JPH10157053A - Method for forming ink jet type plate-making printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming an ink jet type plate-making printing plate for obtaining a printed matter of a clear image with excellent plate wear resistance. SOLUTION: This printing plate is formed as a lithographic printing plate with a hydrophilic surface by injecting oil base ink in a liquid droplet state from a nozzle onto an image receiving layer of a lithographic printing original plate to form an image in an ink jet type, and then desensitizing a non-image part of the layer by a chemical reaction process. In this case, the layer is disposed on a water resistant support, and contains at least one type of a functional group for forming at least one of -CO2 H group, -SO3 H group and PO3 H2 group and contains at least partly crosslinked resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a lithographic printing plate using an ink-jet recording method, and more particularly, to a method for preparing an ink-jet type plate using an oil-based ink and having good printing quality. About the method.

[0002]

2. Description of the Related Art With the recent development of office equipment and the development of OA, in the field of light printing, a direct-drawing lithographic printing plate precursor having a hydrophilic surface image-receiving layer on a water-resistant support is produced by various methods. 2. Description of the Related Art Offset lithographic printing, in which a plate is made, that is, an image is formed to create a printing plate, has become widespread.

[0003] A conventional plate material for direct drawing type lithographic printing is obtained by forming an image receiving layer (including an inorganic pigment, a water-soluble resin and a water-proofing agent) on a support made of water-resistant paper or a plastic film. Or an image receiving layer).
Using a lipophilic ink on such a lithographic printing plate, a lipophilic image is formed by a typewriter or handwriting, or an image is thermally melt-transferred from an ink ribbon by a thermal transfer printer, or a liquid ink is used. There is known a method of forming a printing plate by forming an oleophilic image with an ink jet printer using the same.

However, the printing plate prepared by such a method has insufficient mechanical strength of the image portion, and the image portion is easily missing when printed.

In plate making using an ink jet printer, a method of eliminating the problem of diffusion and absorption of an image forming agent in a liquid on a plate material, which occurs when liquid ink is used, and reducing bleeding of an image has been proposed. Japanese Patent Application Laid-Open No. 64-27953 discloses a hot-melt ink-jet method (also referred to as a solid jet method) in which a solid ink is converted into a liquid by heat melting. The surface of the image receiving layer of the printing original plate used here is hydrophilic.

However, even in this method, when a printing plate is actually formed and printed, bleeding of an image portion is seen, and the number of printed sheets is limited to several hundred at most, which is insufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method of producing an ink-jet type plate making printing plate capable of printing a large number of prints of clear images.

[0008]

The above object is achieved by the following.
This is achieved by the present invention of (1) to (5).

(1) An oil-based ink is ejected from a nozzle in the form of droplets on an image receiving layer of a lithographic printing plate precursor to form an image by an ink jet method, and then a non-image portion of the image receiving layer is subjected to a chemical reaction treatment. A method for preparing an ink-jet plate-making printing plate to be desensitized by a lithographic printing plate having a hydrophilic surface, wherein the image-receiving layer is on a water-resistant support, and is decomposed by a chemical reaction treatment. -CO ₂ H group, -S
An ink-jet type plate-making printing plate comprising at least one functional group forming at least one of O ₃ H group and PO ₃ H ₂ group and containing at least a partly crosslinked resin (A) How to make. (2) The resin (A) is decomposed to have a —CO ₂ H group,
At least one of —SO ₃ H groups and PO ₃ H ₂ groups;
A copolymer component containing at least one functional group that forms two groups, and when the group is formed by decomposition,
(1) The method for producing an ink-jet type plate-making printing plate according to the above (1), which is a resin cross-linked in advance so as to be hardly soluble or insoluble in water. (3) the oil-based ink has an electrical resistance of 10 ⁹ Ωcm or more;
The method for producing an ink-jet type plate making plate according to the above (1) or (2), wherein solid and hydrophobic resin particles are dispersed at least at room temperature in a non-aqueous solvent having a dielectric constant of 3.5 or less. (4) The method for producing an ink-jet type plate-making printing plate according to any one of (1) to (3), wherein the resin particles in the oil-based ink are positive or negative voltage detecting particles. (5) The method for producing an ink-jet plate-making printing plate according to any one of (1) to (4), wherein the surface of the support on the side adjacent to the image receiving layer has a Beck smoothness of 300 (sec / 10 cc) or more. .

[0010]

According to the present invention, the chemical reaction process, particularly by decomposition in the desensitizing step, functional to generate at least one of the radicals -CO ₂ H group, -SO ₃ H group and PO ₃ H ₂ group A lithographic printing plate precursor having an image-receiving layer containing a resin (A) containing at least one group and at least partially crosslinked on a water-resistant support, wherein an oil-based ink is used on the image-receiving layer. A hydrophobic ink image is formed by the ink jet method, and the non-image area is then made hydrophilic.Therefore, compared to a case where an image is formed on the hydrophilic image receiving layer with the hydrophobic ink by the ink jet method, The image quality of both the plate-making image and the print image is remarkably improved, and the printing durability is also excellent.

[0011]

Embodiments of the present invention will be described below in detail.

[0012] inkjet plate making printing plate according to the method of the invention, be on the water-resistant support, by decomposition of a chemical reaction treatment, -CO ₂ H group, -SO ₃ H group and PO ₃
On the image-receiving layer on the hydrophobic surface having an image-receiving layer containing at least one functional group that forms at least one of the H ₂ groups and containing at least a partially crosslinked resin (A) Then, using an oil-based ink, an image is formed by an ink-jet method, and then the non-image portion of the image receiving layer is desensitized by a chemical reaction treatment to provide a lithographic printing plate that becomes a hydrophilic surface that can be flat-printed during printing. The formed image layer has a sufficient affinity for the image receiving layer to be adhered or adhered thereto, and becomes a strong image portion in which the image layer is hardly dropped.

The image receiving layer contains a resin (A) containing a functional group in which a hydrophilic group is protected, the surface of which is hydrophobic, and a hydrophilic group is formed by a chemical reaction when treated with a desensitizing solution. In addition, the surface is modified to be hydrophilic so that the surface can be printed.

The image receiving layer contains a carboxy group, a sulfo group, -P (= O) (OH) contained in the resin (A).
_It contains a polymer component (a) having a functional group that produces at least one of the two groups. This polymer component (a)
In the above, one or two hydrophilic groups may be generated by a chemical reaction from one functional group.

First, a functional group that forms at least one carboxy group by a chemical reaction will be described.

According to a preferred embodiment of the present invention, examples of the carboxy group-forming functional group include a functional group represented by the following formula (I).

-COO-L ¹ (I) In the formula (I), L ¹ represents the following group.

[0018]

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Here, R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom or a hydrocarbon group;
X represents an aromatic group; Z is a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group, a cyano group, a —NO ₂ group,
—SO ₂ Z ¹ (Z ¹ represents a hydrocarbon group) group, —COO
Z ² (Z ² represents a hydrocarbon group) group, —OZ ³ (Z ³ represents a hydrocarbon group) or —COZ ⁴ (Z ⁴ represents a hydrocarbon group) group, and n and m are respectively 0, 1 or 2
Represents However, when both n and m are 0, Z is not a hydrogen atom.

R ¹⁴ , R ¹⁵ and R ¹⁶ and R ²⁰ and R ²¹ may be the same or different and represent a hydrocarbon group or a —OZ ⁵ (Z ⁵ is a hydrocarbon group) group. Y ²
Represents an organic residue forming a cyclic imide group. R ²⁰ , R ²¹
May be the same or different and represent a hydrocarbon group.

The details will be described below.

R ¹¹ and R ¹² may be the same or different from each other, and are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, ethyl group). Group, propyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-chloropropyl group, etc. Preferably substituted phenyl group or naphthyl group (for example, phenyl group, methylphenyl group, chlorophenyl group, dimethylphenyl group,
Represents a chloromethylphenyl group, a naphthyl group or the like, and Z is preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Fluorine atom), trihalomethyl group (for example, trichloromethyl group, trifluoromethyl group, etc.),
A linear or branched alkyl group which may be substituted (for example, methyl group, chloromethyl group, dichloromethyl group, ethyl group, propyl group, butyl group, hexyl group, tetrafluoroethyl group, octyl group, cyanoethyl group, chloroethyl group, etc.), - CN group, -NO ₂ group, -SO ₂ Z
¹ [Z ¹ represents an aliphatic group (for example, an alkyl group which may be substituted and has 1 to 12 carbon atoms: specifically, a methyl group, an ethyl group,
Propyl, butyl, chloroethyl, pentyl,
An aralkyl group having 7 to 12 carbon atoms which may be substituted, such as an octyl group: specifically, a benzyl group, a phenethyl group, a chlorobenzyl group, a methoxybenzyl group, a chlorophenethyl group, a methylphenethyl group, etc.) or an aromatic group ( For example, a phenyl group or a naphthyl group which may contain a substituent: specifically, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a methoxyphenyl group, an acetylphenyl group, an acetamidophenyl group, a methoxycarbonylphenyl group, Naphthyl group, etc.) group, —CO
An OZ ² (Z ² has the same meaning as Z ¹ ), —OZ ³
Wherein Z ³ is as defined above for Z ¹ , or —COZ ⁴
(Z ⁴ has the same meaning as Z ¹ above). n and m each represent 0, 1 or 2. However, when both n and m are 0, Z is not a hydrogen atom.

