JPH05294083A - Base plate for direct drawing type planographic printing and production of printing plate - Google Patents

Abstract

PURPOSE:To produce a base plate for direct drawing type planographic printing generating no uniform or spot-like scumming and enhanced in desensitizing properties as an offset base plate by adding one or more kind of a resin containing one or more kind of a polymer component having a functional group represented by a specific formula to the binder resin of the image receiving layer on a support. CONSTITUTION:A resin containing one or more kind of a functional group represented by formula I (wherein at least one of -X and -X' is an electron withdrawing group and -X and -X' may be came or different when the sum of the values of Hammett sigmap of them is 0.45 or more and R0 is a hydrogen atom or a 1-6C alkyl group) is added to a part or more of the binder resin of the image receiving layer of a base plate for direct drawing type planographic printing. By the addition of this resin, even when the resin develops hydrophilicity after desensitizing treatment, the printing base plate has water resistance. Therefore, the printing base plate has the image receiving layer good in smoothness and reproduces a copy image faithful to the original picture and, since the hydrophilicity of a non-image part is good, no scumming is generated and printing durability is excellent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor, more specifically to a direct-drawing lithographic printing plate precursor suitable as an office printing plate precursor, and a method for producing a printing plate from the printing plate precursor.

[0002]

2. Description of the Related Art At present, a direct drawing type lithographic printing original plate having an image receiving layer on a support is widely used as an office printing original plate. In order to carry out plate making, that is, to form an image on such a printing original plate, a method of drawing an oil-based ink by hand on the image receiving layer, or printing by a typewriter, an ink jet method or a transfer heat sensitive method is generally employed. In addition, a method of transferring and fixing a toner image formed on a photosensitive member to an image receiving layer through a process of charging, exposing and developing using a plain paper electrophotographic copying machine (PPC) has begun to be used in recent years. In any case, the printing original plate after plate making is
The surface is treated with a desensitizing solution (so-called etchant) to desensitize the non-image area, and then used as a printing plate for lithographic printing.

In a conventional direct drawing type lithographic printing plate precursor, a back surface layer was provided on one surface of a support such as paper, and an image receiving layer was provided on the other surface as a surface layer via an intermediate layer. The back surface layer or the intermediate layer is formed of a water-soluble resin such as PVA and starch, a water-dispersible resin such as a synthetic resin emulsion, and a water-proofing agent. A typical example of such a direct drawing type lithographic printing plate precursor is US Pat.
As described in Japanese Patent No. 532865, the image receiving layer mainly comprises a water-soluble resin binder such as PVA, an inorganic pigment such as silica and calcium carbonate, and a water-proofing agent such as a melamine-formaldehyde resin precondensate. It is configured as an ingredient.

[0004]

However, in the conventional printing plate thus obtained, in order to improve printing durability, the amount of the waterproofing agent added is increased or a hydrophobic resin is used. When the hydrophobicity is increased to improve the printing durability, the hydrophilicity is reduced and the printing stain is generated. On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is deteriorated. there were. Especially under high temperature environment of 30 ℃ or more,
The surface layer (image-receiving layer) is dissolved in the immersion water used for offset printing, and there are major drawbacks such as deterioration of printing durability and printing stains. Further, the lithographic printing plate precursor is one in which an oil-based ink or the like is drawn as an image portion on the image-receiving layer, and if the binding property between the image-receiving layer and the oil-based ink is not good, the hydrophilicity of the non-image portion is sufficient. Even if the above-mentioned print stain does not occur, there is a problem that the oil-based ink in the image portion is lost during printing, resulting in a decrease in printing durability.

The present invention solves the above-mentioned problems of the direct drawing type lithographic printing plate precursor. An object of the present invention is to provide a method for producing a direct-writing type lithographic printing original plate which is excellent in desensitizing property and does not cause spot stains as well as uniform stain stains on the entire surface as an offset master. Another object of the present invention is to improve the adhesiveness between the oil-based ink in the image area and the image-receiving layer, and keep the hydrophilicity of the non-image area sufficiently even if the number of printed sheets is increased during printing, thus causing scumming. do not do,
It is an object of the present invention to provide a method for producing a direct drawing type lithographic printing plate having high printing durability. A further object of the present invention is that the effect of the hydrophilicity of the non-image area is further improved, it is stable even when stored under extremely harsh conditions, and hydrophilicity is easily expressed in a short time during the hydrophilic treatment. It is an object of the present invention to provide a direct drawing type lithographic printing plate precursor and a method for producing a printing plate that can be produced.

