JPH1076625A - Method for forming ink jet plate making printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming an ink jet plate making printing plate for obtaining clear image printed matter and excellent plate wear resistance. SOLUTION: Normal temperature solid ink composition is hot-melted, droplet of ink is injected from a nozzle in this hot-melted state to form an image on an intermediate transfer, and an image is formed by a hot-melt ink jet system for forming an image by contact transfer on an image receptive layer of a lithographic printing original plate. Then, a non-image portion of the receptive layer is desensitized by chemical reaction treatment to form a hydrophilic surface of the printing plate. In this case, the receptive layer is disposed on a water resistant support, contains at least one type of functional groups for forming at least one group of-CO2 H group,-SO3 H group and PO3 H2 group by decomposition of chemical reaction treatment, and contains 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 system, and more particularly to a method for preparing a hot-melt ink-jet type plate-making printing plate having good plate making quality and printing quality. .

[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 for preparing a hot-melt 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 (4). (1) An ink composition which is solid at room temperature is melted by heat, and in this melted state, ink droplets are ejected from a nozzle to form an image on an intermediate transfer member. After forming an image by hot-melt inkjet method that forms an image by contact transfer on the image receiving layer, the non-image part of this image receiving layer is desensitized by a chemical reaction treatment and lithographic printing on a hydrophilic surface. A method for producing an ink-jet type plate-making printing plate to be a plate, 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 produces 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 above resin (A) is decomposed to have a —CO ₂ H group,
It contains a copolymer component containing at least one functional group that forms at least one of an SO ₃ H group and a PO ₃ H ₂ group, and is difficult to dissolve in water when the group is generated by decomposition. 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 dissolved or insoluble. (3) The method for producing an ink-jet type plate-making printing plate according to (1) or (2) above, 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. . (4) The ink composition is at least 50 to 150 ° C.
Containing a wax having a melting point of 80%, a resin, and a coloring material;
The above-mentioned (1) to (1), wherein the liquid becomes a hot-melt liquid by heating to a temperature of not less than 1 ° C.
(3) A method of preparing an ink-jet type plate-making printing plate of 3.

[0009]

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 kind of group and at least partially crosslinked on a water-resistant support, wherein an intermediate transfer member is formed on the image receiving layer. A hydrophobic ink image is formed by a hot-melt ink jet method via a hot melt ink jet method, and then the non-image area is hydrophilized. Therefore, an image is formed on the hydrophilic image receiving layer by a hot-melt ink jet method using a hydrophobic ink. Compared with the case, the image quality of both the plate-making image and the printed image of the original plate is remarkably improved, and additionally, the printing durability is also excellent.

[0010]

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

The ink-jet type plate-making printing plate according to the method of the present invention is provided on a water-resistant support, and is decomposed by a chemical reaction treatment to form -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 partly crosslinked resin (A) In addition, normal temperature of hydrophobic (35 ℃ or less)
Hot-melt ink-jet method or solid-jet method that forms an image by ejecting droplets from a nozzle in a hot-melt state, and forms an image via an intermediate transfer body After that, the non-image portion of the image receiving layer is subjected to a desensitizing treatment by a chemical reaction treatment to provide a lithographic printing plate that becomes a hydrophilic surface that can be flat printed during printing, and the formed image layer is Affinity with the image receiving layer which is adhered or adhered is sufficiently maintained, and a strong image portion which is unlikely to cause a missing or the like of the image layer is obtained.

In this case, the image receiving layer contains a resin (A) containing a functional group in which a hydrophilic group is protected, and its surface is hydrophobic, and is treated with a desensitizing solution to be hydrophilic by a chemical reaction. It is characterized by forming a group and modifying the surface to be hydrophilic so that the surface can be printed.

The degree of hydrophobicity of the surface of the image receiving layer is 50 ° or more in terms of contact angle with water, and is preferably 50 ° to 130 °, more preferably 50 ° to 120 ° in consideration of ink receptivity. °, particularly preferably 55 ° to 110 °.

When the contact angle with water is within the above range, the strength of the image layer as described above is sufficiently maintained, and a clear image is formed without disturbing the image such as fine lines, fine characters and halftone dots. Is done.

The contact angle is a value measured by a contact angle meter using a droplet method with distilled water.