R ¹⁴ , R ¹⁵ and R ¹⁶ and R ²⁰ and R ²¹ may be the same or different from each other, and are preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted. Group, an alkenyl group, an aralkyl group or an alicyclic group; examples of the substituent include a halogen atom,
A —CN group, a —OH group, a —OZ ⁶ (Z ⁶ represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group) and the like], and an optionally substituted aromatic group having 6 to 18 carbon atoms. groups (such as phenyl group, tolyl group, chlorophenyl group, a methoxyphenyl group, acetamidophenyl group, a naphthyl group, etc.) or -OZ ⁵ (Z ⁵ which may be substituted aralkyl group having 7 to 12 carbon atoms, 5 carbon atoms A to alicyclic group which may be substituted, or an optionally substituted aryl group having 6 to 18 carbon atoms).

Y ² represents an organic residue forming an imide group, and preferably represents an organic residue represented by the formula (A) or (B).

[0025]

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In the formula (A), R ²² and R ²³ may be the same or different and each may be a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), or a substituted one having 1 to 18 carbon atoms. Good alkyl groups (e.g. methyl, ethyl, propyl, butyl, hexyl, octyl,
Decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 2-
A cyanoethyl group, a 3-chloropropyl group, a 2- (methanesulfonyl) ethyl group, a 2- (ethoxyoxy) ethyl group, etc.], an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc., and optionally substituted alkenyl groups having 3 to 18 carbon atoms (for example, allyl group, 3-methyl- 2-propenyl group,
2-hexenyl group, 4-propyl-2-pentenyl group,
12-octadecenyl group, etc.), -SZ ⁸ [Z ⁸ is
A substituent having the same contents as the alkyl group, aralkyl group and alkenyl group represented by ²² or R ²³ , or an aryl group which may be substituted (for example, phenyl, tolyl, chlorophenyl, bromophenyl, methoxyphenyl, ethoxy) Phenyl, ethoxycarbonylphenyl, etc.) or —NHZ ⁹ (Z ⁹ has the same meaning as Z ⁸ ). Further, a residue forming a ring by R ²² and R ²³ may be represented [eg, a 5- or 6-membered monocyclic ring (eg, a cyclopentyl ring, a cyclohexyl ring), or a bicyclo ring containing a 5- or 6-membered ring (eg, Bicycloheptane ring, bicycloheptene ring, bicyclooctane ring, bicyclooctene ring, etc.), and these rings may be substituted, and the substituents include those described above for R ²² and R ²³ ] . q represents an integer of 2 or 3.

[0027]

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In the formula (B), R ²⁴ and R ²⁵ may be the same or different and represent the same contents as R ²² and R ²³ . Further, R ²⁴ and R ²⁵ may represent an organic residue that continuously forms an aromatic ring (for example, a benzene ring, a naphthalene ring, etc.).

The functional group which forms at least one sulfo group by a chemical reaction includes, for example, the following formula (II)
And a functional group represented by

-SO ₂ -OL ² (II) In the formula (II), L ² represents the following groups.

[0031]

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Here, R ¹¹ , R ¹² , X, Z, n, m, Y
² represents R ²⁰ and R ²¹ the same contents as each of the. R ²⁶ ′ and R ²⁷ ′ each represent a hydrogen atom or a hydrocarbon group (the same contents as the hydrocarbon groups represented by R ²² and R ²³ ).

Further, -P (= O) (O
H) The functional group that forms the group ₂ includes, for example, the following formula (II)
And functional groups represented by I).

[0034]

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In the formula (III), L ³ and L ⁴ may be the same or different and each represent the same content as L ¹ . R ¹
Represents the same content as described above.

Specific examples (a-1) to (a-30) of the respective functional groups represented by the above formulas (I) to (III) are shown below. However, the content of the present invention is not limited to these. In addition, in the following specific examples, each symbol is as shown below. Usually, one or two of these functional groups are contained in the resin of the organic copolymer component (a) in an amount of 20 to 90 wt.
% To more preferably about 25 to 80 wt%.

[0037]

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[0038]

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[0039]

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[0040]

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The above-mentioned -CO ₂ H group, -SO ₃ H group, -P (= O) which can be used in the present invention.
The functional group that expresses the (OH) ₂ group by a chemical reaction is a functional group that protects these hydrophilic groups, and a method of introducing these protective groups to the hydrophilic group by chemical bonding is a conventionally known method. Can be easily performed.

For example, JFWMcOmie “Protective group
s in Organic Chemistry ”(PlenumPress. 1973), TWGreene“ Protective groups in Organic Syn ”
Thesis "(Wiley-Intersciience. 1981), The Chemical Society of Japan," New Chemistry Laboratory Course, Vol. 14, Synthesis and Reaction of Organic Chemistry "(Maruzen Co., Ltd., 1978), Yoshio Iwakura and Keisuke Kurita," Reactivity " Each unit reaction described in “Polymer” (Kodansha) or the like is used.

As a method for introducing these functional groups into the resin (A), a —COOH group, a —SO ₃ H group, a —P (=
A method using a so-called polymer reaction in which a polymer containing at least one hydrophilic group selected from O) (OH) ₂ groups and the like is converted into a functional group in which each hydrophilic group is protected by a reaction; After synthesizing one or more monomers containing one or more of the functional groups represented by the formulas (I) to (III), To a polymer by a polymerization reaction of

In the polymer, the functional group required for the present invention can be arbitrarily adjusted, or impurities (in the case of a polymer reaction,
For the reason that the catalyst or by-products to be used are not mixed, it is preferable to produce the compound by the latter method (a method of obtaining a desired monomer in advance and then performing a polymerization reaction).

For example, when a functional group that generates a carboxyl group is introduced, specifically, a carboxylic acid containing a polymerizable double bond or a halide of the acid is converted according to the method described in the above-mentioned known literature. After converting the carboxyl group into a functional group represented by the formula (I), the reaction can be carried out by a method of producing by conducting a polymerization reaction.

As described above, examples of the copolymer component containing the functional groups of the formulas (I) to (III) include a component represented by the following formula (VI). However, the present invention is not limited to these copolymer components.

[0047]

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Represents an aromatic group or a heterocyclic group, provided that Q ¹ , Q ² , Q ³ , and Q ⁴ each represent a hydrogen atom, a hydrocarbon group, or (-Y'-W in formula (IV)) ), And n represents an integer of 0 to 18]. Y ′ represents a carbon-carbon bond which connects the bonding group X ′ and the bonding group [W] and may be via a hetero atom (hetero atoms represent an oxygen atom, a sulfur atom, and a nitrogen atom); For example,

[0049]

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[0050] -COO -, - CONH -, - SO 2 -,
It is composed of a single or a combination of bonding units such as —SO ₂ NH—, —NHCOO—, and —NHCONH— (provided that b ₃ , b ₄ , and b ₅ each represent a hydrogen atom or a ₁ , a ₂ Represents the same content as the hydrocarbon represented by. W represents a functional group represented by formulas (I) to (III). a ₁ and a ₂ may be the same or different and include a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group) , Butoxycarbonyl, hexyloxycarbonyl, etc.) or a hydrocarbon group (eg, methyl, ethyl, propyl, butyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, etc.) C1-C6 alkyl group, benzyl group, aralkyl group such as phenethyl group,
Aryl group such as phenyl group, tolyl group, xylyl group and chlorophenyl group). Further, the [-X′-Y ′] binding residue in the formula (III) is

[0051]

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The part and the -W part may be directly connected.

Other copolymerizable components that can be copolymerized with the copolymer component (a) of the present invention include vinyl acetate,
Aliphatic vinyl carboxylate or allyl ester such as vinyl propionate, allyl acetate, allyl propionate, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like; Esters or amides of saturated carboxylic acids, styrene, vinyl toluene, styrene derivatives such as α-methylstyrene, α-olefins, acrylonitrile, methacrylonitrile, vinyl-substituted heterocyclic compounds such as N-vinylpyrrolidone, etc. No.

The resin (A) of the present invention is further characterized in that at least a part thereof is crosslinked in an image receiving layer of an ink-jet type original plate for plate making.

The above formula (I) contained in the resin (A)
When the functional group represented by (III) generates the hydrophilic group by decomposition, the resin becomes a hardly soluble or insoluble resin in an acidic or alkaline aqueous solution.

In the present invention, a resin having a crosslinkable functional group which undergoes a curing reaction by heat and / or light together with the above-mentioned hydrophilic group-forming functional group is used to form a crosslinked structure in a subsequent master production step. Preferably.