[0006]

The present invention is directed to solving the above problems by providing an image-receiving layer on a support, and a binder resin of the image-receiving layer having a functional group represented by the following general formula (I). The problem is solved by a direct-drawing type lithographic printing plate precursor containing at least one resin containing at least one combination component. General formula (I)

[Chemical 3] [However, in the above formula (I), at least one of -X and -X 'is an electron-withdrawing group, and Ha of -X and -X' is
If the sum of the values of mmet σ _P is 0.45 or more,
R ₀ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.] In the present invention, at least one polymer component having a functional group represented by the above general formula (I) is used. The contained resin may be preliminarily cross-linked, and in this case, the resin has water resistance when it exhibits hydrophilicity by reacting with a hydrophilic treatment liquid, which is preferable. Further, the resin containing at least one kind of the polymer component having a functional group represented by the general formula (I) of the present invention further contains at least one kind of functional group which causes a curing reaction by heat and / or light. It may be a resin. Furthermore, in the present invention, a direct drawing type lithographic plate containing at least one resin containing at least one polymer component having a functional group represented by the above general formula (I) as a binder resin for the image receiving layer. After forming an image on the printing plate precursor, the non-image portion of the image-receiving layer is insensitive to a treatment liquid containing a hydrophilic compound containing a substituent having a nucleophilic constant n of at least a value of 5.5 or more. A method for producing a printing plate by subjecting it to an oily treatment is provided.

[0007]

According to the present invention, at least a part of the binder resin of the image receiving layer of the lithographic printing plate precursor for direct drawing comprises a resin containing at least one functional group represented by the general formula (I), and preferably, Since the binder resin in the image-receiving layer after film formation is cross-linked, it has water resistance even if the resin exhibits hydrophilicity after being subjected to desensitizing treatment as a printing original plate. The binder resin of the present invention exhibits hydrophilicity by a hydrolysis reaction during desensitizing treatment, but more preferably, by treating with a treatment liquid containing at least one nucleophilic reactive hydrophilic compound, It is desensitized, whereby the binder resin can exhibit hydrophilicity, and at the same time, it is characterized by being hydrophilic or insoluble or hardly soluble in water. As a result, the direct drawing type lithographic printing plate according to the present invention has good smoothness of the image receiving layer, reproduces a copied image faithful to the original image, and has good hydrophilicity in the non-image area, so that scumming is also prevented. It has advantages that it does not occur and the printing durability is excellent. Further, the lithographic printing plate precursor of the present invention is not affected by the environment at the time of plate-making processing, is very excellent in the preservability before the processing, and is characterized in that the hydrophilization processing is rapidly performed.

The binder resin containing the functional group represented by the general formula (I) contained in the image receiving layer of the present invention will be described. The functional group of the general formula (I) is characterized in that it undergoes a decomposition reaction by a desensitizing treatment to produce sulfinic acid. General formula (I)

[Chemical 4] In formula (I), -X and -X 'are the same as long as at least one of them is an electron-withdrawing group and the sum of Hammet's substituent constant σ _P values of -X and -X' is 0.45 or more. But it may be different. The Hammett σ _P value is usually used as an index for estimating the degree of electron withdrawing / donating of a substituent, and the larger it is on the + side, the stronger the electron withdrawing group is treated.
Specific numerical values for each substituent are described in Naoki Inamoto, "Hammett's Rule-Structure and Reactivity," Maruzen (1984) and the like. In addition, Hammet in this system
The σ _P value of is considered to be additive, and −X, −X ′
Both need not be electron withdrawing groups. Therefore, for example, when -X is an electron-withdrawing group, the other -X 'substituent may be any as long as the sum of the σ _P values of -X, -X' is 0.45 or more. There are no particular restrictions. Specific examples of -X and / or -X 'as an electron withdrawing group, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, _{etc.), - CF 3, -CN,} -NO 2,
-COR ', - COOR', - SO 2 R ' , and the like. However, R'represents a hydrocarbon group having 1 to 18 carbon atoms. Preferably an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, trifluoromethyl group, chloromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group,
2-ethoxyethyl group, 3-hydroxypropyl group, 2
-Methoxycarbonylethyl group, etc.), an alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group,
A heptenyl group, an octenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a 2-naphthylethyl group,
Methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms which may be substituted (eg cyclopentyl group, cyclohexyl group, cycloheptyl group etc.), aryl group which may be substituted ( For example, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group,
Bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.) and the like. Further, as the other substituents of -X and -X ', as described above, H of each substituent of -X and -X' can be used.
Any value may be used as long as the total number of the ammett substituent constant σ _P values is 0.45 or more. As a preferred example, a hydrogen atom,

[Chemical 5] Etc. Wherein R _1, R ₂ may be the same or different, represent a hydrogen atom or a hydrocarbon group, further R _1, R
_{When 2} is a hydrocarbon group, those having the same contents as R'described above can be mentioned. Further, -R ₀ in the formula (I) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group).

Specific examples of the functional group represented by the general formula (I) are shown below, but the scope of the present invention is not limited thereto. In a-1) to a-28), R is -C _h H.
_{2h + 1} (h represents an integer of 1 to 4).

