JP2001054984A - Original plate for direct depicting lithographic printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To avoid scumming as an offset original plate and to print numbers of sheets of printed matter of clear image quality without image missing and image distortion. SOLUTION: An image receiving layer containing a composite of a resin containing metal sulfide particles 0.01-5 μm in average particle size (metal: An, Ag, Se, Fe, Pb, Sb, Cd, Cr, Co, Zr, Sn, Ti, Ni, Mg, Mo, La, Pd, Y, In, or Ir) and hydrous metal oxide particles 0.01-5 μm in average particle size (metal: Al, Zn, Ge, Co, Zr, Sn, Fe, Cu, Ni, Pb, Ti, Pd, Cd, Cr, Ga, Mn, V, Mo, Ce, or La) in a mass ratio of 5:95 to 50:50, a resin containing siloxane linkages, and an organic polymer containing groups capable of forming hydrogen bonds with the resin is provided 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, cellulose derivatives such as carboxymethyl cellulose and 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 composed of a hydrophilic layer containing titanium oxide, polyvinyl alcohol and hydrolyzed tetramethoxysilane or tetraethoxysilane as an image receiving layer (for example, JP-A-3-42679, 10-268)
No. 583). 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
(Where the metal atoms constituting the metal sulfide are Zn, Ag, Se, Fe, P
b, Sb, Cd, Cr, Co, Zr, Sn, Ti, N
i, Mg, Mo, La, Pd, Y, In and Ir) and an average particle diameter of 0.01 to 5 μm
(Where the metal atoms constituting the hydrated metal oxide are Mg, Al, Zn, G
e, Co, Zr, Sn, Fe, Cu, Ni, Pb, T
i, Pd, Cd, Cr, Ga, Mn, V, Mo, Ce and La) at least 5 to 95
Composite of a siloxane bond-containing resin containing 50:50 (mass ratio) and further having Si linked via an oxygen atom, and an organic polymer containing a group capable of forming a hydrogen bond with the siloxane bond-containing resin A direct-drawing lithographic printing plate precursor comprising an image receiving layer containing at least a binder resin composed of a body.

(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. According to the present invention, the water-resistant support has an average particle size of 0.1.
Specific metal sulfide particles having an average particle diameter of 0.0 to 5 μm;
With specific hydrous metal oxide particles of 1 to 5 μm, Si
Is provided with an image-receiving layer on a hydrophilic surface containing a binder resin containing a complex of a siloxane bond-containing resin linked via an oxygen atom and an organic polymer containing a specific polar group having hydrogen bonding property This is a direct drawing type lithographic printing original plate.

One of the inorganic particles used in the image receiving layer of the present invention has an average particle size of 0.01 to 5 μm, preferably 0.0 to 5 μm.
Metal atoms of 2-3 μm are Zn, Ag, Se, Fe, P
b, Sb, Cd, Cr, Co, Zr, Sn, Ti, N
i, Mg, Mo, La, Pd, Y, In and Ir. The metal sulfide may be any sulfide particle having no problem in stability and material safety, but is preferably Zn, Se, Fe, Zr, Ti,
It is a sulfide of Ni, Mg or Pb.

The metal sulfide is produced by a conventionally known method,
For example, edited by The Chemical Society of Japan, “Experimental Chemistry Course 9, Synthesis and Purification of Inorganic Compounds”, published by Maruzen Co., Ltd. (1958), edited by the Chemical Dictionary Editor's Committee, “Chemical Dictionary 9”, pages 645-683, Kyoritsu Shuppan ( This is specifically described in, for example, K.K. (1963). These compounds are also marketed as commercial products (for example, Kanto Chemical Co., Ltd., Wako Pure Chemical Industries, Ltd.)
), And also by the Color Materials Association, “Color Material Handbook” 25
0, Asakura Shoten (1989), "Paints and Pigments" by Akira Misono, etc., page 184, published by Nikkan Kogyo Shimbun (1960).