The crosslinkable functional group may be any one that can form a chemical bond by causing a chemical reaction between molecules. That is, it is possible to utilize a reaction mode in which heat and / or light causes a bond between molecules by a condensation reaction, an addition reaction, or the like, or a cross-linking by a polymerization reaction, or the like. Specifically, the functional group [for example -COOH groups having a dissociative hydrogen atom, -PO ₃ H ₂ group, -OH group, -SH
Group, -NHR ¹ "group (R ¹ " is a hydrogen atom or a methyl group,
Represents an alkyl group having 1 to 4 carbon atoms such as an ethyl group, a propyl group and a butyl group)]

[0058]

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At least a combination of a functional group selected from the group consisting of an isocyanate group (including a protected isocyanate group (blocked isocyanate)), a thioisocyanate group, and a group containing a cyclic dicarboxylic anhydride is used. 1
Group, or -CONHCH ₂ OR ² "(C
R ² "is a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, an alkyl group having 1 to 6 carbon atoms such as ^{hexyl), Si (OR 3")} l (R 3 ") k [R ³ "is R ¹ "
Represents an alkyl group having 1 to 4 carbon atoms. However, (l + k =
3), 1 represents 2 or 3, k represents 0 or 1], or a polymerizable double bond group.

Further, for example, Tsuyoshi Endo, "Refinement of thermosetting polymer (CMC Corporation, 1986), Yuji Harazaki,
"Latest Binder Technology Handbook" Chapter II-1 (General Technology Center, 1985), Takayuki Otsu "Synthesis and Design of Acrylic Resin and Development of New Applications" (Chubu Management Development Center Publishing Division, 1985)
Yearly), Eizo Omori "Functional Acrylic Resin" (Techno System 1985), Hideo Inui and Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha, 1977) Takahiro Tsunoda, "New Photosensitive Resin" (Printing Society) Publishing Department, 1981), GGEreen and, B.
P.Star R, J.Macro.Sci Revs Macro.Chem, C21 (2), 187
273 (1981-82), CGRoffey, `` Photopolymerization
of Surface Coatings "(A. Wiley Interscience Pub.1
982) and the like.

These crosslinkable functional groups may be contained together with a hydrophilic group-forming functional group in one copolymer component, or may be contained in a copolymer component containing a hydrophilic group-forming functional group. It may be contained in a separate copolymer component.

Specific examples of the monomer corresponding to the copolymer component containing a crosslinkable functional group include, for example, a vinyl compound containing the functional group which can be copolymerized with the above formula (IV). Any may be used.

For example, it is described in “Polymer Data Handbook [Basic Edition] Baifukan (1986)” edited by the Society of Polymer Science, Inc. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (eg, α-acetoxy) Form, α-acetoxymethyl form, α- (2-aminomethyl form, α-chloro form, α
-Promo form, α-fluoro form, α-tributylsilyl form,
α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-ester acid, itaconic acid semiamides , Crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid,
4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl group or allyl of dicarboxylic acids Half-ester derivatives of these groups, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the crosslinkable functional groups in the substituents of the amide derivatives.

The proportion of the “copolymer component containing a crosslinkable functional group” in the resin of the present invention is preferably 1
5 to 80 wt%. More preferably, it is 20 to 50% by weight.

It is preferable to add a crosslinking agent in order to sufficiently crosslink the resin (A) in the image receiving layer of the present invention and to further improve the film strength. Here, examples of the crosslinking agent include compounds generally used as a crosslinking agent. To be more specific, refer to "Bridge Handbook, Basic Edition", edited by Fuzo Yamashita and Tosuke Kaneko, "Crosslinking Agent Handbook" Taiseisha (1981), Baifukan (198)
6 years) can be used.

For example, organic peroxides, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
silane coupling agents such as γ-aminopropyltriethoxysilane, etc.), polyisocyanate compounds (eg, toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene) Diisocyanates, isophorone diisocyanates, polymer polyisocyanates, etc.), polyol compounds (eg, 1,4-butadiol, polyoxypropylene glycol, polyoxyethylene glycol, 1,
1,1-trimethylolpropane, etc.), polyamine-based compounds (eg, ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling-based Compounds (eg, tetrabutoxytitanate, tetrachloroepoxytitanate, isopropyltristearoyltitanate, etc.), aluminum-coupling compounds [eg, aluminum butyrate, aluminum acetylacetate, aluminum oxide octate (aluminum tris (acetylacetate))], poly Epoxy 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 Kangyo Kogyo Shimbun (1969) and the like, melamine resins (for example, compounds described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, etc. in Nikkan Kogyo Shimbun (1969)), Poly (meth) acrylate compounds [for example, “Oligomers” edited by Shin Ogawara, Takeo Saegusa, Toshinobu Higashimura, Kodansha (1976),
Eizo Omori "Functional Acrylic Resin" Techno System (19
Compounds published in 1985). The addition amount of these crosslinking agents is preferably about 0.1 to 50 mol%, more preferably about 0.5 to 10 mol%, based on the copolymer component containing a crosslinkable functional group of the resin.

In the present invention, a reaction accelerator may be added as necessary to accelerate the crosslinking reaction in the image receiving layer.

In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.) and phenols (phenol, phenol, Chlorophenol, nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonato zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamine) Acid salts), tinouram disulfide compounds (tetramethyltinouram disulfide, etc.), carboxylic anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride,
3,3 ', 4,4'-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.).
When the cross-linking reaction is of a polymerizable reaction mode, a polymerization initiator (a peroxide, an azobis-based compound, or the like is used. The addition amount of these reaction accelerators is 0.05 to 30 mol of the cross-linking agent.
%, More preferably about 0.1 to 20 mol%.

The image-receiving layer provided in the present invention preferably contains an inorganic pigment together with the above-mentioned resin (A) and another compound which promotes crosslinking.

Examples of the inorganic pigment used in the present invention include titanium oxide, kaolin, mica, talc, diatomaceous earth, clay, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate, magnesium hydroxide, Examples include zinc oxide, magnesium oxide, zirconium oxide, silica, and alumina.

These inorganic pigment particles usually have an average particle diameter of preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm.

The preferable use ratio of the inorganic pigment is 50 wt% based on 100 parts by weight of the total composition in the image receiving layer.
~ 90wt%, more preferably 70wt% ~ 85wt%
It is. The ratio of the pigment to the resin in each image receiving layer is generally from 10 to 50 parts by weight, preferably from 13 to 30 parts by weight, based on 100 parts by weight of the pigment.

In this range, the film strength of the image receiving layer is further improved, the film strength is sufficiently maintained at the time of printing, and moderate irregularities are formed on the film surface due to the presence of the pigment particles. By maintaining appropriate gaps, the ink image portion formed on the image receiving layer is sufficiently adhered to the image receiving layer by the improvement of the adhesion area and the anchor effect. Even when the number of prints increases, sufficient printing durability can be obtained without causing image loss. The porosity of this image receiving layer is usually 3 to 50 vol.
%, Preferably about 10 to 40 vol%.

Further, due to the unevenness of the surface and the voids in the film, water as a printing plate can be sufficiently retained at the time of printing, high hydrophilicity can be maintained, and background stain on printed matter is suppressed. .

The smoothness of the surface of the image receiving layer is preferably 30 to 400 (sec / 10 cc), more preferably 45 to 300 (sec / 10 cc) in Beck smoothness. The space of the film of the image receiving layer is preferably 5 to 50 vol%, more preferably 15 to 40 vol%.

In the image receiving layer of the present invention, the resin (A)
Is preferably cured by light and / or heat after applying the image receiving layer composition. In order to carry out thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional receiving layer production. For example, it is preferable to set the drying conditions to a high temperature and / or a long time, or to further heat after drying the coating solvent. For example, 60 ° C to 150 ° C
For 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

Further, a specific functional group in the resin may be photo-cured, and the method of curing by light irradiation may include a step of irradiating light with a chemically active light beam. The chemical actinic rays may be any of visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, γ-rays, α-rays, etc., but are preferably ultraviolet rays, more preferably from 310 nm to 500 nm.
Light rays in the nm range.

In general, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. The light irradiation treatment can be sufficiently carried out by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

The thickness of the image receiving layer in the present invention is preferably about 3 to 30 g, as indicated by the coating amount (after drying) of the image receiving composition per 1 m ² of the original plate.

The image receiving layer of the present invention is provided on a water-resistant support. As the water-resistant support, paper, a plastic film or a paper or a plastic film laminated with a metal foil, which has been subjected to a water-resistant treatment can be used.

The support used in the present invention has a surface smoothness on the side adjacent to the image receiving layer having a Beck smoothness of 300.
(Sec / 10cc) or more, preferably 900 to 3000 (sec / cc).
It is preferably adjusted to 10 cc), more preferably 1000 to 3000 (sec / 10 cc).

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, an underlayer and an overcoat layer described later are provided on the support. In this case, it refers to the surface of the underlayer or overcoat layer.

As a result, the image receiving layer whose surface condition has been adjusted as described above is sufficiently retained without receiving any irregularities on 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.

In the present invention, as a method for melt-bonding the resin, it is preferable that the resin is coated by an extrusion lamination method. By coating by this extrusion lamination method, a support having a desired smoothness can be produced. The extrusion laminating method is a method in which a resin is melted, formed into a film, immediately pressure-bonded to base paper, and then cooled and laminated, and various apparatuses are known.

The thickness of the resin layer laminated in this manner is at least 10 μm, preferably 1 μm, from the viewpoint of production stability.
0 μm to 30 μm.