[Chemical 6]

[Chemical 7]

[Chemical 8]

Examples of the copolymer component containing a functional group represented by the general formula (I) used in the present invention include those represented by the following general formula (II). General formula (II)

[Chemical 9] [In the above formula (II), Z is -COO-, -OCO-, -O.
-, -CO-,

[Chemical 10] _{-CONHCOO -, - CONHCONH-, CH 2} C
OO-, CH ₂ OCO-,

[Chemical 11] Represents. Y represents an organic residue bonded to or directly connected to -Z- and -W _0. further

[Chemical 12]

[Chemical 13] And -W ₀ may be directly bonded. -W ₀ is the general formula (I)
Represents a functional group represented by. a ₁ and a ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. ]

The general formula (II) will be described in more detail. Preferably Z is

[Chemical 14] Represents. However, r ₁ represents the same content as R ₁ and R ₂ .

Y is a direct bond for connection, or -Z- and -W ₀
Represents an organic residue linking. When Y represents an organic residue to be linked, this linking group represents a carbon-carbon bond which may be through a hetero atom (as a hetero atom, an oxygen atom,
Indicating a sulfur atom or a nitrogen atom), for example

[Chemical 15] And the like, each of which is composed of a single or a combination of bonding units (provided that r ₂ , r ₃ , r ₄ , r ₅ and r ₆ have the same contents as r ₁ ).

A ₁ and a ₂ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group). , Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
An optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group,
And an aryl group such as a chlorophenyl group).

Furthermore, in the general formula (II)

[Chemical 16]

[Chemical 17] And -W ₀ may be directly linked.

The following is represented by the general formula (II) of the present invention.

[Chemical 18] A specific example of the part is shown. However, the scope of the present invention is not limited to these. Also, example (b-1)
During ~ (b-17), b represents -H or -CH _3, n represents 2-8.

[Chemical 19]

[Chemical 20]

The resin containing the polymer component having a functional group represented by the general formula (I) of the present invention as described above can be synthesized by a conventionally known synthesis method. That is,
A method of polymerizing a functional group represented by the general formula (I) and a monomer having a polymerizable double bond group in the molecule (for example, a monomer corresponding to the repeating unit of the general formula (II)). And reacting a low molecular weight compound containing a functional group of the general formula (I) with a polymer compound containing a polymer component containing a functional group that chemically reacts with the low molecular weight compound (that is, a polymer reaction).
Therefore, a method of synthesizing is possible. It can be easily synthesized by a conventionally known method for synthesizing a sulfone compound in the above-described monomer synthesis or polymer reaction synthesis.
For example, "New Experimental Chemistry Course, Vol. 14, Synthesis and Reactions of Organic Compounds (III)," edited by The Chemical Society of Japan, p1761, Maruzen Co., Ltd.
(Published in 1978) and the like, and can be synthesized by a method similar to the method specifically described.

In the general formula (I) in the binder resin of the present invention,
The polymer component containing the indicated functional group is
When it is a united product, it is 50 to 99 weight in the total copolymer.
%, Particularly preferably 50 to 95% by weight. Well
The molecular weight of the polymer of the resin is 10³-10⁶, Especially 3
× 10³~ 5 x 10 ^FiveIs preferred.

The resin of the present invention may further have at least a part thereof crosslinked in the direct-drawing type lithographic printing plate precursor. As such a resin, a resin which has been cross-linked in advance during application of the image-receiving layer forming material in the plate making process may be used, or a resin containing a cross-linkable functional group which causes a curing reaction by heat and / or light. It may be used for crosslinking during the process of producing the lithographic printing plate precursor (for example, during the drying process).
Further, these may be used in combination.

When a resin in which a part of the polymer is pre-crosslinked (a resin having a crosslinked structure in the polymer) is used as the binder resin, the functional group of the above formula (I) contained in the resin is A resin that is hardly soluble or insoluble in an acidic or alkaline aqueous solution when it is subjected to desensitization treatment to exhibit hydrophilicity is preferable. Specifically, it has a solubility in distilled water of preferably 50% by weight or less, more preferably 10% by weight or less at a temperature of 20 to 25 ° C.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of a monomer containing a functional group of the above formula (I), a polyfunctional monomer (a monomer containing two or more polymerizable functional groups) or a polyfunctional oligomer is allowed to coexist. By a method of cross-linking between molecules by polymerizing, and a method of containing a functional group that promotes a cross-linking reaction in the polymer, and then polymerizing a compound containing a group of the above formula (I) to cross-link is there.

Specifically, a method of polymerizing a polyfunctional monomer with a monomer containing at least one functional group of the general formula (I) of the present invention, or the polyfunctional monomer is generally used. A polar group (for example, a functional group of formula (I)) (for example,

[Chemical 21] Etc.) to produce a copolymer, and then the resin of the present invention is produced by a method of introducing a low molecular weight compound containing a functional group of the general formula (I) by a polymer reaction. be able to.

Specifically as the polymerizable functional group,

[Chemical formula 22] Etc., but the monomer having two or more polymerizable functional groups is a monomer having two or more of the same or different polymerizable functional groups. Good.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohol ( For example, ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol # 200, # 400, # 60
0, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenols (eg hydroquinone, resorcin, catechol and their derivatives) Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinylamides or allylamides of:
A condensate of a polyamine (for example, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allylacetic acid, etc.) Can be mentioned.