On the other hand, the apparatus disclosed in Japanese Patent Application Laid-Open No. 64-27953 uses the solid jet method as in the present invention, but unlike the present invention, the surface of the image receiving layer of the printing original plate is hydrophilic. And the contact angle with water is 20 ° or less. In such a case, the image reproducibility is remarkably inferior and the printing durability is remarkably reduced as compared with the present invention.

In the present invention, the smoothness of the surface of the image receiving layer is preferably 30 (sec / 10 cc) or more, more preferably 45 to 300 (sec / 10), in Beck smoothness.
cc).

When the smoothness of the surface of the image receiving layer is within the above-mentioned range, a clear image with no image defects or the like is formed, and the adhesion between the image area and the image receiving layer is improved. The printing durability is significantly improved to 1000 sheets or more.

Here, the Beck smoothness can be measured by a Beck smoothness tester. A Beck smoothness tester is a tester in which a test piece is pressed at a constant pressure (1 kg / cm ² ) on a highly smooth finished circular glass plate having a hole at the center, and a fixed amount (10 cc) is obtained under reduced pressure. It measures the time required for air to pass between the glass surface and the specimen.

The effect of improving the adhesion between the image area and the image receiving layer and improving the printing durability is as follows: the smoothness of the surface of the image receiving layer is within the above range, and a solid ink composition at room temperature is used. It is particularly improved by using a material which contains a wax having a melting point of １５０150 ° C., a resin, and an adhesion modifier and becomes a hot melt liquid having a viscosity of 1 to 20 cps by heating to 80 ° C. or more. It is considered that the reason for this is that the affinity between the surface of the image receiving layer and the ink composition that has become a hot-melt liquid is increased, and the image reproducibility is improved without ink bleeding.

Further, in the present invention, the smoothness of the surface of the support on the side adjacent to the image receiving layer is determined by a Beck smoothness of 300.
(Seconds / 10 cc) or more can further improve image reproducibility and printing durability. Such an improvement effect can be obtained even if the smoothness of the image receiving layer surface is the same, and the adhesion between the image portion and the image receiving layer is improved by increasing the smoothness of the support surface. Conceivable.

Next, the image receiving layer will be described in detail.

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 functional groups represented by the following formula (I).

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

[0027]

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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 [the aliphatic group is an alkyl group. 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).

[0034]

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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.

[0036]

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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 that 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.

[0040]

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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).

[0043]

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

The specific examples (a-1) to (a-30) of the 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 10 to 90 wt.
% To more preferably about 15 to 80 wt%.

[0046]

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[0047]

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[0048]

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[0049]

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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

The functional groups required for the present invention can be arbitrarily adjusted in the polymer, 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.

[0056]

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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 ), 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,

[0058]

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[0059] -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

[0060]

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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 and vinyl acetate, as examples of monomers corresponding thereto.
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 cross-linked in the image receiving layer of the ink-jet type plate making plate.

The formula (I) contained in the resin (A)
When the functional group represented by (III) forms the hydrophilic group by decomposition, this 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 causes 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 the subsequent master production step. Preferably.

The crosslinkable functional group may be any one as long as it can cause a chemical reaction between molecules to form a chemical bond. 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)]

[0067]

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At least a combination of functional groups 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 in one copolymer component together with a hydrophilic group-forming functional group, 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, etc. 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 ratio of the “copolymer component containing a crosslinkable functional group” in the resin of the present invention is preferably 1% in the resin.
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 30 mol%, based on the copolymer component containing a crosslinkable functional group of the resin.

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

In the case of the reaction mode in which the 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.), 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 can be used.
%, More preferably about 0.1 to 25 mol%.

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

The average particle diameter of these inorganic pigment particles is usually preferably from 0.05 to 5 μm, more preferably from 0.1 to 3 μm.

The preferred 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 appropriate unevenness is 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 can be sufficiently retained as a printing plate at the time of printing, and high hydrophilicity can be maintained. .

The smoothness of the surface of the image receiving layer is preferably from 30 to 400 (sec / 10 cc), more preferably from 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. As a method of curing by light irradiation, a step of irradiating light with a chemically active ray may be included. 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, low-pressure, high-pressure or ultra-high-pressure mercury lamps, halogen lamps and the like are 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 applied amount of the image receiving composition per 1 m ² of the original plate (after drying).