Here, examples of the resin include a polyethylene resin, a polypropylene resin, an acrylic resin, a methacrylic resin, an epoxy resin, and a copolymer thereof. Also, two or more of these resins can be used. Among them, polyethylene resin is preferable. Among polyethylene-based resins, a mixture of low-density polyethylene and high-density polyethylene is particularly preferred. Thereby, the coating film has uniformity and excellent heat resistance. Furthermore, by using this mixture, when a conductive substance as described later is added to the resin layer, the conductivity becomes more excellent.

The low-density polyethylene has a density of 0.915 to 0.930 g / cc and a melt index of:
The high-density polyethylene preferably has a density of 0.940 to 0.970 g / cc and a melt index of 1.0 to 30 g / 10 minutes. As the blend ratio, low density polyethylene 10
９０90 wt% and high density polyethylene 90９０10 wt% are preferred.

When a base paper is used as the base, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, an ethylene-acrylate copolymer are pre-coated on the base paper in order to improve the adhesive strength between the base paper and the resin layer. Methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylonitrile-acrylic acid copolymer, ethylene-acrylonitrile-
It is preferable to apply a polyethylene derivative such as a methacrylic acid copolymer or to perform corona discharge treatment on the surface of the base paper. As another method, JP-A-49-24126, 5
Nos. 2-36176, 52-121683 and 53-
No. 2612, No. 54-111331 and Japanese Patent Publication No. 51
The surface treatment described in each publication of JP-A-25337 can be applied to the base paper.

A calender strengthening method mentioned as another method is achieved by, for example, calendering a substrate such as paper described below or a support having an underlayer formed on the substrate. Here, the calendering conditions are appropriately controlled depending on the composition of the substrate and the underlayer, and the types and combinations of rolls such as metal rolls, resin rolls, and cotton rolls, the number of calender rolls,
Conditions such as the roll nip pressure and the roll surface temperature can be appropriately selected.

In the present invention, as described above, an under layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a curl prevention is provided on the surface of the support opposite to the image receiving layer. A back coat layer (back layer) can be provided for the purpose, but the back coat layer preferably has a smoothness in the range of 150 to 700 (sec / 10 cc).

Thus, when a printing plate is supplied to an offset printing press, the printing plate is accurately set on the printing press without causing displacement or slippage.

When the smoothness of the underlayer and the backcoat layer of such a support are individually adjusted, for example, a calendering process is performed once after the underlayer is formed, and a calendering process is performed again after the backcoat layer is formed. In addition, the process of calendar processing is performed multiple times,
It is desirable to control the smoothness by a combination of adjusting the composition of the under layer and the back coat layer, for example, the proportion and particle size of the pigment, and adjusting the calendering conditions as described below.

Examples of the substrate to be used in the original plate of the present invention include wood pulp paper, synthetic pulp paper, mixed paper of wood pulp and synthetic pulp, non-woven fabric, plastic film, cloth, metal sheet, and composite sheet materials thereof. The substrate can be used as it is. Further, in order to obtain the smoothness specified in the present invention, and to adjust the water resistance and other properties, a hydrophobic resin used for an under layer or a back coat layer described below on the substrate, water dispersibility or A coating made of a water-soluble resin, a pigment, or the like may be impregnated.

In the present invention, underprintability such as recording characteristics, water resistance and durability required for a lithographic printing plate precursor is satisfied, and an undercoat is formed on the substrate to adjust to a desired smoothness as described above. It is preferable to use a support provided with a layer and a back coat layer. Such an under layer and a back coat layer are formed by applying a coating solution containing a resin, a pigment, and the like on a support, drying and laminating the coating solution. Various resins are appropriately selected and used as the resin used here. 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.

Examples of the pigment include clay, kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica and the like. These pigments are used to achieve the desired smoothness.
It is preferable to select the particle size appropriately and use it. For example, since a relatively high degree of smoothness is required in the under layer, small particles or large particles are cut to specifically 8 μm or less. Preferably, a pigment having a particle size of about 0.5 to 5 μm is used. Further, since a lower smoothness is required in the back coat layer as compared with the under layer, a larger particle size, specifically, 0.5 to 10
Pigments having a particle size of about μm are preferably used. The above pigment is preferably used in an amount of 80 to 150 parts by weight in the under layer and 80 to 200 parts by weight in the back coat layer, based on 100 parts by weight of the resin. In order to obtain excellent water resistance, it is effective for the under layer and the back coat layer to contain a water-resistant agent such as a melamine resin or a polyamide epichlorohydrin resin. The particle size can be measured by a scanning electron microscope (SEM) photograph. Also,
When the particles are not spherical, the diameter is obtained by converting the projected area into a circle.

To prepare the lithographic printing plate precursor according to the present invention, a solution containing an under layer component is coated on one side of the support, if necessary, and dried to form an under layer. A solution containing a component of a back coat layer is applied to the surface and dried to form a back coat layer, and then a coating solution containing a component of an image receiving layer is applied and dried to form an image receiving layer. Note that the image-receiving layer, the under layer, the coating amount of the backcoat layer are each 1 to 30 g / m ^2, in particular 6~20g / m ²
Is appropriate.

More preferably, the water-resistant support provided with an under layer or a back coat layer has a thickness of 9
0 to 130 μm, preferably 100 to 120 μm
Range.

The oil-based ink used in the present invention will be described below.

The oil-based ink used in the present invention is prepared in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less.
At least at room temperature, solid and hydrophobic resin particles are dispersed.

The electric resistance used in the present invention is 10 ⁹ Ωcm or more,
And a non-aqueous solvent having a dielectric constant of 3.5 or less, preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon,
Or, there are aromatic hydrocarbons and halogenated products of these hydrocarbons. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; a product of Exxon) ), Shellsol 70 (Shellsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits) and the like are used alone or in combination. The upper limit of the electric resistance of such a non-aqueous solvent is about 10 ¹⁶ Ωcm, and the lower limit of the dielectric constant is about 1.9.

The reason why the electric resistance of the non-aqueous solvent used is in the above range is that if the electric resistance is low, the electric resistance of the ink will not be appropriate and the ejection of the ink by the electric field will be poor. The reason for setting the range is that when the dielectric constant is high, the electric field in the ink is easily relaxed, whereby the ejection of the ink is easily deteriorated.

The resin particles dispersed in the non-aqueous solvent may be any particles of a hydrophobic resin which is solid at a temperature of 35 ° C. or lower and has a good affinity for the non-aqueous solvent. Glass transition point is -5 ° C to 110 ° C or softening point 33 ° C
The resin (P) having a glass transition point of 10 to 100 ° C or 38 to 120 ° C is more preferable.
And more preferably a glass transition point of 15 ° C to 80 ° C.
° C or a softening point of 38 ° C to 100 ° C.

By using such a resin having a glass transition point or a softening point, the affinity between the surface of the image receiving layer of the printing original plate and the resin particles increases, and the bonding between the resin particles on the printing original plate becomes weak. Therefore, the adhesion between the image portion and the image receiving layer is improved, and the printing durability is improved. On the other hand, regardless of whether the glass transition point or the softening point is low or high, the affinity between the surface of the image receiving layer and the resin particles is reduced, and the bonding between the resin particles is weakened.

The weight average molecular weight Mw of the resin (P) is 1 ×
10 ³ to 1 × 10 ⁶ , preferably 5 × 10 ³ to 8
× 10 ⁵ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁵ .

Specific examples of the resin (P) include:
Olefin polymers and copolymers (eg, polyethylene, polypropylene, polyisobutylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer,
Ethylene-methacrylate copolymer, ethylene-methacrylic acid copolymer, etc.), vinyl chloride copolymer (eg, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc.),
Vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer, allyl alkanoate polymer and copolymer,
Polymers and copolymers of styrene and its derivatives (eg butadiene-styrene copolymer, isoprene-
Styrene copolymer, styrene-methacrylate copolymer, styrene-acrylate copolymer, etc.), acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic ester polymer and copolymer, methacryl Acid ester polymers and copolymers, itaconic acid diester polymers and copolymers,
Maleic anhydride copolymer, acrylamide copolymer, methacrylamide copolymer, phenolic resin, alkyd resin, polycarbonate resin, ketone resin, polyester resin, silicone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, Polyvinyl acetal resin, urethane resin, rosin resin, hydrogenated rosin resin, petroleum resin, hydrogenated petroleum resin, maleic acid resin, terpene resin, hydrogenated terpene resin, chroman-indene resin, cyclized rubber-methacrylic acid ester copolymer Copolymer, cyclized rubber-acrylate copolymer, copolymer containing a nitrogen-free heterocycle (for example, as a heterocycle, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, Benzo Orchid ring, benzothiophene ring, 1,3-dioxetane ring), and epoxy resins.

The content of the dispersed resin particles in the oil-based ink of the present invention is preferably 0.5 to 5% of the whole ink.
0 wt%, more preferably 1 to 20 wt%. When the content is low, it is difficult to obtain an affinity between the ink and the image receiving layer of the printing original plate, and a good image cannot be obtained, or problems such as reduced printing durability are likely to occur. If the content is too high, it is difficult to obtain a uniform dispersion, or the ink tends to be clogged in the discharge head, and it is difficult to obtain stable ink discharge.

The oil-based ink used in the present invention preferably contains a coloring material as a coloring component together with the above-mentioned dispersed resin particles, for example, for plate inspection of a plate after plate making.