As a polyfunctional monomer or oligomer having different polymerizable functional groups, for example, a carboxylic acid containing a vinyl group [for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propion] Acid, itaconiloyl acetic acid, itaconiloyl propionic acid, a reaction product of an alcohol or amine with a carboxylic acid anhydride (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. ) Etc. containing a vinyl group-containing ester derivative or amide derivative (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl). Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl oxycarbonyl methyloxycarbonyl ethyl ester acrylate, N- allyl acrylamide, N- allyl methacrylamide, N- Ariruitakon acid amide,
Methacryloylpropionic acid allylamide etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol etc.) and a condensate of a carboxylic acid containing a vinyl group, etc. Can be mentioned.

The monomer or oligomer having two or more polymerizable functional groups which can be used in the present invention is polymerized by using 20% by weight or less, preferably 15% by weight or less of the total monomers, and preliminarily crosslinked. Resin can be formed.

On the other hand, in the method of cross-linking a polymer containing a functional group which promotes a cross-linking reaction by a macromolecular reaction, the functional group can be a chemical bond between molecules to form a chemical bond. Either is fine. That is, it is possible to use a reaction mode in which a bond between molecules due to a condensation reaction, an addition reaction or the like or a cross-link due to a polymerization reaction is caused by heat and / or light. Specifically, functional groups {e.g. -COOH group having a dissociative hydrogen atom, -PO ₃ H ₂ group,

[Chemical formula 23] [R ₃ represents an aliphatic group, preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a dichloromethyl group, A trichloromethyl group, a trifluoromethyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a hydroxyethyl group, a 3-chloropropyl group, etc. or an -OR ₄ group (R ₄ is the same as the group of R ₃ ). Represents)], —OH group, —SH group, —NH.R ₅ group (R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. )}When,

[Chemical formula 24] Containing at least one combination of functional groups each selected from the group such as, or —CONHCH ₂ OR ₆
(R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group) or

[Chemical 25] (R ₇ represents —OR ₆ or an alkyl group having 1 to ₆ carbon atoms), a polymerizable double bond group and the like. Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Further, for example, Takeshi Endo, "Refinement of Thermosetting Polymers", CMC Co., Ltd. (published in 1986), Yuji Harasaki, "Latest Binder Technology Handbook", Chapter II-1, Comprehensive Technology. Center (1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" Chubu Business Development Center Publishing Department (1985), Eizo Omori "Functional acrylic resin"
Techno System (1985), Hideo Inui, Mototaro Nagamatsu "Photosensitive Polymer" Kodansha (1977), Takahiro Tsunoda "New Photosensitive Resin" Press Society Press (1981), G.
E.Green and BPStar, RJ Macro.Sci. Revs. Macr
Chem., C21 (2), pp. 187-273 (1981).
~ 82), CGRoffey "Photopolymerization of Sur
face Cortings ", A. Wiley Interscience Pub. (19
The functional groups, compounds, etc. cited in the review articles such as 1982) can be used.

These crosslinkable functional groups may be contained in one copolymer component together with the functional group represented by the general formula (I), or the copolymerization group containing the functional group of the formula (I). It may be contained in a copolymer component separate from the coalescence component.

Specific examples of the monomer corresponding to the copolymer component containing these crosslinkable functional groups include, for example, those functional groups copolymerizable with the polymer component of the general formula (II). Any vinyl compound may be included. Such vinyl compounds are described in, for example, “Polymer Data
Handbook [Fundamental Edition] ", Baifukan (1986), etc. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) ethyl form, α-
Chloro compound, α-bromo compound, α-fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α-chloro-β-methoxy compound, α, β-dichloro compound, etc. ), Methacrylic acid, itaconic acid, half-esters of itaconic acid, half-amides of itaconic acid, crotonic acid, 2-alkenylcarboxylic acids (for example, 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, dicarboxylic acid salts Examples thereof include a half-ester derivative of a vinyl group or an allyl group, an ester derivative of these carboxylic acids or sulfonic acids, and a compound having the crosslinkable functional group in the substituent of the amide derivative. The proportion of the "copolymer component containing a crosslinkable functional group" in the resin of the present invention is preferably 1 to 60% by weight based on the total amount of the binder resin. More preferably, it is 5 to 40% by weight.

A small amount of a light and / or thermosetting resin and / or a cross-linking agent may be contained in order to improve the curability of the film. The amount thereof used is 0.01 to 20 relative to 100 parts by weight of the total amount of the binder resin [A] (hereinafter sometimes abbreviated as resin [A]) containing a functional group of the formula (I) of the present invention. %, Preferably 0.1 to 15% by weight. The light and / or thermosetting resin may be any conventionally known curable resin, and examples thereof include a functional group-containing resin similar to the curable group described in the binder resin [A] of the present invention. Specifically, Takeshi Endo “Refining thermosetting polymers”
(CMC Co., Ltd., published in 1986), Yuji Harazaki "Latest Binder Technology Handbook" II-1 Ministry (General Technology Center,
1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Business Development Center Publishing Department, 198)
5 years), Eizo Omori "functional acrylic resin" (Technosystem, published in 1985) and the like, conventionally known resins are used.