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 provided 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 under layer 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.

Various methods known in the art can be used to set the smoothness within the above range. 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 way is 10 μm or more from the viewpoint of production stability. Preferably it is 10 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 material, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, an ethylene-acrylic ester 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.

The 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 support surface 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 is individually adjusted, for example, calendering is performed once after the underlayer is formed, and calendering 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 used for 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 of these. 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 original plate 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.

In order to prepare the lithographic printing plate precursor according to the present invention, a solution containing an underlayer component is coated on one side of the support, if necessary, and dried to form an underlayer. 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.

Next, a description will be given of a solid ink which is an ink composition which is solid at room temperature and which is used in a hot-melt type ink jet system (or a solid jet system).

As described above, the solid ink used in the present invention is a solid at a temperature of 35 ° C. or less, and has a temperature of 80 ° C. to 1 ° C.
It becomes a hot-melt liquid when heated to 50 ° C., and has a viscosity at the time of hot-melt in the range of 1 cps to 20 cps, preferably 2 cps to 15 cps, and a conventionally known liquid can be used.

More specifically, the hot-melt ink of the present invention comprises
30% of a wax which is solid at ordinary temperature and has a melting point of 50 ° C to 150 ° C, contains at least a resin, a coloring material, and an adhesion modifier, and preferably has a melting point of 50 ° C to 150 ° C. ~ 90wt%, resin is 5 ~ 70wt%,
0.1 to 10% by weight of dye or pigment as a coloring material,
The ink composition contains 2 to 40% by weight of an adhesion modifier.

Melting point 5 used as one component of vehicle
As a wax at 0 ° C. to 150 ° C., a so-called room-temperature solid wax, a wax that is thermally stable at least at the ink discharge temperature of an inkjet printer in a heated and melted state at a melting point or higher is used.

Examples of the wax include petroleum wax, preferably paraffin wax or microcrystalline wax; vegetable wax, preferably candelilla wax, carnauba wax, rice wax, or jojoba solid wax; animal wax; Preferably beeswax, lanolin or spermaceti; mineral waxes, preferably montan wax; synthetic hydrocarbons;
Preferably Fischer-Tropsch wax or polyethylene wax; hydrogenated wax, preferably hydrogenated castor oil or hydrogenated castor oil derivative;
Preferably a montan wax derivative, a paraffin wax derivative, a microcrystalline wax derivative or a polyethylene wax derivative; a higher fatty acid, preferably behenic acid, stearic acid, palmitic acid, myristic acid, or lauric acid; a higher alcohol, preferably stearyl alcohol; Or behenyl alcohol or;
Hydroxystearic acid, preferably 12-hydroxystearic acid or a 12-hydroxystearic acid derivative; ketone, preferably stearone or lauron; fatty acid amide, preferably lauric amide, stearic amide, oleic amide, erucamide,
Ricinoleic acid amide, 12-hydroxystearic acid amide, special fatty acid amide or N-substituted fatty acid amide; an amine, preferably dodecylamine, tetradecylamine or octadecylamine; an ester, preferably methyl stearate, octadecyl stearate;
Any of conventionally known waxes such as glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, or polyoxyethylene fatty acid ester; and polymerized wax, preferably α-olefin maleic anhydride copolymer wax; Can be used without any particular limitation. These waxes may be used alone or as a mixture of two or more kinds. It is desirable that the wax be contained in the range of 30 to 90% by weight based on the whole ink.

The resin used as a component of the vehicle together with the wax not only functions to impart adhesiveness to printing paper, control the viscosity of the ink, and further prevent crystallinity of the wax, but also imparts transparency to the ink. It also works to give.

The resin is preferably an oil-soluble resin. As the oil-soluble resin, for example, an olefin resin,
Preferably a polyethylene resin, a polypropylene resin or a polyisobutylene resin; or a vinyl resin, preferably an ethylene-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate copolymer resin or a vinyl acetate resin or ethylene-
Vinyl chloride-vinyl acetate resin; acrylic resin, desirably methacrylate resin, polyacrylate resin, ethylene-ethyl acrylate copolymer resin or ethylene-methacrylic acid copolymer resin; phenol resin; polyurethane resin; Polyamide resin, polyester resin, ketone resin, alkyd resin, rosin resin, hydrogenated rosin resin, petroleum resin, hydrogenated petroleum resin, maleic acid resin, butyral resin, terpene resin, Hydrogenated terpene resins; chroman-indene resins; and the like. These resins (polymer materials) may be used alone or as a mixture of two or more kinds.
Desirably, the content is in the range of wt%.