Another inorganic particle used in the image receiving layer of the present invention has an average particle diameter of 0.01 to 5 μm, preferably 0.02 to 3 μm, and contains metal atoms of Mg, Al, Zn, G
e, Co, Zr, Sn, Fe, Cu, Ni, Pb, P
d is a hydrated metal oxide selected from Ti, Cd, Cr, Ga, Mn, V, Mo, Ce and La. The hydrated metal oxide may be any hydrated oxide particle having no problem in stability and material safety, but is preferably Mg,
It is a hydrated oxide of Al, Fe, Ti or Zn.

The hydrated metal oxide refers to a hydrated oxide of each of the above metals, and includes those represented by M (O) (OH) _n or M _x O _y · χH ₂ O (where M is Represents a metal atom,
n, m, x, y, and そ れ ぞ れ each represent an integer). Specifically, edited by Nihon Kagaku, “Experimental Chemistry Course 9, Synthesis and Purification of Inorganic Compounds”, published by Maruzen Co., Ltd. (1958), “Dictionary of Inorganic Compounds and Complexes”, published by Kodansha (1979), ) Coloring Material Association, “Coloring Material Handbook”, 250 pages, published by Asakura Shoten (19)
89), "Paints and Pigments" by Akira Misono, p. 184, published by Nikkan Kogyo Shimbun (1960) and the like.

The ratio between the metal sulfide particles and the hydrated metal oxide particles is 5:95 to 50:50 (mass ratio), preferably 10:50.
The ratio is 90 to 40 to 60 (mass ratio).

According to the present invention, the use of the above-mentioned inorganic particles makes it possible to obtain a desirable smoothness of the surface of the image receiving layer, and does not cause stains or the like of printing ink on non-image areas. Furthermore, by using metal sulfide particles, both the hydrophilicity of the surface of the image receiving layer and the strength of the image area after image formation are improved. Details of these effects are unknown, but the metal sulfide particle surface has better adhesion with the image forming material than other inorganic particles, and furthermore, by containing metal sulfide particles at the time of dispersion, water-containing particles are simultaneously dispersed. It is considered that the dispersibility and interaction of the metal oxide particles and the binder are affected, and as a result, an image receiving layer capable of exhibiting the above performance can be formed.

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.

A siloxane polymer refers to a polymer mainly containing a bond consisting 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 group, propenyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group and the like) 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 a nitrogen atom, an oxygen atom and a sulfur atom (for example, a heterocyclic ring includes 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 content as R ¹ or an aromatic group having 6 to 12 carbon atoms which may be substituted (the aromatic group is the same as R ⁰ in the above R ⁰ ). 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, but are not limited to, the following.

[0033] 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). .

Examples of the polymer having the specific bonding group of the present invention in the polymer main chain include an amide resin having a —N (R ¹¹ ) CO— bond or a —N (R ¹¹ ) SO ₂ — bond;
A ureide resin having an 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 in the ureide resin, and the diols used in 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 other polymers 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 derivatives thereof.

[0042]

Embedded image

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 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.

[0049]

Embedded image

[0050]

Embedded image

On the other hand, the hydroxyl-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, “New Water-Soluble Polymer Applications and Markets” ( 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 acrylic 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 10 ³ to 10 ⁶ , more preferably 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 siloxane polymer / organic polymer mass ratio is 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 solution for the image receiving layer is preferably an aqueous solvent, and furthermore, a water-soluble solvent is also used for uniform liquefaction by suppressing precipitation during preparation of the coating solution. 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. However, 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, 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 obtained by substituting R of the structural formula RCOOH with other elements or substituents, sulfonic acids such as benzenesulfonic acid, 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 constituent components in addition to the above components. As other components, inorganic pigment particles other than the specific metal sulfide and 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 mass based on 100 parts by mass of the total amount of the metal sulfide and the hydrated metal oxide particles of the present invention. Preferably, it is within 20 parts by mass.

