue oil-based ink (IK-1) was obtained. Created.

Using the master obtained as described above, a servo plotter DA manufactured by Graphtec Co., Ltd. capable of drawing a personal computer output.
8400 was modified and the ink ejection head shown in FIG. 2 was attached to the pen / plotter part, and the oil-based ink (IK-1) was applied to the lithographic printing plate precursor placed on the counter electrode spaced 1.5 mm apart. ) And printing was performed. At the time of plate making, the under layer provided immediately below the image receiving layer of the printing original plate and the counter electrode were electrically connected using a silver paste. The plate thus prepared was adjusted to a plate surface temperature of 70 ° C., and an ink image was fixed with a Ricoh fuser (manufactured by Ricoh Co., Ltd.) for 10 seconds. The drawing image of the obtained plate-making product was observed and evaluated with an optical microscope at a magnification of 200 times. The image was clear with no bleeding or missing of fine lines and characters.

Next, the printing plate created as described above is
As a printing machine, Oliver 94 (manufactured by Sakurai Seisakusho)
A solution obtained by diluting EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 100 times with distilled water as a dampening solution is placed in a dampening solution tray, and black ink for offset printing is used.
Printing was performed through a plate-making product on printing paper. When the printed image of the tenth printed material was visually evaluated using a 20-fold magnification, no background stain due to the adhesion of the printing ink to the non-image portion was observed, and the uniformity of the solid image portion was good. . 20 more
Observation with an optical microscope of 0 times showed that fine lines and fine characters were not thinned or missing and the image quality was good. 4000 prints of the same print quality were obtained.

Example 3b Example 3 was repeated except that the hydrous titanium oxide in the image receiving layer composition was changed to hydrous magnesium hydroxide (manufactured by Kyowa Chemical Co., Ltd.).
A lithographic printing original plate was prepared in the same manner as in a.

Using this master, a Servo Proter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing output from a personal computer, was modified. The ink ejection head shown in FIG. 4 was mounted on the pen / plotter part, and the counter electrodes spaced 500 μm apart. Printing was performed on the lithographic printing plate precursor placed above using the oil-based ink (IK-1) shown in Example 3a. Subsequently, the surface temperature of the ink image surface was set to 8 using RICOH FUSER model 592 (manufactured by Ricoh Co., Ltd.).
The temperature was adjusted to 0 ° C. and heated for 1 minute to sufficiently fix the image area.

Next, printing was performed in the same manner as in Example 3a. When the printed image of the tenth printed material was visually evaluated using a 20-fold magnification, no background stain due to the adhesion of the printing ink to the non-image portion was observed, and the uniformity of the solid image portion was good. . Further, when observed with an optical microscope at a magnification of 200 times, fine lines and fine characters were not thinned or missing, and good image quality was obtained. As a result, 3,500 prints having the same print quality were obtained.

Examples 4 to 20 Each lithographic printing plate precursor was prepared in the same manner as in Example 3b except that the compounds shown in Table 1 below were used in place of hydrous magnesium hydroxide. The Beck smoothness of the surface of each of the obtained masters is 200 to 350 (sec / 10 c
In c), the contact angles with water were all 5 degrees or less. Using each of the obtained masters, plate making was performed in the same manner as in Example 3a.
Printed. The obtained printed matter has no background stain on the non-image area,
It had a clear image with no bleeding or distortion in fine lines and characters. As shown in Table 1, each printing plate showed good printing durability of 3,000 sheets or more.

[0149]

[Table 1]

Examples 21a to 27a In Example 1a, 24 g of an organic polymer and 24 g of a silane compound shown in Table 2 below were used in place of polyvinyl alcohol PVA203 and tetramethoxysilane of the coating solution for the image receiving layer, respectively. A lithographic printing plate precursor was prepared in the same manner as in Example 1a.

[0151]

[Table 2]

The Beck smoothness of the surface of each of the obtained masters was in the range of 120 to 150 (sec / 10 cc), and the contact angle of the surface with water was 5 degrees or less. When a plate and a printing plate were prepared and printed in the same manner as in Example 1a, the resulting printed matter was of a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 1a. The printing durability was as good as 3,000 or more.

Examples 21b to 27b In Examples 21a to 27a, except that the hydrous titanium oxide in the image receiving layer composition was changed to hydrous magnesium hydroxide (Starbrand 200, manufactured by Kamishima Chemical Industry Co., Ltd.),
Each planographic printing original plate was prepared in the same manner as in Examples 21a to 27a.

The Beck smoothness of the surface of each of the obtained masters was in the range of 120 to 150 (sec / 10 cc), and the contact angle of the surface with water was 5 degrees or less. When a plate was made and a printing plate in the same manner as in Example 1b, and printing was performed, the obtained printed matter had clear image quality with no stain on the non-image area, similarly to the printing plate in Example 1b. The printing durability was as good as 3,000 or more.