As the coloring material, any dyes and pigments conventionally used in oil-based ink compositions 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 dye, azo dye, metal complex dye,
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 an appropriate combination, but are preferably contained in the range of 0.1 to 10% by weight based on the whole ink. .

The adhesion modifier used effectively imparts plasticity and tackiness to the solid-state hot-melt ink without significantly changing the viscosity, melting point and melting energy of the ink as a whole. It functions to dramatically improve the fixing property to the recording sheet and the fixing property between the recording dots. Examples of the adhesion modifier include polyolefins and derivatives thereof (for example, polyolefin-based polyols) and the like.
Desirably, the content is in the range of ４０40 wt%.

In addition to the above, the ink of the present invention may contain various additives such as a dispersant and a rust preventive. The ink of the present invention is obtained by mixing the above materials in a heated state. The melting point of each ink can be set to various values by changing the type of constituent components to be used, and when mixing and using them, the mixing ratio.
The melting point of the ink can be measured by using a general melting point measuring device or a thermal analyzer such as DSC or DTA.

Next, a method for 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 system shown in FIG. 1 has an ink jet recording apparatus 1 of a solid jet system using solid 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 path 4 to a solid. The ink is supplied to the ink jet recording apparatus 1 based on the jet method. In the inkjet recording head unit 10 of the recording apparatus 1, the solid ink is melted and stored in an ink tank, and fine droplets of the ink are sprayed on the surface of an intermediate transfer body 28 described later in accordance with the information. Thus, the ink adheres to the surface of the intermediate transfer member 28 in the pattern. The adhesion thickness, that is, the thickness of the ink layer is usually 1 to 50
μm, preferably 3 to 35 μm.

FIGS. 2 to 4 show examples of the structure of an ink jet recording apparatus as in the apparatus system of FIG. 2 to 4, 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. The ink jet recording apparatus of FIG. 2 transfers an ink image from an intermediate transfer surface onto a master in a rapid process. The printhead 11 deposits the supported molten ink on the intermediate transfer member 28 in a fixed or movable state with a suitable housing and support elements (not shown). The intermediate transfer body 28 may be a web or a platen other than the drum, and may be formed of an appropriate material. The intermediate transfer member 28 is not particularly limited, but a metal containing aluminum, nickel, iron phosphate, or the like, an elastomer containing fluoroelastomer, perfluoroelastomer, silicon rubber, polybutadiene, or the like, or polyphenylene sulfide is added. Even when molded using plastic containing polytetrafluoroethylene, thermoplastic resin containing polyethylene, nylon, FEP (fluorinated ethylene / propylene resin), thermosetting resin such as acetal, ceramic, etc. good. Regardless of which material is used, the exposed surface of the intermediate transfer member 28 has sufficient hardness, and the master 2 can smoothly pass between the intermediate transfer member 28 and the transfer roller 32, and It does not matter as long as there is no problem in supporting the ink. A preferred material for the intermediate transfer member 28 is anodized aluminum. The surface has a Beck smoothness of 300 seconds / 10 cc or more, preferably 800 seconds / 10 cc or more, more preferably 1000 seconds / 10 cc.
More than 3000 seconds / 10cc or less is good.

The master guide 30 shown in FIG. 2 allows the master 2 to pass from a sheet feeding device (not shown) and guides the master 2 to an intermediate transfer section 37 sandwiched between the roller 32 and the intermediate transfer member 28. A plurality of strip fingers 38 (only one is shown) are provided in the printer device 10 so that the master 2 can be peeled off from the surface of the intermediate transfer body 28. The roller 32 has a core portion 33 made of metal (preferably made of steel), and is provided around the periphery thereof with an elastomer having a Shore D hardness of about 40 to 45. Suitable elastomeric materials can be silicone, urethane, nitrile, EPDM, or other elastic materials. The master 2 is pressed by the elastomer covering the rollers 32, and the ink image 36 is melted or fixed, and the ink image is expanded, extended and fixed.