The ratio of the pigment (metal sulfide and hydrated metal oxide particles of the present invention and other inorganic pigment particles used as required) / binder resin in the image receiving layer is generally 10%.
The ratio of the binder resin is 8 to 50 parts by mass, and preferably 10 to 30 parts by mass with respect to 0 parts by mass. Within this range, the effects of the present invention are effectively exhibited, the film strength during printing is maintained, and the high hydrophilicity of the non-image area is maintained. Further, the image portion is sufficiently adhered to the image receiving layer, and sufficient printing durability can be obtained without causing image defects even when the number of printed sheets increases.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. Examples of the 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 using 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 ml) or more in terms of 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 ml), more preferably 50-150
(Second / 10 ml). 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 30 (seconds / 10 ml) or more, and the higher the better, the better, 150 to 3000 (seconds / 10 ml), more preferably 200 to 2500 (seconds / ml). 10 ml). 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 ml) 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 unevenness is formed at a high level and the interval is dense.
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 used 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 m
l) above, more preferably 900-3000 (sec / 10m
l), more preferably 1000 to 3000 (sec / 10 ml). By controlling the smoothness of the surface of the support on the side adjacent to the image receiving layer to a Beck smoothness of 300 (seconds / 10 ml) 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 under layer, and an over layer 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 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 according to 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 conductive water-resistant support 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 lamination of 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, a 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 2 μm thick as a water resistant substrate
Paper having a water resistance of 00 μm, plastic film or paper laminated with metal foil, plastic film, or the like 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.
Apply at m-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 surface 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 ml). 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 100 to 120 μm.

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

As an electrophotographic recording method, any of conventionally known recording methods can be used. For example, Electrophotography Society of Japan, "Basics and Application of Electrophotography Technology", published by 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 flat bed 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.

In order to remove excess developer after development, 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 for drying and 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 the 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 Laid-Open No. 10-2
No. 59366, No. 10-316920, No. 10-20
No. 4354, No. 10-204356, No. 10-315
No. 617 and No. 11-43638.

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 the 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 system 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.

The head 10 provided in the ink jet recording apparatus has a slit sandwiched between the upper unit 101 and the lower unit 102 as shown in FIGS. Has become
The ejection electrode 10b is arranged in the slit, and the oil ink 11 is filled in the slit.

In the head 10, a voltage is applied to the ejection electrode 10b in accordance with a digital signal of pattern information of an image. 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 in order 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.
By setting the distance between b and the counter electrode 10c to 1.5 mm and applying a voltage of 3 kV for 0.1 millisecond between the electrodes, 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 tip of the partition wall 19 at the center of the cell forms the discharge 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 '.

Ink is supplied to the head from the direction I by ink supply means (not shown) through an ink groove, and ink is supplied to a 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.

[0111]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Examples 1 and 2 and Comparative Examples A and B The materials shown in Table 1 below were dispersed together with glass beads for 30 minutes using a paint shaker (manufactured by Toyo Seiki Co., Ltd.). In addition, 20 of the previously hydrolyzed tetraethoxysilane
% By mass (water / ethanol (1/1) mass ratio) solution 110
g and colloidal silica (Snowtec C (20% by mass aqueous dispersion) manufactured by Nissan Chemical Industries, Ltd.) were added and dispersed for 3 minutes, and then the glass beads were separated by filtration to obtain a dispersion.

[0113]

[Table 1]

The above dispersion was used as a support for ELP-2X type master (manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic lithographic printing original plate for light seals [Under side Beck smoothness: 2000 (sec / sec.)] 10 ml)], and the above-mentioned image-receiving layer composition was dried using a wire bar so that the coating amount after drying was 5%.
g / m ² , and oven at 100 ° C, 1
After drying for 0 minutes, an image receiving layer was prepared and used as a lithographic printing original plate.