As the cross-linking agent, a compound usually used as a cross-linking agent can be used. In particular,
Compounds described in "Crosslinking Agent Handbook", edited by Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook, Basic Edition", edited by The Society of Polymer Science, Baifukan (1986), etc. can be used. .. For example, organic silane compounds (for example, silane coupling agents such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc.), polyisocyanate compounds (For example, toluylene diisocyanate, o-
Toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate,
Polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Polymer poisocyanate isocyanate, etc.), polyol compound (eg 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane etc.), polyamine compound (eg, Ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxy titanate,
Tetrapropoxy titanate, isopropyl tristearoyl titanate, etc.), aluminum coupling compound (for example, aluminum butyrate, aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
"Epoxy Resin", edited by Hiroshi Kakiuchi, Shokoido (published in 1985),
"Epoxy resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (196
9)), melamine resin (for example, compounds described in “Yulia Melamine Resin” edited by Ichiro Miwa, Hideo Matsunaga, Nikkan Kogyo Shimbun (1969), etc.), poly (meta). Acrylate compounds (for example, compounds described in "Oligomer" Kodansha (Published in 1976) edited by Shin Ogawara, Takeo Saegusa, and Toshinobu Higashimura, Eizo Omori "Functional Acrylic Resin" Techno System (published in 1985), and the like. Further, a monomer containing a polyfunctional polymerizable group (vinyl methacrylate, allyl methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinic acid ester, divinyl adipate ester, diallyl succinic acid ester,
2-methylvinyl methacrylate, trimethylolpropane trimethacrylate, divinylbenzene, pentaerythritol polyacrylate, etc.) and the like.

As described above, the binder resin for the image receiving layer of the present invention is preferably used in a crosslinking reaction in the coexistence of a curable compound in a combination in which a chemical bond between polymer chains easily proceeds. For example, as a polymer reaction by a combination of functional groups, a well-known method can be mentioned, and the following Table 1
A combination of the functional group of group A and the functional group of group B as described above is exemplified. However, it is not limited to these.

[0033]

[Table 1] In Table -1, R ₈ represents an alkyl group. R ₉ ~ R ₁₁
Represents an alkyl group or an alkoxy group, and at least one of the substituents represents an alkoxy group.

In the present invention, the resin [A] having the functional group-containing polymer component represented by the general formula (I) further contains a polymer component having a "light and / or thermosetting functional group". May be. Examples of the "thermo / photocurable functional group" -containing monomer of the present invention include a monomer capable of copolymerizing with the monomer corresponding to the above-mentioned "polymer represented by the formula (II)". Any one may be used as long as it contains the curable functional group in the substituents in the body. The repeating units (c-1) to (c-32) are exemplified below as specific examples of the copolymer component containing the "thermo / photocurable functional group" of the present invention.

[0035]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to accelerate the crosslinking reaction in the image receiving layer film. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.),
Organometallic compounds (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, etc., dibutoxytin dilaurate, etc.), dithiocarbamic acid compounds (diethyldithiocarbamate, etc.), thiuram disulfide compounds (tetramethylthiuram disulfide, etc.), carboxylic acids Anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butylsuccinic anhydride, etc., 3,3 ′, 4,4′-tetracarboxylic acid benzophenone dianhydride, trimellitic anhydride, etc.) and the like can be mentioned. .. When the crosslinking reaction is a polymerizable reaction mode, a polymerization initiator (such as a peroxide and an azobis compound) can be used.

The binder resin having a crosslinked structure in the image-receiving layer can be formed by the method described above in the production of the resin of the present invention, or the functional group represented by the general formula (I). By using a resin containing a crosslinkable functional group that causes a curing reaction with heat and / or light as described above,
Crosslinking may be carried out in the process of forming the image receiving layer or in the process of heating and / or light irradiation before the desensitizing treatment.
Usually, it is preferable to carry out crosslinking by thermosetting treatment. This heat curing treatment can be carried out by making the drying conditions strict when the conventional direct-writing type lithographic printing plate precursor is prepared. For example, the treatment may be performed at 60 ° C. to 120 ° C. for 5 minutes to 120 minutes. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method for curing a specific functional group in the resin of the present invention by irradiation with light, a step of irradiation with "chemically active light" may be included. The "chemically active light ray" used in the present invention may be any of visible light ray, ultraviolet ray, far ultraviolet ray, electron beam, X-ray, γ ray, α ray, and the like, and preferably ultraviolet ray. More preferably,
It can emit light in the wavelength range of 310 nm to 500 nm, and generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. The light irradiation process is usually 10 seconds to 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 minutes is sufficient.