The process, ie, the ink used in the system of the present invention, is initially solid and becomes liquid when heated to a temperature of about 85 ° C. to about 150 ° C. A rise in temperature outside of this range will cause ink degradation or chemical decomposition. The molten ink is ejected from the ink jet holes of the print head 11 onto the surface of the intermediate transfer member 28 in a raster scanning manner. Here, the ink cools and solidifies to a soft state, and is transferred to the master 2 sandwiched between the intermediate transfer body 28 and the roller 32 by contact transfer at the intermediate transfer unit 37. The temperature at which the ink is maintained in this flexible state is between about 30C and 80C.

The ink image in the soft state is applied to the roller 32.
When the ink image 36 is sandwiched between the intermediate transfer member 28 and the intermediate transfer member 28, the ink image 36 is deformed to a final image state, and the ink image 36 is fixed on the master 2 by the pressure from the roller 32 or by the heat from the heater 29 or the heater 31. . Further, a heater 34 may be provided to facilitate the processing at this point. The pressure applied to the ink image 36 is about 1 to
150 kgf / cm ² , more preferably about 30 to
About 100 Kgf / cm ² , the most preferred value being about 5
0 to about 60 Kgf / cm ² . This pressure must be strong enough to fix the ink image 36 to the master 2.

The ink image once fixed on the master 2 cools down to an environmental temperature of about 20 to 25 ° C. The ink in this ink image must be ductile and must be deformable without breaking even when maintained at a temperature above the glass transition temperature. Below the glass transition temperature, the ink becomes hard. The temperature of the transferred ink image which maintains the ductile soft state is in the range of about -10 ° C to 120 ° C, preferably 10 ° C to 90 ° C. That is, since the master 2 is usually porous as described above, the ink penetrates into the image receiving layer of the master 2 and is received.

In FIG. 2, the heater 29 may be a heat-dissipating resistance heater arranged as shown in the figure, but is best arranged in the intermediate transfer member 28. The heaters 31 and 34 are connected to the master guide 30 and the
They may be arranged in the fixing roller 32, respectively. The heater 29 reduces the temperature of the intermediate transfer member 28 from about 25 ° C. to about 100 ° C.
° C. A more desirable temperature range is about 40
° C to 80 ° C.

Preferably, the master 2 is preheated to about 70 ° C. to 130 ° C. by the heater 31 before fixing the ink image 36. With heater 34, the temperature of roller 32 is raised from about 25 ° C to about 200 ° C. The heater 34 may be provided inside the roller 32.

Ink is ejected from the ink jet head 11 onto the surface of the intermediate transfer member 28 as described above.

FIG. 3 is a schematic structural view of the head section 10 in the above-mentioned ink jet recording apparatus. As shown in FIG. 3, the head unit 10 is roughly composed of an ink jet head 11 and an ink tank 20. And a means 21 for heating and melting the solid ink 25,
Such a device uses, for example, a heating resistor. Here, an example using a heating resistor will be described. A heating resistor 21 is provided in the ink tank 20 of the head unit 10.
The ink 22 melted by the above is stored, and a tank cap 23 is attached to the ink tank 20. Further, the head unit 10 is provided with the inkjet head 1.
1 has an ink supply path 24 for supplying the molten ink 22 in the ink tank 20.

When the solid ink 25 is supplied to the ink tank 20 by an operator or the like, the solid ink 25 is heated and melted by the heating resistor 21 provided so as to surround the ink tank 20, and passes through the ink supply path 24. The ink is supplied to the inkjet head 11.

FIG. 4 is a schematic configuration diagram for explaining the ink-jet head 11. As shown in FIG.
The inkjet head 11 includes a nozzle 12, a pressure chamber 13, a piezoelectric element 14 that pressurizes ink in the pressure chamber 13,
It is composed of a common ink chamber 15, an ink supply port 15a, a heating resistor 21a for heating and maintaining the temperature of the molten ink 22, and an electrode 21b. The molten ink 22 supplied to the pressure chamber 13 from the common ink chamber 15 is kept at a temperature optimum for ink ejection by the heating resistor 21 a in the pressure chamber 13, and is ejected from the nozzle 12 by driving the piezoelectric element 14. You. Then, the jetted molten ink 22
After being attached to the intermediate transfer member 28, the image is transferred to the master 2,
Fixing is completed by penetrating into the master 2 and solidifying.