Example 28a The following composition was dispersed with a paint shaker for 20 minutes to give a dispersion, and a wire bar was applied on a support for ELP-2X so that the coating amount after drying was 6 g / m ^2. Apply using
Dry to the touch. Subsequently, it was heated at 150 ° C. for 30 minutes to prepare a lithographic printing original plate.

<Image Receiving Layer Composition> 45 g of Hydrous Titanium Hydroxide PC-101 Silica: Sylysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 5 g Succinic acid-modified starch PEONN-F3 (manufactured by Nisseki Chemical Co., Ltd.) 30 g tetraethoxy Silane 28 g Benzyltrimethoxysilane 2 g 1 N hydrochloric acid 2 g Water 300 g

The Beck smoothness of the surface of the obtained image receiving layer was 300 (sec / 10 cc), and the contact angle with water on the surface was 5 degrees or less.

[0158] Plate making was performed using an electrostatic discharge type ink jet recording apparatus described in International Patent Publication No. WO93 / 11866, and using the oil ink (IK-1) described in Example 3a as the oil ink. The image quality of the obtained plate-making product was clear without distortion and blurring in fine images such as fine lines and fine characters.

Next, when printing was performed in the same manner as in Example 3a,
The obtained printed matter had a clear image quality with no stain on the non-image area, similarly to the printing plate of Example 3a. The printing durability was as good as 10,000 sheets or more.

Example 28b A lithographic printing plate precursor was prepared in the same manner as in Example 28a, except that the hydrous titanium oxide in the image receiving layer composition was changed to hydrous iron oxide. The surface of the obtained image receiving layer had a Beck smoothness of 350 (sec / 10 cc) and a contact angle with water of 5 ° or less.

Using this original plate, plate making was performed in the same manner as in Example 28a. The image quality of the obtained plate-making product was clear without distortion and blurring in fine images such as fine lines and fine characters. Next, when printing was performed in the same manner as in Example 3b, the obtained printed matter had clear image quality with no stain on the non-image portion, similarly to the printing plate of Example 3b. 1 printing durability
It was good with more than 10,000 sheets.

[0162]

By using the original plate for direct drawing type lithographic printing of the present invention, it is possible to obtain an excellent image in which not only a uniform background stain but also a dot-like background stain is not generated. Further, it is possible to print a large number of prints of a clear image without any loss or distortion of the image.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system that can be used for image formation of a printing original plate of the present invention.

FIG. 2 is a schematic configuration diagram showing a main part of an ink jet recording apparatus that can be used for forming an image on a printing original plate of the present invention.

FIG. 3 is a partial cross-sectional view of a head of an ink jet recording apparatus that can be used for forming an image on a printing original plate of the present invention.

FIG. 4 is a schematic diagram of a main part of a head of another ink jet recording apparatus that can be used for image formation of a printing original plate of the present invention.

FIG. 5 is a schematic diagram for explaining a head of the embodiment of the ink jet recording apparatus shown in FIG. 4;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ink jet recording apparatus 2 Master 3 Computer 4 Bus 10 Head 10a Discharge slit 10b Discharge electrode 10c Counter electrode 11 Oil-based ink 101 Upper unit 102 Lower unit 13 Ink jet recording head 14 Head body 15, 16 Meniscus regulating plate 17 Discharge electrode 18 Ink groove 19 Partition wall 20, 20 'Discharge unit 21 Partition wall 22 Tip

Claims (3)

[Claims] An average particle size of 0.01 on a water-resistant support.
~ 5 μm, Mg, Al, Zn, Ge, Ti, Co, Z
r, Sn, Fe, Cu, Ni, Pb, Pd, Cd, M
o, Cr, Ga, Mn, V, Ce or La at least one kind of particles selected from hydrated metal oxides consisting of metal atoms consisting of metal atoms, and a resin containing a siloxane bond Si is connected via an oxygen atom, Direct drawing lithographic printing, characterized by having an image receiving layer containing at least a binder resin comprising a complex of the siloxane bond-containing resin and an organic polymer containing a group capable of forming a hydrogen bond. Original version. 2. The image receiving layer according to claim 1, wherein the resin containing a siloxane bond is a polymer obtained by hydrolytic polycondensation of at least one silane compound represented by the following general formula (I). A lithographic printing plate for direct drawing. General formula (I) (R ⁰ ) _n Si (Y) _4-n [In general formula (I), R ⁰ represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. Y is a hydrogen atom, a halogen atom, -O
R ¹ , —OCOR ² or —N (R ³ ) (R ⁴ ) (R ¹ and R ² each represent a hydrocarbon group; R ³ and R ⁴ may be the same or different; Represents a hydrogen group). n represents 0, 1 or 2. However, the number of Si atoms is 3
Excludes cases where more than one hydrogen atom is bonded. ] 3. The direct drawing type lithographic printing plate precursor according to claim 1, wherein the smoothness of the surface of the image receiving layer is 30 (sec / 10 cc) or more in Beck smoothness.