As the coloring material, any pigments and dyes conventionally used in oil-based ink compositions or liquid developers for electrophotography can be used.

As the pigments, those generally used in the technical field of printing can be used irrespective of inorganic pigments and organic pigments. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, viridian, titanium cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigments, phthalocyanine-based Pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, and other conventionally known pigments are particularly limited. Can be used without.

As the dyes, azo dyes, metal complex dyes,
Naphthol dye, anthraquinone dye, indigo dye,
Oil-soluble dyes such as carbonium dyes, quinone imine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred.

These pigments and dyes may be used alone or in appropriate combination, but may be contained in the range of 0.01 to 5% by weight based on the whole ink. desirable.

These coloring materials may be dispersed in a non-aqueous solvent as the dispersed particles themselves, or may be contained in the dispersed resin particles, separately from the dispersed resin particles. In the case of containing, pigments and the like are generally coated with the resin material of the dispersed resin particles to obtain resin-coated particles, and dyes and the like are formed by coloring the surface of the dispersed resin particles into colored particles. General.

The resin particles dispersed in the non-aqueous solvent of the present invention, and also the colored particles and the like, preferably have an average particle diameter of 0.05 μm to 5 μm. It is more preferably 0.1 μm to 1.0 μm, and further preferably 0.1 μm to 1.0 μm.
The range is from μm to 0.5 μm. This particle size is CAPA-
500 (trade name, manufactured by Horiba, Ltd.).

The non-aqueous dispersed resin particles used in the present invention can be produced by a conventionally known mechanical pulverization method or polymerization granulation method. As the mechanical grinding method,
If necessary, a material as resin particles is mixed, melted and kneaded, and then directly pulverized by a conventionally known pulverizer to obtain fine particles, a dispersing polymer is used in combination, and a wet disperser (for example, a ball mill paint shaker) , Keddy mill, Dyno mill, etc.), a material to be a resin particle component,
A method of kneading a dispersion-assisting polymer (or a coating polymer) in advance to form a kneaded product, pulverizing the mixture, and then dispersing the mixture in the presence of a dispersing polymer, etc. Specifically, a method for producing a paint or a liquid developer for electrostatography can be used. For example, these methods are described in "Paint Flow and Pigment Dispersion" translated by Kenji Ueki, Kyoritsu Shuppan (1971), "Solomon , Paint Science, '' Paint and Surface Coating Theory and
Practice ", Yuji Harazaki" Coating Engineering "Asakura Shoten (1971), Yuji Harasaki" Basic Science of Coating "Maki Shoten (1977) and other books.

Examples of the polymerization granulation method include a conventionally known non-aqueous dispersion polymerization method. Specifically, the latest technology of ultrafine polymer supervised by Soichi Muroi, Chapter 2, CMC Publishing (1991) ), Koichi Nakamura, "Development and Practical Use of Recent Electrophotographic Developing Systems and Toner Materials", Chapter 3, (Nippon Scientific Information Co., Ltd., 1985), KEJ Barrett, "Dispersion Polyme"
rization in Organic Media "by John Wiley (1975).

Usually, in order to stabilize the dispersion of the dispersed particles in a non-aqueous solvent, a dispersed polymer is used in combination. The dispersed polymer contains a repeating unit soluble in a non-aqueous solvent as a main component, and has an average molecular weight of 1 × 10 in weight average molecular weight Mw.
^It is preferably ³ to 1 × 10 ⁶ , more preferably 5 × 10 ³
５5 × 10 ⁵ .

As a preferable soluble repeating unit of the dispersion polymer used in the present invention, a polymerization component represented by the following formula (V) can be mentioned.

[0119]

Embedded image

In the formula (V), X ₁ is -COO-,-
Represents OCO- or -O-.

R represents an alkyl or alkenyl group having 10 to 32 carbon atoms, preferably an alkyl or alkenyl group having 10 to 22 carbon atoms, which may be linear or branched, and unsubstituted. Those are preferable, but may have a substituent.

Specifically, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl, docosanyl, decenyl,
A dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linolel group and the like.

A ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, and a C 1 -C 1 atom.
3 alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), - COO-Z ¹ or -CH ₂ COO-Z ¹
[Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.)].

Specifically, Z ¹ represents a hydrogen atom or a hydrocarbon group. Preferred examples of the hydrocarbon group include an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group and an ethyl group). Group, propyl group, butyl group, heptyl group,
Hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group,
2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), having 4 to 4 carbon atoms.
18 alkenyl groups which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, a benzyl group, a phenethyl group,
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), and an optionally substituted aromatic group having 6 to 12 carbon atoms (For example, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl) , Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecylylamidophenyl, etc.) Listed .

In the dispersion polymer, another repeating unit may be contained as a copolymer component together with the repeating unit represented by the formula (V). As the other copolymer component, any compound may be used as long as it is composed of a monomer copolymerizable with a monomer corresponding to the repeating unit of the formula (V).

The proportion of the polymer component represented by the formula (V) in the dispersion polymer is preferably at least 50% by weight, more preferably at least 60% by weight.

Specific examples of these dispersion polymers include:
Dispersion stabilizing resin (Q-1) used in Examples,
(Q-2), (Q-3) and the like, and a commercially available product (Solprene 1205, manufactured by Asahi Kasei Corporation) can also be used.

When the above-mentioned resin (P) particles are produced as an emulsion (latex) or the like, the dispersion polymer is preferably added in advance during the polymerization.

When the dispersing polymer is used, the amount added is about 0.05 to 4% by weight based on the whole ink.

The dispersed resin particles and the colored particles (or the coloring material particles) in the oil-based ink of the present invention are preferably positively or negatively chargeable particles.

[0131] The particles can be imparted with an electric detecting property by appropriately utilizing a technique of a developer for wet electrostatography. Specifically, the above-mentioned “Recent development and practical use of electrophotographic development systems and toner materials”, pp. 139-148,
The Society of Electrophotography, "Basics and Application of Electrophotographic Technology" 497-
505 (Corona Co., 1988), Yuji Harasaki "Electrophotography" 16 (No. 2), page 44 (1977), and the like, using an electric test material and other additives.

More specifically, for example, British Patent No. 8934
No. 29, No. 934038, U.S. Pat. No. 112239
No. 7, No. 3900412, No. 460989,
JP-A-60-179751, JP-A-60-185963
And JP-A-2-13965.

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight with respect to 1000 parts by weight of the dispersion medium as the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electrical resistance of the oil-based ink. That is, if the electric resistance of the ink from which the dispersed particles are removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, it is necessary to control the amount of each additive within this limit. It is.

Next, a method of forming an image on the lithographic printing plate precursor (hereinafter, also referred to as “master”) will be described. FIG. 1 shows an example of an apparatus system for performing such a method.

The apparatus 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 2 is transmitted from an information source such as a computer 3 through a transmission means such as a bus 4 to an oil-based ink. Is supplied to the ink jet recording apparatus 1 that uses. 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.

[0137] Thus, the image formation on the master 2 is completed.
Obtain a plate making master (plate making printing plate).

FIGS. 2 and 3 show examples of the construction of an ink jet recording apparatus as in the apparatus system of FIG. 2 and 3, members common to 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 FIGS. 2 and 3, the head 10 provided in the ink jet recording apparatus has a slit sandwiched between the upper unit 101 and the lower unit 102. 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 the 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 to form an image on the master 2 provided on the counter electrode 10c. Is done.

The width of the discharge electrode 10b is preferably as narrow as possible to form a high-quality image, for example, for printing.

For example, the head 10 shown in FIG. 3 is filled with oil-based ink, the tip of the ejection electrode 10b having a width of 20 μm is used, and the distance between the ejection electrode 10b and the counter electrode 10c is set to 1.5 mm.
By applying a voltage of 3 KV between the electrodes for 0.1 millisecond, a dot of 40 μm can be formed on the master 2.

As described above, on the lithographic printing original plate,
A plate making master obtained by forming an image by an ink-jet method using an oil-based ink is subjected to a surface treatment with a desensitizing treatment liquid to desensitize a non-image portion to prepare a printing plate.

In order to perform the desensitization treatment, a deprotection reaction using a chemical optical active ray may be used in addition to the reaction using the treatment solution, or these may be used in combination. That is, in the resin (A) cross-linked by the desensitization treatment, -CO ₂ H
The functional groups, ie, the —SO ₃ H group and the PO ₃ H ₂ group, are decomposed and become hardly soluble or insoluble in water.

As the treatment liquid, an aqueous solution adjusted to a predetermined pH is usually used. A known pH adjuster can be used for adjusting the pH. The pH range to be applied may be any of acidic to neutral to alkaline.
The above alkaline region is preferred. As the compound to be used as the alkaline treatment liquid, any of conventionally known inorganic compounds or organic compounds may be used.For example, carbonate, sodium hydroxide, potassium hydroxide, potassium silicate, sodium silicate, an organic amine compound or the like alone or They can be used in combination.