The above-described ink jet head 11
Has been described using an example in which an electromechanical transducer such as a piezoelectric element is used. However, the same effect can be obtained by using other pressing means such as a wire-type pressing mechanism. As the heating means, a heating means such as a ceramic heater can be used in addition to the heating resistor. The temperature of the molten ink 22 in the ink tank 20 may not be as high as the temperature of the ink in the pressure chamber 13 immediately before ejection. For this reason, the heating resistor 21 provided outside the ink tank 20 and the heating resistor 21a provided outside the pressure chamber 13 may be individually heated to suppress a rise in temperature in the ink jet recording apparatus.

On the other hand, when heating the ink tank 20 and the inkjet head 11 to the same temperature, the heating method is as follows.
May be individually heated by the heating resistors 21 and 21a as described above. However, a method in which the ink tank 20 and the inkjet head 11 are covered in a single housing by a heating mechanism incorporating a nichrome wire or the like may be adopted. Good.

[0138] The heating temperature of the head of the ink jet recording apparatus is set in the range of 80 ° C to 150 ° C, preferably 90 ° C to 130 ° C.

As the recording head, it is desirable to use a recording head capable of making full use of a technique using solid ink and having a high resolution.

For example, when a solid ink is supplied to the ink tank 20 of the ink jet recording apparatus shown in FIG. 3 and plate making is performed at a head heating temperature of 120 ° C., a piezoelectric element driving voltage of 70 V, and an ink viscosity at the time of ejection of 20 cps, a 40 μm nozzle is used. A sharp image can be formed at a resolution of 600 dpi by ejecting ink particles of 60 μm.

The ink image 36 on the surface of the intermediate transfer member 28 is cooled to the intermediate state of the rollable solid as the intermediate transfer member 28 rotates, and enters the intermediate transfer portion 37 between the roller 32 and the intermediate transfer member 28. Go. The ink image 36 is deformed to a final image state by applying pressure, and is transferred to the surface of the master 2. Thus, the ink image 36 is transferred to the master 2 by the pressure received from the elastic body surface of the roller 32.

As described above, on the lithographic printing plate precursor,
A plate making master obtained by forming an image by a solid jet method is subjected to surface treatment with a desensitizing solution to desensitize non-image portions 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 with 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.
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 solutions 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.

[0152]

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.

Example 1 100 g of titanium oxide, 20 g of resin (A-1) having the following structure
And a mixture of 250 g of toluene and a wet dispersion homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 1 × 10 ^4.
After dispersion at 10 rpm for 10 minutes, 0.2 g of phthalic anhydride and 0.02 g of 0-chlorophenol were added to this dispersion, and further dispersed at 1 × 10 ³ rpm for 1 minute. .

A support of ELP-1 type master (trade name, manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic planographic printing plate 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

[0155]

Embedded image

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 an air volume of 10 cc.
Was measured.

The smoothness of the support shown above was measured in the same manner.

Next, a Phaser 340JS printer (Sony-Tektronix), which is commercially available as a solid jet printer for forming an image on a recording medium via an intermediate transfer member, is used.
And a black solid ink (Instec Black: accessory to the printer) to make a lithographic printing plate precursor.

The printer is based on the configuration shown in FIGS. 2 to 4. The black solid ink contains a wax having a melting point of about 100 ° C., and is heated at a temperature of about 120 ° C. to melt the ink. The viscosity was about 20 cps.
The material of the intermediate transfer drum is anodized aluminum, and its Bekk smoothness is 3000 seconds / 10 cc.
That is all. The temperature of the intermediate transfer section was 50 ° C.

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 fine characters in Mincho font 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 There is a drop, or bleeding occurs in fine lines and fine characters, and is extremely poor. Next, after making the plate as described above, the plate is placed in a desensitizing solution (E-1) having the following content at a temperature of 35 ° C for 20 seconds. After immersion, the plate was sufficiently washed with water to prepare a lithographic printing plate.