A conventionally known resin can be used in combination with the binder resin used in the present invention described above. For example, the above-mentioned silicone resin, alkyd resin, vinyl acetate resin, polyester resin, styrene-butadiene resin, acrylic resin and the like can be mentioned. Specifically, Ryuji Kurita and Jiro Ishiwatari, Kogaku, Vol. 17, Vol. 278 Page (19
68), Harumi Miyamoto, Hidehiko Takei, Imaging, 197
3 (No. 8) page 9 and the like include cited publicly known materials. The resin according to the present invention and a known resin can be mixed in any proportion, but the content of the functional group component of the present invention in the total amount of the resin is 1 to 95% by weight, preferably 5 to 90%.
Must be contained by weight percent.

The above-mentioned binder resin of the present invention has the effect of improving the hydrophilicity of the non-image area by developing the hydrophilic group by the desensitizing treatment. Further, in the original plate of the present invention, when the binder resin has a crosslinked structure in at least a part of the polymer, the hydrophilic group-containing resin produced by the desensitizing treatment becomes water-soluble while maintaining hydrophilicity It also has a function of preventing elution from the part, that is, water resistance. Therefore, the effect of further enhancing the hydrophilicity of the non-image area by the hydrophilic group formed in the resin is improved and the durability is improved. Alternatively, even when printing conditions such as an increase in the size of a printing machine or fluctuations in printing pressure become strict, it is possible to print a large number of prints with clear image quality without scumming.

An inorganic pigment is used as another component of the image receiving layer of the present invention, and examples of the inorganic pigment include kaolin clay, calcium carbonate, silica, titanium oxide, and the like.
Examples thereof include zinc oxide, barium sulfate, and alumina. The ratio of the binder resin / pigment in the image receiving layer varies depending on the type of material and the particle size of the pigment, but is generally 1 / (0.5 to 5) by weight, preferably 1 / (0.8). ~ 2.
About 5) is appropriate.

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. As the cross-linking agent, commonly used ammonium chloride, organic peroxide,
A metal soap, an organic silane, a polyurethane crosslinking agent, an epoxy resin curing agent, or the like can be used. Specific examples include those described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), and the like.

Examples of the support used in the present invention include high-quality paper, wet reinforced paper, plastic film such as polyester film, and metal plate such as aluminum plate.

In the present invention, an intermediate layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a back coat layer is provided on the side of the support opposite to the image receiving layer for curling prevention. (Back surface layer) can be provided. Here, the intermediate layer is an emulsion resin such as acrylic resin, ethylene-butadiene copolymer, methacrylic acid ester-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, epoxy resin, polyvinyl butyral. , A solvent-based resin such as polyvinyl chloride or polyvinyl acetate, or a water-soluble resin such as those described above as a main component, and if necessary, an inorganic pigment or a waterproofing agent may be added. it can. The structure of the back coat layer is almost the same as that of the intermediate layer.

When used as a PPC plate-making, in order to further reduce the background stain of the printing original plate of the present invention, an image receiving layer is further added so that the volume resistivity of the printing original plate becomes 10 ¹⁰ to 10 ¹³ Ωcm. A dielectric agent can be added to the intermediate layer and / or the back coat layer. The dielectric agent may be an inorganic type or an organic type, and if it is an inorganic type, it may be one of Na, K, Li, Mg, Zn, Co, Ni and the like.
Polyvalent or polyvalent metal salts, and in the case of organic type, polyvinyl benzyl trimethyl ammonium chloride, high molecular cationic conductive agents such as acrylic resin-modified quaternary ammonium salts and high molecular anionic dielectric agents such as high molecular sulfonates. Can be mentioned. The amount of these conductive agents added is 3 to 40% by weight of the amount of binder used in each layer, preferably 5 to 2%.
It is 0% by weight.

In order to prepare the direct drawing type lithographic printing plate precursor of the present invention, generally, an aqueous solution containing an intermediate layer component is applied and dried on one surface of a support to form an intermediate layer, and then an image receiving layer. An aqueous solution containing the components is applied and dried to form an image receiving layer,
If necessary, an aqueous solution containing a backcoat layer component may be applied to the other surface and dried to form a backcoat layer.
Incidentally image receiving layer, an intermediate layer, the deposition amount of the back coat layer, respectively ^{1~30g / m 2, 5~20g / m} 2 are suitable.

A printing plate using the direct drawing type lithographic printing plate precursor of the present invention is prepared by forming and fixing an image on the direct drawing type lithographic printing plate precursor having the above-mentioned structure by a known technique,
After desensitizing the non-image area by surface treatment with a desensitizing solution,
Used as a printing plate for lithographic printing.