Further, as a compound that can be used in combination to accelerate the hydrophilic reaction, a nucleophilic constant n of Pearson (RG Pearson & H. Sobel, J. Amer. Chem. So
c., 90, 319 (1968)] contains a substituent having a value of 5.5 or more, and dissolves at least 1 part by weight in 100 parts by weight of distilled water.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.) lead thiosulfate, etc., and a mercapto containing at least one polar group selected from a hydroxyl salt, a carboxyl salt, a sulfo group, a phosphono group, and an amino group in the molecule. Examples include compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as mercapto compounds, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) -2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenecarboxylic acid, 2-mercaptoenesulfonic acid, 2-mercaptoethylphosphonic acid, Mercaptobenzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl- 2-mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid The dicarboxylate benzene sulfinic acid, a hydrazide compound, 2- hydrazino ethanol sulfonic acid, 4-hydrazino butanoic acid,
Hydrazinobenzenesulfonic acid, hydrazinobenzoic acid,
Hydrazinobenzenecarboxylic acid or the like, primary or secondary
Examples of the secondary amine compound include N- (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, and tri (2-hydroxyethyl) ethylenediamine , N- (2,3-dihydroxypropyl) amine,
N, N-di (2,3-dihydroxypropyl) amine,
2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2-carboxyethylmorpholine, 3
-Carboxypiperazine and the like.

The amount of the nucleophilic compound present in these treatment liquids is preferably 0.05 to 10 mol / l, more preferably 0.1 to 5 mol / l. In addition,
The pH is preferably 8 or more.

The treating solution is composed of the above-mentioned nucleophilic compound and pH.
In addition to the regulator, other compounds may be contained. As described above, examples of the water-soluble organic solvent include alcohols (methanol, ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.) and ketones (acetone, methyl ethyl tetone, cyclohexanone, acetophenone, etc.). , Ethers (dioxane, trioxane, tetrahydrofuran,
Ethylene glycol dimethyl ether, propylene glycol diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc., amides (dimethylformamide, pyrrolidone, N-methylpyrrolidone, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate) , Ethyl formate, sulfolane, tetramethylurea, etc.)
And the like. These may be used alone or in combination of two or more.

Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, chaotic, or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi, “New Surfactants” (1975), published by Sankyo Publishing Co., Ltd., Ryohei Oda, Kazuhiro Teramura, “Synthesis of Surfactants and Their Applications” (1980, Maki Shoten) Can be used.
Furthermore, in order to improve the antiseptic property and the antifungal property during storage of the treatment liquid, a conventionally known antiseptic compound and antifungal compound may be used in combination. The treatment temperature is preferably 15 to 60 ° C., and the immersion time is preferably 10 seconds to 5 minutes. Further, at the time of processing, physical operations such as application of ultrasonic waves or mechanical sliding (rubbing with a brush or the like) may be used together.

On the other hand, light rays used for deprotection by irradiation with chemically active light rays include visible light rays,
Any of ultraviolet rays, far ultraviolet rays, electron beams, X-rays, γ-rays, α-rays and the like may be used.
It is a light beam in the range of 10 nm to 500 nm. Generally, a high-pressure or ultra-high-pressure mercury lamp or the like is used. The light irradiation treatment can usually be sufficiently performed by irradiation from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes. After the light irradiation in this manner, the printing plate can be easily obtained by dipping in the above-mentioned aqueous solution.

[0154]

EXAMPLES The present invention will be described in detail with reference to examples below, but the contents of the present invention are not limited to these examples.

First, a production example of the ink resin particles (PL) will be described.

Production Example 1 Production of Resin Particles (PL-1) A mixed solution of 10 g of a dispersion stabilizing resin (Q-1) having the following structure, 100 g of vinyl acetate and 384 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. Warmed. 2,2'-azobis (isovaleronitrile) as a polymerization initiator
0.8 g (abbreviation AIVN) was added and reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of this initiator was added, and after reacting for 2 hours, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to distill off 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 degree of polymerization of 90% and an average particle size of 0.23 μm and having good monodispersibility. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

A part of the white dispersion was centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 60 minutes), and the sedimented resin particles were collected and dried. The weight average molecular weight (Mw: GPC value in terms of polystyrene) of the resin particles is 2
× 10 ⁵ , and the glass transition point (Tg) was 38 ° C.

[0158]

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Production Example 2 Production of Resin Particles (PL-2) A mixed solution of 14 g of a dispersion stabilizing resin (Q-2) having the following structure and 382 g of Isopar G was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. 20 g of methyl methacrylate, 80 g of methyl acrylate and 2,2'-
A mixture of 0.8 g of azobis (2-cyclopropylpropionitrile) (abbreviated as ACP) was added dropwise for 1 hour, and the reaction was continued for another 1 hour. Further, A.
C. P. P. 0.8 g was added and reacted for 2 hours.
I. V. N. 0.8 g and heated to a temperature of 80 ° C. for 2 hours. I. V. N. 0.5 g was added and the reaction was carried out for 2 hours.

Next, the temperature was increased to 100 ° C.
After distilling off unreacted monomers under 〜20 mmHg, cool and cool
After passing through a 00 mesh nylon cloth, the resulting white dispersion was a latex having a degree of polymerization of 98% and an average particle size of 0.17 μm and having good monodispersibility. Mw of resin particles is 2 × 10 ⁵ ,
Tg was 30 ° C.

[0161]

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Production Example 3 Production of Resin Particles (PL-3) A mixed solution of 12 g of a dispersion stabilizing resin (Q-3) having the following structure and 553 g of Isopar H was heated to a temperature of 50 ° C. while stirring under a nitrogen stream.

To this were added 50 g of methyl methacrylate, 50 g of ethyl acrylate, 1.3 g of methyl 3-mercaptopropionate and A.I. C. P. P. 1.0 g of the mixture was added dropwise over 30 minutes, and the reaction was continued for another 1.5 hours. Further, A.I. C. P. 0.8 g of P was added and reacted for 2 hours. I. V. N. Add 0.8g and add temperature 8
Set at 0 ° C. for 2 hours, C. P. P. 0.5 g was added and the reaction was carried out for 2 hours.

After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was obtained at a conversion of 99% and an average particle size of 0.1%.
It was a 5 μm monodisperse good latex. The Mw of the resin particles was 3 × 10 ⁴ and the Tg was 37 ° C.

[0165]

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Production Example 4 Production of Resin Particles (PL-4) A styrene-butadiene copolymer having a softening point of 45 ° C. [(48/52) weight ratio] (Sorprene 303, Asahi Kasei Corporation) as the thermoplastic resin (A) The solid content is coarsely pulverized with a trib blender, 5 g of the pulverized material, 4 g of dispersion stabilizing resin (Solbren 1205, manufactured by Asahi Kasei Corporation) and 51 g of Isopar H. (Manufactured by Toyo Seiki Co., Ltd.) and preliminarily dispersed for 20 minutes. This pre-dispersion is treated with a Dynomill KDL type (Shinmaru Enterprises Co., Ltd.) using glass beads having a diameter of 0.75 to 1 mm as a medium.
And wet-dispersed at 4500 rpm for 6 hours. A white dispersion obtained by passing these through a 200 mesh nylon cloth was a latex having an average particle size of 0.35 μm. The Mw of the resin particles was 1 × 10 ⁵ .

Next, examples of the lithographic printing plate will be described.

Example 1 A mixture of 100 g of titanium oxide, 20 g of a resin (A-1) having the following structure and 250 g of toluene was mixed with a wet disperser homogenizer (manufactured by Nippon Seiki Co., Ltd.).
After dispersing at 1 × 10 ⁴ rpm for 10 minutes using
0.2 g of phthalic anhydride and 0.02 g of 0-chlorophenol were added to this dispersion, and the number of revolutions was 1 × 10 ^3.
Dispersed at rpm for 1 minute. .

Support for ELP-1 type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as electrophotographic lithographic printing plate precursor for light printing (smoothness of support underlayer: 500 (sec / 10 cc)) ), And the above dispersion was applied thereon using a wire bar, heated at 100 ° C. for 30 seconds, and further heated at 140 ° C. for 1 hour. The coating amount of the image receiving layer of the obtained printing plate precursor was 20 g / m ² , the porosity was 28%, and the Bekk smoothness of the surface was 200 (sec / 10 cc). The above printing original plate was used as a sample No. 1
And

[0170]

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The sample No. 1. In place of the ELP-1 type master support used as the water-resistant support in E.1,
Sample No. 1 was used except that a support of LP-1X type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) [smoothness of support underlayer: 1800 (sec / 10 cc)] was used. In the same manner as in Example 1, a lithographic printing original plate was obtained. This is the sample No. Let it be 2.

Further, the sample No. As No. 3, a commercially available direct-printing original plate having a hydrophilic image-receiving layer surface was used. Table 1 shows the results.

Sample No. With respect to 1 to 3, the contact angle with water and the smoothness on the surface of the image receiving layer were measured as follows.

1) 2 μl of distilled water was placed on the surface of the printing original plate, and the surface contact angle (degree) after 30 seconds was measured using a surface contact angle meter (CA-D, manufactured by Kyowa Interface Science Co., Ltd.). It was measured. The lower the value, the better the wettability to water and the more hydrophilic.

2) Smoothness of Image Receiving Layer Using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.), the printing master was smoothed (seconds / 10 cc) under the condition of an air volume of 10 cc.
Was measured.

Incidentally, the smoothness of the support shown above was also measured in the same manner.