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 of the tenth printed matter (ground fog, uniformity of the flat screen portion, and solidity of the image portion) 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 and 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.

[0172]

[Table 1]

Consider the results in Table 1.

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 shown in 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. Sample No. 2 had sufficient desensitization of the non-image area, no background stain due to the adhesion of the printing ink was observed, and a printing number of 2000 or more was obtained. On the other hand, No. In No. 3, the printing durability of the printed matter was extremely poor.

Further, 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. Further, the printing plate of the present invention provided a clear image-free printed image of 2000 sheets or more regardless of the type of the color ink in any case.

Further, when printing was performed using the printing plate of the present invention and then printing was performed using the PS plate in a normal 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> Fine paper weighing 100 g / m ² was used as a substrate, and an underlayer paint having the following composition was applied to one surface of the substrate using a wire bar. 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 of 25 ° C)-110 parts by weight of clay (45 wt% aqueous dispersion)-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 kaolin (50% aqueous dispersion) 60 parts polyvinyl alcohol aqueous solution (10%) 60 parts 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 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.

[0183]

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, and 2,000 or more such images were obtained, and it was found that both the printed image and the printing durability were excellent.

Example 3 < Preparation of Water-Resistant Support> An aqueous latex of ethylene-methyl acrylate-acrylic acid copolymer (molar ratio 65: 30: 5) was dried on both sides of a high-quality paper weighing 95 g / m ^2. After coating and drying so that the coating amount becomes 0.2 g / m ² , the density is 0.920 g / cc and the melt index is 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.

[0190]

Embedded image

[0191]

Embedded image

This dispersion was applied to the above 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 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.

[0194] The printed matter obtained 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, and 2,000 or more such images were obtained, and 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 on 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 was dried by touch. 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).

[0197]

[Table 2]

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

The printed material obtained 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, and 2,000 or more such images were obtained, and it was found that both the printed image and the printing durability were excellent.

Examples 9 to 12 < Preparation of a lithographic printing plate> A lithographic printing plate was prepared by using the printing original plate prepared in the above example and performing a desensitizing treatment as described below. 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.

[0201]

[Table 3]

[0202]

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 schematic configuration diagram showing a head section of an ink jet recording apparatus used in the present invention.

FIG. 4 is a schematic configuration diagram for explaining an ink jet head of a head section of the 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 part 11 Ink jet head 12 Nozzle 13 Pressure chamber 14 Piezoelectric element 15 Common ink port 15a Ink supply chamber 20 Ink tank 21, 21a Heating resistor 21b Electrode 22 Melt ink 23 Tank cap 24 Ink supply path 25 Solid ink 28 Intermediate transfer member 29 Heater 30 Master guide 31 Heater 32 Roller 33 Core part 34 Heater 36 Ink image

Claims (4)

[Claims] Claims: 1. An ink composition which is solid at room temperature is melted by heat.
In this hot melt state, an ink droplet is ejected from a nozzle to form an image on an intermediate transfer body, and the image of this intermediate transfer body is formed on the image receiving layer of the lithographic printing plate precursor by contact transfer to form an image by hot melt. After forming an image by the inkjet method, a non-image part of the image receiving layer is subjected to a desensitizing treatment by a chemical reaction treatment to produce a lithographic printing plate having a hydrophilic surface, and a method of producing an ink-jet type plate-making printing plate, The image receiving layer is on a water-resistant support, and has a function of generating at least one group of a —CO ₂ H group, a —SO ₃ H group, and a PO ₃ H ₂ group by decomposition in a chemical reaction treatment. A method for producing an ink-jet type plate making plate containing a resin (A) containing at least one group and at least a part of which is crosslinked. 2. The resin (A) is decomposed to form --CO ₂
A copolymer component containing at least one functional group that forms at least one of an H group, a —SO ₃ H group and a PO ₃ H ₂ group, and when the group is generated 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 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. 4. The method according to claim 1, wherein the ink composition has at least 50
4. An ink-jet method according to claim 1, which comprises a wax having a melting point of 150 [deg.] C., a resin and a coloring material, and becomes a hot-melt liquid by being heated to 80 [deg.] C. or higher, wherein the viscosity of the hot-melt liquid is 1 to 20 cps. How to make a printing plate.