Table 2 shows the performance evaluation results of the respective masters obtained as described above.

[0116]

[Table 2]

The evaluation items shown in Table 2 were performed according to the following contents.

Note 1) Smoothness A lithographic printing original plate was converted to a Beck smoothness tester (Kumaya Riko Co., Ltd.)
And its smoothness (second / 10
Measure 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 using a surface contact angle meter (C).
AD, Kyowa Interface Science Co., Ltd. product name).

Note 3) Image reproducibility Using the lithographic printing plate precursor prepared as described above, a servo plotter DA8400 manufactured by Graphtec Co., Ltd., capable of drawing output from a personal computer, was modified and shown in FIG. An ink ejection head was mounted, and printing was performed on the lithographic printing original plate placed on the counter electrode spaced at a distance of 500 μm using the following oil-based ink (IK-1) to make a plate. Subsequently, the surface temperature of the ink image surface was set to 8
The temperature was adjusted to 0 ° C. and heated for 1 minute to sufficiently fix the image area. A copy image of the obtained plate (ie, printing plate) was visually observed at a magnification of 200 times with an optical microscope.

<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 increased to 100 ° C., and the mixture was stirred for 1 hour to remove unreacted vinyl acetate. 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 CA
It was measured with PA-500 (manufactured by Horiba, Ltd.).

(Preparation of Ink) Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 98/2 mass ratio) 1
0 g, 10 g of alkali blue and 30 g of Shellsol 71 were put together with glass beads into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine blue dispersion of alkali blue. 50 g of the above resin particles
The black oil-based ink (IK-1) was prepared 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). Created.

Note 4) Printing durability A lithographic printing plate was prepared by performing image formation and fixing on a lithographic printing original plate in the same manner as in the evaluation of image reproducibility described above. Using this printing plate, a PS plate treating agent (EU-3,
Using a solution obtained by diluting Fuji Photo Film Co., Ltd.) 50 times with water, printing was performed with black ink for offset printing using Oliver 94 type (manufactured by Sakurai Seisakusho) as a printing machine. The number of printed sheets having a clear image free of background stains and free of fine lines, characters and the like is represented as printing durability.

From the results in Table 2, the surface smoothness of the image receiving layers of Examples 1 and 2 and Comparative Examples A and B are almost the same.
The contact angle with water was 0 degree in both Examples 1 and 2, and the hydrophilicity of the surface was good. In the plates that were actually made, in Examples 1 and 2 and Comparative Examples A and B, there were no bleeding or distortion in thin lines and fine characters, and the density of solid portions was sufficient, and the dot image on the plate was a perfect circle. Was good. When printing was actually performed using the obtained printing plate, in Examples 1 and 2, a clear image printed matter having no printing ink adhesion stains on the non-image portion was obtained.
While 50,000 or more sheets were obtained, in Comparative Examples A and B, stains on the non-image area were generated on about 2500 sheets and 1200 sheets, respectively.

Example 3 <Preparation of Direct-Drawing Lithographic Printing Precursor> Paint shaker (Toyo Seiki Co., Ltd.) containing the following contents together with glass beads
After dispersion at room temperature for 20 minutes, the glass beads were separated by filtration to obtain a dispersion.

Iron sulfide (manufactured by Toshin Chemical Co., Ltd.) (average particle size: 3.0 μm) 10 g Hydrous aluminum hydroxide: 90 g Alumina White A (manufactured by Daimei Chemical Industry Co., Ltd.) (average particle size: 1.5 μm) ) 10 wt% aqueous solution of gelatin (Wako Pure Chemical Industries, Ltd.) 300 g Tetraethoxysilane 4.2 g Ethanol 8.6 g Colloidal silica 20% aqueous solution; 182 g Snowtec C (Nissan Chemical Industries, Ltd.) Fluoroalkyl ester : FC-430 (manufactured by 3M) 0.25 g Curing agent CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH ₂ 1.0 g 1N (mol / L) hydrochloric acid 4 g Water 150 g

Using a support of ELP-2X type master,
The above composition was applied thereon using a wire bar so as to have a coating amount after drying of 6 g / m ² , dried by touch, and further heated at 110 ° C. for 30 minutes to form an image receiving layer. The original plate was used for printing. The surface of the obtained master had a Beck smoothness of 900 (sec / 10 cc) and a contact angle with water of 5 ° or less.