As a method for desensitizing the binder resin of the present invention containing a functional group represented by the general formula (I) (that is, imparting hydrophilicity), an aqueous solution of pH 8 to 14, preferably pH 10 is used.
There is a method of performing alkaline hydrolysis with an aqueous solution of -13. Further, it can be achieved by treating with a solution (aqueous solution or a mixed solution of a water-soluble organic solvent) having a compound containing a hydrophilic group which easily undergoes a nucleophilic reaction with a sulfonyl group under the above pH conditions. Examples of the hydrophilic compound that undergoes a nucleophilic substitution reaction on the functional group represented by the general formula (I) include Pearso (Pearso).
n) nucleophilic constant n [R. G. Pearson, H. Sobel, J. So
ngstad, J. Amer. Chem. Soc., 90 , 319 (196).
8)] is a hydrophilic compound containing a substituent having a value of 5.5 or more and soluble in 1 part by weight or more in 100 parts by weight of distilled water. Specific compounds include, for example, hydrazine, hydroxylamine, sulfites (ammonium salt, sodium salt, potassium salt, zinc salt, etc.), thiosulfate salt, and the like.
A mercapto compound, a hydrazide compound, a sulfinic acid compound containing at least one polar group selected from a carboxyl group, a sulfo group, a phosphono group and an amino group.
Examples thereof include secondary amine compounds and secondary amine compounds.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic 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 Dicarboxybenzenesulfinic acid and the like, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid and the like as hydrazide compounds As the primary or secondary amine compound, for example, N- (2-hydroxyethyl) amine, N,
N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, 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
-Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

These nucleophilic compounds are used by being contained in a treatment liquid for treating the binder resin. The amount of the nucleophilic compound present in these treatment liquids is 0.1 mol / liter to 10 mol.
Mol / l, preferably 0.5 mol / l
It is 5 mol / liter. The processing condition is a temperature of 15 ° C
The immersion time at 60 ° C. is preferably 10 seconds to 5 minutes. The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. For example, a water-soluble organic solvent may be contained in 1 to 50 parts by weight in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, Trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), etc. These may be used alone or in admixture of two or more. Further, the surfactant is added in an amount of 0.1 to 100 parts by weight of water.
You may contain 20 weight part. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, Hiroshi Horiguchi "New Surfactant" Sankyo Publishing Co., Ltd. (Published in 1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (198
The compounds described in, for example, 0 years) can be used.
The scope of the present invention is not limited to the specific compounds described above.

[0051]

EXAMPLES Examples of the present invention will be illustrated below.
The content of is not limited to these. Synthesis Example of Resin [A] 1: Resin [A-1] 89 g of a monomer (M-1) having the following structure, glycidylmethac
Relate 10 g, acrylic acid 1.0 g and toluene 20
While stirring 0 g of the mixed solution under a nitrogen stream, the temperature was 60 ° C.
Warmed to. 2,2'-azobis (isovaleronitri
4 hours (adding 0.8 g) (hereinafter abbreviated as A.I.V.N.)
React, add 0.5g A.I.V.N. and react for 3 hours
It was The weight average molecular weight of the obtained polymer [A-1] is
7.3 x 10 ^FourMet. Monomer (M-1)

[Chemical 35] Resin [A-1]

[Chemical 36]

Synthesis Example 2 of Resin [A]: Resin [A-2] 90 g of monomer (M-2) having the following structure, 5 g of glycidyl methacrylate, and 5-hydroxyethyl methacrylate 5
A mixed solution of g and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. While stirring, 1.0 g of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added and reacted for 4 hours, and 0.4 g of AIBN was further added and reacted for 3 hours. The weight average molecular weight of the obtained polymer [A-2] was 4.3 × 10 ⁴ . Monomer (M-2)

[Chemical 37] Resin [A-2]

[Chemical 38]

Synthesis Example 3 of Resin [A]: Resin [A-3] 88 g of a monomer (M-3) having the following structure, 10 g of 3- (triethoxysilyl) propyl methacrylate, 2.0 g of divinylbenzene and 200 g of toluene. The mixed solution of was heated to a temperature of 60 ° C. under a nitrogen stream. AIVN under stirring
1.5 g was added and reacted for 4 hours. Further AIVN 0.5
g and reacted for 3 hours. The weight average molecular weight of the obtained polymer [A-3] was 2 × 10 ⁵ . Monomer (M-3)

[Chemical Formula 39] Resin [A-3]

[Chemical 40]

Synthesis Examples 4 to 16 of Resin [A]: [A-4]
~ [A-16] Each polymer in Table 2 below was synthesized in the same manner as in the synthesis example of the resin [A-1]. Each of the obtained polymers [A-4] to [A-
16] had a weight average molecular weight of 5 × 10 ^{4 to} 7 × 10 ⁴ .

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

Synthesis Examples 17 to 24 of Resin [A]: [A-1
7] to [A-24] In the synthesis example of the resin [A-3], divinylbenzene 2.
A polymer was synthesized in the same manner as in the synthesis example of [A-3] except that the polyfunctional monomer shown in Table 3 below was used instead of 0 g. The weight average molecular weight of the obtained polymers [A-17] to [A-24] was in the range of 8 × 10 ⁴ to 2 × 10 ⁵ .