Using the sample Nos. 1 to 3 of the lithographic printing plate precursor prepared as described above, a servo plotter DA8400 manufactured by Graphtec Co., Ltd. capable of drawing the output from a personal computer.
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) having the following content was applied to the lithographic printing plate placed on the counter electrode spaced 1.5 mm apart. ) And printing was performed.

<Oil-based ink (IK-1)> Dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 95/5)
(Weight ratio), 10 g of nigrosine and 30 g of Shellsol 71 were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

Preparation of Resin Particles for Ink 6 g (as solid content) of resin particles (PL-1) of Example 1, 2.5 g of the above nigrosine dispersion, FOC-1400 (Nissan Chemical Co., Ltd.)
15 g of octadecene-half-maleic acid octadecylamide copolymer 0.0
A black oil-based ink was prepared by diluting 8 g to 1 liter of Isopar G.

The image quality of the copied image of the plate-making product thus obtained was evaluated as follows. Table 1 shows the results.

3) Image quality of plate making The copied image of the plate making obtained was examined with an optical microscope for 200 hours.
It was observed and evaluated at a magnification of 1 ×. In the table, ◎, ○, △,
×, xx.

◎ There is no problem in the copied image, and fine lines and fine characters are very good. ○ There is no problem in the copied image, fine lines and fine characters are good. △ Fine lines and Mincho fine characters are slightly missing. , Fine lines and fine characters are slightly blurred and slightly defective × fine lines and fine characters are slightly missing, and fine lines and fine characters are slightly blurred and defective × × fine lines and fine characters of Mincho Extremely poor due to missing or blurring of thin lines and characters

Next, after making the plate as described above, the plate was immersed in a desensitizing solution (E-1) having the following content at a temperature of 35 ° C. for 20 seconds, and then sufficiently washed with water to prepare a lithographic printing plate. did.

Desensitizing solution (E-1) PS plate treating agent (DP-4, manufactured by Fuji Photo Film Co., Ltd.) 143 g N, N-dimethylethanolamine 80 g was diluted with distilled water to make the total volume 1 liter. (PH 1
2.3) Immersion water for PS plate (SG-23)
Using an aqueous solution (pH 7.0) obtained by diluting Tokyo Ink Co., Ltd.) with distilled water 130 times, using Oliver 94 type (manufactured by Sakurai Seisakusho) as a printing machine, and using neutral paper as printing paper. Then, printing was performed using various color printing inks.

However, the sample No. In No. 3, a surface of the image receiving layer was a hydrophilic printing plate precursor in advance, and printing was performed as it was without making it desensitized after plate making.

The printed images of these prints were evaluated as follows, and the printing durability was evaluated as follows. Table 1 shows the results.

4) Printed Image The printed image (ground fog, uniformity of the flat screen portion, uniformity of the image portion) of the tenth printed material was visually evaluated using a 20-fold loupe. In the table, they are indicated by △, △, Δ, ×, XX.

◎ There is no problem in the copied image, and fine lines and fine characters are very good. ○ There is no problem in the copied image, fine lines and fine characters are good. △ Fine lines and fine characters in Mincho font are slightly missing. , Slightly blurred fine lines and fine characters, slightly poor × fine lines and Mincho fine characters are slightly missing,
Fine lines and fine characters are slightly blurred and defective. ×× Fine lines and fine Mincho fonts are missing, or fine lines and fine characters are blurred and extremely poor. 5) Printing durability The number of printed sheets until the missing of the image could be visually discriminated was examined.

[0189]

[Table 1]

Consider the results in Table 1.

The sample No. The smoothness of the surface of the image receiving layer of each of Nos. 1 to 3 was almost the same value in Beck smoothness. Samples Nos. 1 and 2 had a high contact angle with water and were extremely hydrophobic. Sample No. 3 had a low contact angle with water and was extremely hydrophilic.

The image quality after plate-making is the same as that of sample No. 2 is very good and clear, and the sample No. The sample No. 1 had good reproducibility of fine lines and fine characters. That is, it shows that the higher the smoothness of the surface of the support underlayer adjacent to the image receiving layer, the better the plate-making image. However, sample No. In No. 3, image bleeding was remarkable in fine lines and fine characters. This is presumed to be due to the large affinity between the hydrophobic surface of the image receiving layer and the lipophilic ink.

Sample N prepared as a printing plate by desensitization
o. No. 1 and No. In No. 2, the desensitization of the non-image area was sufficient and no background stain due to the adhesion of the printing ink was observed, and a printing durability of 3000 or more was obtained. On the other hand, No. In No. 3, the printing durability of the printed matter was extremely poor.

Furthermore, the image quality of the printed matter obtained by offset printing using each plate as a printing plate is determined by the sample No. 1 and sample N
o. Sample No. 2 reproduced the same level as the plate-making quality, and 2,000 such sheets were obtained. On the other hand, sample No. In No. 3, the image blurred, and when printing was performed, about 50 sheets were missing. In addition, the printing plate of the present invention provided a clear image-free image of 3000 sheets or more in any case regardless of the type of the color ink.

Further, when printing was performed using the printing plate of the present invention and then printing was performed using the PS plate in the usual operation, no problem occurred. That is, it was confirmed that the same printing press can be easily shared with another lithographic printing press such as a PS plate.

Example 2 <Preparation of Water-Resistant Support> Using a high-quality paper having a basis weight of 100 g / m ² as a substrate, a coating for an under layer having the following composition was applied to one surface of the substrate using a wire bar. And dry coating amount 10
An under layer of g / m ² was provided. The smoothness of the under layer surface was 150 sec / 10 cc, and the smoothness was adjusted to 1500 (sec / 10 cc) by calendering.

<Coating for Under Layer> ・ 10 parts by weight of silica gel ・ 92 parts by weight of SBR latex (50 wt% aqueous dispersion, Tg 25 ° C.) 110 parts by weight of clay (45 wt% aqueous dispersion) 110 parts by weight ・ Melamine (80 wt% aqueous solution) 5 191 parts by weight of water 191 parts by weight Further, a coating material for a back coat having the following composition was applied to the other surface of the substrate using a wire bar, and the dry coating amount was 1
After providing a back coat layer of ² g / m ² , calender treatment was performed by setting calender conditions so that the smoothness of the back coat layer was about 50 (second / 10 cc).

<Coating for Back Coat Layer> 200 parts of kaolin (50% aqueous dispersion) 60 parts of aqueous polyvinyl alcohol solution (10%) 100 parts of SBR latex (solid content 49%, Tg 0 ° C.) 100 parts Melamine resin initial condensation 5 parts (solid content 80%, Sumiretz Resin SR-613) <Preparation of lithographic printing plate precursor> A mixture of 80 g of titanium oxide, 20 g of silica gel, 21 g of resin (A-2) having the following structure and 180 g of toluene was mixed with a homogenizer. After dispersing at 1 × 10 ⁴ rpm for 8 minutes, 0.3 g of pyromellitic anhydride and 0.01 g of acetylacetone zirconium salt were added to this dispersion, and the mixture was further rotated at 1 × 10 ^3.
Dispersed at rpm for 1 minute.

This dispersion was applied on the above-mentioned water-resistant support using a wire bar so as to have a coating amount of 15 g / m ² , heated at 110 ° C. for 20 minutes, and further heated at 140 ° C. for 1 hour. Thus, a lithographic printing original plate having a surface smoothness of 240 (sec / 10 cc) was prepared.

[0200]

Embedded image

This printing original plate was subjected to plate making in the same manner as in Example 1, and then treated with a desensitizing solution E-2 having the following contents to form a printing plate, and offset printing was performed.

Desensitizing solution (E-2) PS plate treating agent (DP-4 manufactured by Fuji Photo Film Co., Ltd.) 120 g Benzyl alcohol 50 g N-propylethanolamine 30 g was diluted with distilled water, and the total amount was 1 Liters (pH 1
2.4) The obtained printed matter is the sample No. of Example 1. As in the case of No. 2, the image quality was clear with no stain on the non-image area. 3000 or more sheets were obtained, and it was found that both the printed image and the printing durability were excellent.

Example 3 <Preparation of Water-Resistant Support> Aqueous latex of ethylene-methyl acrylate-acrylic acid copolymer (molar ratio 65: 30: 5) on both sides of a high-quality paper weighing 95 g / m ^2. Was applied and dried so that the dry coating amount was 0.2 g / m ^2, and the density was 0.920 g / cc and the melt index was 5.
70% of low density polyethylene with 0g / 10min, density 0.95
0 g / cc, 1.5 g of high-density polyethylene of 8.0 g / 10 min with a melt index of 15 g, and 15% of conductive carbon were laminated and extruded at a thickness of 25 μm by extrusion using pellets obtained by roasting and kneading. A layer (surface resistivity 6 × 10 ⁹ Ω) was provided. Next, the smoothness was adjusted to 2000 (seconds / 10 cc) by calendering.

Further, the other surface of the substrate was coated using a coating wire bar for a backcoat layer having the following composition, and a backcoat layer having a dry coating amount of 20 g / m ² (surface resistivity: 8 × 10 ⁷⁾
Ω), calendering was performed by setting calendering conditions so that the smoothness of the back coat layer was 450 (sec / 10 cc).