<Preparation of Electrophotographic Photoreceptor> 2 g of X-type metal-free phthalocyanine (manufactured by Dainippon Ink Co., Ltd.), 14.4 g of binder resin (P-1) shown below, and binder resin (P-2) 3 shown below .
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 dispersed with a paint shaker (manufactured by Toyo Seiki Seisaku-sho) for 60 minutes. Liquid.

[0129]

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, and is read in advance from a document by a color scanner, color-separated, and subjected to several system-specific operations. After making corrections related to color reproduction, based on information stored on the hard disk in the system as digital image data, a semiconductor laser drawing apparatus is used as an exposure apparatus.
Exposure was performed with 88 nm light at a beam spot diameter of 15 μm at 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 photoreceptor at this time was 25 erg / cm ² (mJ / m 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 at which the surface temperature of the photosensitive member became 50 ° C. The remaining amount of Isopar G is (10 mg / g of toner mass)
And dried. 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 original plate, and transferred by applying a negative corona discharge from the electrophotographic photosensitive member side. .

<Preparation of 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. 1 part by mass of this crushed material and Isopar H4
The parts by mass were dispersed with a paint shaker for 6 hours to obtain a dispersion. 1 g of this dispersion is added to the toner solids per liter.
Thus, a liquid developer was prepared by diluting with Isopar G and simultaneously containing 0.1 g per liter of basic barium petrone as a charge control agent for imparting negative charge.

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

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. When the image of the obtained plate-making product was observed by an optical microscope at a magnification of 200 times and evaluated, it was a clear image without blurring or missing of fine lines and fine 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, an SLM-OD (Mitsubishi Paper Mills Co., Ltd.).
Was diluted 100 times with distilled water and placed in a fountain solution tray, and printing was performed on printing paper using black ink for offset printing. The print image of the tenth printed matter is 2
As a result of a visual evaluation using a 0x magnification, no background stain due to the adhesion of the printing ink to the non-image area was observed, and the uniformity of the solid image area was good. Furthermore, optical microscope observation of 200 times,
Good image quality was obtained without any thinning or missing thin lines and characters. Further, 10,000 or more prints having the same print quality were obtained.

Example 4 <Preparation of Water-Resistant Support> A high-grade paper weighing 100 g / m ² was used as a substrate, and a back layer paint 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.

(Paint for back coat layer) ・ Kaolin (50% aqueous dispersion) 200 parts ・ Polyvinyl alcohol aqueous solution (10%) 60 parts ・ SBR latex (solid content 50%, Tg: 0 ° C.) 100 parts ・ Melamine resin (Solid content 80%, 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 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 ・ Melamine resin (solid content 80%, Sumiretz Resin SR-613) 4 parts

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 Direct-Drawing Lithographic Printing Plate> The following composition was dispersed together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.) at room temperature for 20 minutes, and the glass beads were filtered off to obtain a dispersion. I got

Lead sulfide (manufactured by Kishida Chemical Co., Ltd.) (average particle size: 1.0 μm) 10 g Hydrous magnesium hydroxide 90 g (manufactured by Kyowa Chemical Co., Ltd.) (average particle size: 3.0 μm) Starch 300 g (PENON ZP-) 2, Nisseki Chemical Co., Ltd.) 10% aqueous solution tetraethoxysilane 30 g methyltrimethoxysilane 3 g Snowtec C (20% aqueous solution) 91 g ethanol 10 g 1N (mol / L) hydrochloric acid 5 g water 150 g

This dispersion was applied 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 printing plate. It was created.

A servo plotter DA840 manufactured by Graphtec Co., Ltd. capable of drawing a personal computer output using the obtained master.
0 was modified, the ink ejection head shown in FIG. 4 was attached to the pen / plotter part, and the oil-based ink (IK-1) was applied to a lithographic printing plate precursor placed on a counter electrode spaced at a distance of 500 μm. Printing was performed using the plate. 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.

Subsequently, RICOH FUSER model 5
Using 92 (manufactured by Ricoh Co., Ltd.), the temperature of the ink image surface was adjusted to 80 ° C. and heated for 1 minute to sufficiently fix the image area.

Next, the printing plate created as described above is
As a printing machine, Oliver 94 (manufactured by Sakurai Seisakusho)
As a fountain solution, a solution obtained by diluting EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 100 times with distilled water was placed in a fountain solution tray, and black ink for offset printing was used.
Printing was performed 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. . Further, even 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. Further, 5,000 or more prints of the same print quality were obtained.

Examples 5 to 22 In Example 4, instead of 90 g of hydrous magnesium hydroxide, the respective compounds shown in Table 3 below (average particle size: 0.03
Each lithographic printing original plate was prepared in the same manner as in Example 4 except that 90 g was used. The Beck smoothness of the surface of each of the obtained masters was 200 to 350 (sec / 10 cc), and the contact angle with water was 5 degrees or less. Each of the obtained master plates was made and printed in the same manner as in Example 4. The obtained printed matter had a clear image with no background stain in the non-image portion and no bleeding or distortion in fine lines and characters. Table 3 shows the results of the printing durability of each of these plates. Each plate showed good printing durability of 5,000 sheets or more.

[0149]

[Table 3]

Examples 23 to 29 In Example 1, the PVA-11 of the coating solution for the image receiving layer was used.
A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that each of the organic polymers and silane compounds shown in Table 4 below were used instead of 7 and tetraethoxysilane.

[0151]

[Table 4]

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 with water on the surface was 5 degrees or less. When the printing plate was made into a printing plate in the same manner as in Example 1, and the printing was performed, the obtained printed matter had clear image quality without stain on the non-image portion, similarly to the printing plate of Example 1. The printing durability was as good as 5,000 or more.

Example 30 A composition having the following content was dispersed in a paint shaker for 20 minutes to form a dispersion, and the composition was dried on a support for ELP-2X so that the coating amount after drying was 6 g / m ^2. Was applied and dried by touch, and then heated at 150 ° C. for 30 minutes to prepare a lithographic printing original plate.

<Image receiving layer composition> Lead sulfide (manufactured by Nacalai Tesque, Inc.) (average particle size: 1.5 μm) 5 g hydrous iron oxide (average particle size: 0.2 μm) 40 g Silica: thyricia 310 (Fuji Silysia) 5 g succinic acid-modified starch PENON-F3 (manufactured by Nisseki Chemical Co., Ltd.) 30 g tetraethoxysilane 28 g benzyltrimethoxysilane 2 g 1 N (mol / L) hydrochloric acid 2 g water 300 g

The Beck smoothness of the surface of the obtained image receiving layer was 400 (sec / 10 cc), and the contact angle with water on the surface was 5 degrees or less.

Plate making was performed using the electrostatic ink jet recording apparatus described in International Patent Publication No. WO93 / 11866 and using the oil ink (IK-1) of Example 1 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 4, the obtained printed matter had clear image quality with no stain on the non-image portion, and the printing durability was 10,000 sheets, similarly to the printed matter in Example 4. The above was good.