<Coating for Backcoat Layer> 200 parts by weight of clay (50% aqueous dispersion) 40 parts by weight of oxidized starch (20% aqueous solution) 150 parts by weight of SBR latex (solid content 49%, Tg10 ° C.) 150 parts by weight Melamine Resin precondensate 10 parts by weight (solid content 80%, Sumiretz Resin SR-613) Then, the surface of the polyethylene layer was coated with 5 KVA · sec / m ^2.
Under the conditions described above, a coating solution for an image receiving layer having the following composition was applied and dried to form an image receiving layer.

<Preparation of a lithographic printing plate precursor> Titanium oxide 10
0 g, 20 g of resin (A-3) having the following structure, 3 g of resin (B-1) having the following structure, and 155 g of toluene at a rotation speed of 1 × 10 ⁴ rpm using a wet dispersing machine Kedimill at a rotational speed of 1 × 10 ⁴ rpm.
Dispersed for 0 minutes.

[0207]

Embedded image

[0208]

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This dispersion was applied on the above-mentioned water-resistant support using a wire bar so as to have an application amount of 14 g / m ^2, and was dried by touching to a condition of a temperature of 50 ° C. and a humidity of 80% RH. The film was left to stand for 3 days to cure the film. The surface smoothness of the obtained lithographic printing plate precursor was 180 (sec / 10 cc).

This printing original plate was prepared in the same manner as in Example 1.
Plate making and desensitization treatment were performed to obtain a printing plate, and offset printing was performed. However, the oil-based ink (IK-
Instead of 1), the following oil-based ink (IK-2) was used.

<Oil-based ink (IK-2)> Ethyl methacrylate / dodecyl methacrylate (85/15 weight ratio) copolymer (resin glass transition point 4
5 ° C., Mw 5 × 10 ⁴ and carbon black # 40 (manufactured by Mitsubishi Kasei) as a color pigment were sufficiently mixed at a weight ratio of 1: 1 and then melt-kneaded in a three-roll mill heated to 100 ° C. . 12 g of this kneaded material was mixed with a styrene-butadiene copolymer (Solprene 1205, Asahi Kasei Corporation)
A mixture consisting of 4 g) and 76 g of Isopar G was dispersed with a Dynomill. The concentrated solution thus obtained was diluted with Isopar G so that the solid concentration became 6 g / liter, and sodium dioctyl sulfosuccinate was further added to 1 × 1.
0 to ⁴ mol / l was added to prepare a black oil-based ink.

[0212] The image quality of the plate thus produced was clear and excellent, as in the case of sample No. 2 of Example 1.

[0213] The printed matter obtained was the sample N of Example 1.
o. As in the case of No. 2, the image quality is clear with no stain on the non-image area, and 10,000 or more such images are obtained.
It was found that both the printed image and the printing durability were excellent.

(Examples 4 to 8) <Preparation of a lithographic printing plate precursor> 100 g of titanium oxide, 20 g of a resin (A (A-4 to 8)) shown in Table 2 below and toluene 1
Using a homogenizer, 50 g of the mixture was rotated at a rotation speed of 1 ×.
After dispersing at 10 ⁴ rpm for 10 minutes, 0.25 g of phthalic anhydride and 0.03 g of phthalic acid were added to the dispersion, and the mixture was further dispersed at 1 × 10 ³ rpm for 30 seconds.

Each of the obtained dispersions was applied to the same water-resistant support as used in Example 2 using a wire bar so as to have an application amount of 15 g / m ^2, and dried by touching. And further heated at 140 ° C. for 1 hour. The surface smoothness of each of the obtained printing original plates was in the range of 200 to 250 (sec / 10 cc).

[0216]

[Table 2]

These printing original plates were subjected to plate making and desensitization treatment to form printing plates in the same manner as in Example 1, and offset printing was performed.

The obtained printed matter was the sample N of Example 1.
o. As in the case of No. 2, the image quality was clear with no stain on the non-image area. 3000 or more sheets were obtained, and it was found that both the printed image and the printing durability were excellent.

(Examples 9 to 12) <Preparation of lithographic printing plate> Using the printing original plate prepared in the above example, a desensitizing treatment was performed as follows to prepare a lithographic printing plate. That is, distilled water was added to 0.2 mol of the nucleophilic compound, 30 g of the organic compound, and 2 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) shown in Table 3 below to make 1 liter, and the pH was adjusted to 12.5. Each treatment solution was adjusted. Each printing original plate was immersed in each processing solution at a temperature of 35 ° C. for 20 seconds, and subjected to a desensitization treatment while gently rubbing.
When printing was performed under the same printing conditions as in Example 1 using the obtained printing plate, the same good results as in Example 1 were obtained.

[0220]

[Table 3]

(Example 13) Sample No. 2 of Example 1
And plate-making and printing were performed in the same manner as in Example 1 except that the oil-based ink (IK-1) used in Example 1 was used instead of the oil-based ink (IK-3) described below.

<Oil-based ink (IK-3)> White dispersion (PL-1) 10 obtained in Production Example 1 of resin particles for ink
A mixture of 0 g and 1.5 g of Sumicalon Black was heated to a temperature of 100 ° C., and heated and stirred for 4 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, whereby a black resin dispersion having an average particle size of 0.24 μm was obtained.

The black oil-based ink was prepared by diluting 32 g of the above black resin dispersion, 0.05 g of zirconium naphthenate, and 10 g of FOC-1600 (hexadecyl alcohol, manufactured by Nissan Chemical Co., Ltd.) into 1 liter of Shellsol 71. Created.

[0224] The printed matter obtained was the sample N of Example 1.
As in the case of o. 2, the image quality was clear with no stain on the non-image area, and the printing durability was 3,000 or more.

(Example 14) In Example 2, the following oily ink (IK-4) was used in place of the oily ink (IK-1) used in Example 2 as the oily ink. Plate making and printing were performed in the same manner as in Example 1.

<Oil-based Ink (IK-4)> 10 g of poly (decyl methacrylate), 30 g of Isopar H and 8 g of alkali blue were placed in a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue. Obtained.

10 g (as solid content) of the white resin dispersion (PL-2) obtained in Production Example 2 of resin particles for ink, 4.2 g of the above-mentioned alkali blue dispersion, 10 g of isostearyl alcohol and [octadecyl vinyl ether] -Dodecylamide maleate] copolymer 0.0
By diluting 9 g to 1 liter of Isopar G, a blue oil-based ink was prepared.

As in Example 2, the obtained printed matter had a clear image quality with no stain on the non-image area, and had a printing durability of 1%.
0000 sheets or more were good.

(Examples 15 and 16) In Example 1, instead of the resin particles (PL-1) of the oil-based ink (IK-1) used in Example 1, resin particles (PL-3) (Example Oily inks were prepared in the same manner as in the oily ink (IK-1) except that 6.0 g (as solid content) of (15) and (PL-4) (Example 16) were used.

When plate making and printing were performed in the same manner as in Example 1 using each of the inks, any plate had the same image quality as that in Example 1, and the printing durability was 3000 sheets or more. there were.

[0231]

According to the present invention, a printing plate having a clear image and excellent printing durability can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus system used in the present invention.

FIG. 2 is a schematic configuration diagram illustrating a main part of an inkjet recording apparatus used in the present invention.

FIG. 3 is a partial sectional view of a head of an ink jet recording apparatus used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ink jet recording apparatus 2 Master 3 Computer 4 Pass 10 Head 10a Discharge slit 10b Discharge electrode 10c Counter electrode 11 Oil-based ink 101 Upper unit 102 Lower unit

Claims (5)

[Claims] 1. An image is formed by jetting oil-based ink from a nozzle into droplets on an image receiving layer of a lithographic printing plate precursor to form an image by an ink jet method, and then a non-image portion of the image receiving layer is subjected to a chemical reaction treatment. What is claimed is: 1. A method for producing an ink-jet type plate-making printing plate, comprising a desensitizing treatment and a lithographic printing plate having a hydrophilic surface, wherein the image receiving layer is on a water-resistant support, and is decomposed by a chemical reaction treatment. The resin (A) contains at least one functional group that forms at least one of a CO ₂ H group, a —SO ₃ H group and a PO ₃ H ₂ group, and is at least partially crosslinked. How to make an ink-jet type plate-making printing plate. 2. The resin (A) is decomposed to form --CO ₂
A copolymer component containing at least one functional group that produces at least one of an H group, a —SO ₃ H group and a PO ₃ H ₂ group, and when the group is produced by decomposition, water 2. The method according to claim 1, wherein the resin is a resin which is cross-linked in advance so as to be hardly soluble or insoluble in water. 3. The method according to claim 1, wherein the oil-based ink has an electric resistance of 10 ⁹ Ωcm.
The method for producing an ink-jet type plate making plate according to claim 1 or 2, wherein solid and hydrophobic resin particles are dispersed at least at room temperature in a non-aqueous solvent having a dielectric constant of 3.5 or less. 4. The method according to claim 1, wherein the resin particles in the oil-based ink are positive or negative voltage detecting particles. 5. The method of claim 1, wherein the surface of the support on the side adjacent to the image receiving layer has a Beck smoothness of 300 (sec / 10 cc) or more.