Examples 31 to 47 Each planographic printing plate was prepared in the same manner as in Example 1 except that 10 g of each compound shown in Table 5 (average particle size: 0.03 to 2 μm) was used instead of 10 g of zinc sulfide. A printing master was created.
The surface smoothness of each of the obtained masters is 500 to 1000 seconds /
At 10 cc, the contact angle with water was 0 degree.
Each original plate was made and printed in the same manner as in Example 1. The obtained printed matter had a clear image with no background stain in the non-image portion and no bleeding in fine lines and fine characters. Each plate showed good printing durability of 6000 sheets or more.

[0158]

[Table 5]

Example 48 A lithographic printing plate precursor similar to that of Example 1 was used and a thermal transfer printer (Alps MD-4000, Alps MD-4000) using an ink ribbon.
Plate making). The copied image of the obtained plate was visually evaluated using a 20-fold loupe.
The plate making quality was good. That is, the plate-making product obtained by the ink transfer from the thermal transfer type printer has no thin lines and fine characters, the solid portion is uniform, no unevenness of the ink transfer is recognized at all, and the non-image portion also has the ink ribbon. The ground fogging due to the unevenness was slight, and was good without practical problems. Next, after making a lithographic printing plate precursor by the same operation as above, using a fully automatic printing machine (AM-2850, AM Co., Ltd., trade name), PS was used as immersion water.
Printing was performed through a plate using a printing machine using a liquid obtained by diluting a plate treating agent EU-3 (manufactured by Fuji Photo Film Co., Ltd.) 50 times with distilled water and using black ink for offset printing. The printed matter obtained had a clear image with no background image stains in the non-image portion and no distortion in fine lines and fine characters.
In addition, 5,000 good printed matters were obtained.

Example 49 The same lithographic printing plate precursor as in Example 1 was used in AM-Straight
Laser printer using dry toner commercially available as Imaging System (AMSIS / 1200-JPl
ate Setter). The copied image of the obtained plate was visually evaluated using a 20-power loupe, and the image quality of the plate was good. That is, the plate-making product obtained by transferring the toner from the thermal transfer type printer has no thin lines and fine characters, the solid portion is uniform, no uneven toner transfer is recognized, and the toner is scattered in the non-image portion. The ground fogging was also slight, and was good without practical problems. Next, after making a lithographic printing plate precursor by the same operation as described above, using a fully automatic printing machine (AM-2850, AM Co., Ltd., trade name), the PS plate treating agent EU was used as immersion water. -3 (Fuji Photo Film Co., Ltd.) with distilled water
Printing was performed through a plate using a printing machine using a liquid diluted to 0-fold and black ink for offset printing. The printed matter obtained had a clear image with no background image stains in the non-image portion and no distortion in fine lines and fine characters. In addition, 4,000 good printed matters were obtained.

[0161]

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. Furthermore, it is possible to print a large number of prints of clear image quality without any missing, blurred, or distorted images.

[Brief description of the drawings]

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

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

[Explanation of symbols]

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

Claims (3)

[Claims] An average particle size of 0.01 to 1 on a water-resistant support.
5 μm of at least one kind of metal sulfide particles (provided that metal atoms constituting the metal sulfide are Zn, Ag, Se, F
e, Pb, Sb, Cd, Cr, Co, Zr, Sn, T
i, Ni, Mg, Mo, La, Pd, Y, In and Ir
At least one selected from the group consisting of
5 μm of at least one hydrated metal oxide particle (provided that
The metal atoms constituting the hydrated metal oxide are Mg, Al, Z
n, Ge, Co, Zr, Sn, Fe, Cu, Ni, P
b, Ti, Pd, Cd, Cr, Ga, Mn, V, Mo,
At least one selected from Ce and La) in a ratio of 5:95 to 50:50 (mass ratio), and a siloxane bond-containing resin in which Si is connected via an oxygen atom; A direct drawing type lithographic printing plate precursor comprising an image receiving layer containing at least a binder resin comprising a complex of a resin and an organic polymer containing a group capable of forming a hydrogen bond. 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.