[0061]

[Table 7]

Example 1 40 g of resin [A-1] (as solid content) and zinc oxide were placed on an intermediate layer of a support in which a back surface layer was provided on one surface of high-quality paper and an intermediate layer was provided on the other surface. 50 g and toluene 150
g of the mixture was dispersed in a ball mill for 2 hours, to which 0.3 g of phthalic anhydride and 0.0 of o-chlorophenol were added.
05 g was added and dispersed for 5 minutes. The thus-obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g / m ² , dried at 100 ° C. for 30 seconds, and then further dried.
A lithographic printing plate precursor was prepared by heating at 40 ° C. for 1 hour. This original plate was treated with a desensitizing treatment solution (E-
It was immersed in 1) for 20 seconds and then washed with water. Desensitizing treatment liquid (E-1) Monoethanolamine 50 g Benzyl alcohol 10 g Emalbon T-20 (manufactured by Toho Chemical Co., Ltd.) 1 g was dissolved in 1 liter of distilled water, and the pH was adjusted to 1 with potassium hydroxide.
Adjusted to 3.0. Place 2 μl of distilled water on it,
The contact angle with the formed water was 0 ° when measured with a goniometer. This indicates that the non-image area of the image receiving layer of the original plate of the present invention changed from lipophilicity to hydrophilicity (usually, the non-image area during printing does not generate print stains or dot stain towers). The degree of conversion is 20 in terms of contact angle with water.
° or less).

Next, a plate was made with a commercially available PPC, and the obtained original plate was subjected to a desensitizing treatment under the same conditions as above to obtain a printing plate. The density of the image area of the obtained printing plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This was applied to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) and printed on high-quality paper. 500
Even if the number of sheets exceeds 0, there is no problem in the background stain of the non-image area and the image quality of the image area of the printed matter. Furthermore, using each of the above original plates,
When an environmental condition of 30 ° C. and 80% RH was used for plate making with a commercially available PPC, the image of the obtained printing plate had a density of 1.0 or more in the image area, no background fog in the non-image area, and The image quality was also clear. When this was printed in the same manner as above, there was no problem even if 5000 sheets were printed. As described above, the original plate did not deteriorate the image quality by PPC plate making even under the condition of high temperature and high humidity.

Examples 2 to 11 Example 1 was repeated except that 40 g of each resin [A] shown in Table 4 below was used instead of 40 g of the resin [A-1] in Example 1.
Each original plate was prepared in the same manner as.

[0065]

[Table 8]

These original plates were subjected to plate making and printing in the same manner as in Example 1. The density of the image area of the obtained printing plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This was applied to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) and printed on high-quality paper. Even if the number of sheets exceeds 5,000, there is no problem in the background stain of the non-image area of the printed matter and in the image quality of the image area. Further, when each of the above-mentioned original plates was subjected to plate making with a commercially available PPC under the environmental conditions of 30 ° C. and 80% RH, the image of the obtained printing plate had a density of 1.0 or more in the image area and a non-image area. There was no background fog and the image quality of the image area was clear. When this was printed in the same manner as above, there was no problem even if 5000 sheets were printed. As described above, these original plates did not deteriorate the image quality in PPC plate making even under high temperature and high humidity conditions.

Examples 12 to 21 On the intermediate layer of a support having a back surface layer on one surface of a wood free paper and an intermediate layer on the other surface, 5 g of resin [B] in Table 5 below, A mixture of 35 g of the resin [A] of -6 (as solid content), 10 g of zinc oxide and 100 g of toluene was dispersed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 ³ rpm for 5 minutes. Further, the crosslinking compound shown in Table 6 below was added to the mixture at a rotation speed of 1 × 10 ³ rpm for 1
After dispersing for a minute, the resulting dispersion has a dry coverage of 18 g.
/ M ² was applied with a wire bar and dried at 140 ° C. for 1 hour to prepare a lithographic printing original plate.

[0068]

[Table 9]

[0069]

[Table 10]

[0070]

[Table 11]

This original plate was operated in the same manner as in Example 1,
Plate making and printing were performed. The density of the image area of the obtained printing plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This was applied to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) and printed on high-quality paper. Even if the number of sheets exceeds 5,000, there is no problem in the background stain of the non-image area of the printed matter and in the image quality of the image area. Further, when using the above-mentioned original plate and making the plate with a commercially available PPC under the environmental conditions of 30 ° C. and 80% RH, the image of the obtained printing plate is
The density of the image area was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. When this was printed in the same manner as above, there was no problem even if 5000 sheets were printed.

Examples 22 to 26 8 g of each resin [B] shown in Table 7 below and each resin [A] shown in Table 8 below.
A mixture of 32 g, 5 g of silica gel, 5 g of alumina and 80 g of toluene was dispersed in a ball mill for 2 hours, and the crosslinking compound shown in Table 8 below was added and dispersed for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g / m ² , dried by touch with a finger, and then heated at 140 ° C. for 1 hour to prepare a lithographic printing plate precursor.

[0073]

[Table 12]

[0074]

[Table 13]

[0075]

[Table 14]

This printing plate was subjected to plate making and printing in the same manner as in Example 1 except that the desensitizing treatment liquid (E-2) prepared by the following formulation was used as the desensitizing treatment liquid. It was Desensitizing treatment solution (E-2) Sodium sulfite 52 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 3 g Benzyl alcohol 80 g These were dissolved in distilled water to make the total volume 1 liter,
The pH was adjusted to 13.0 with sodium hydroxide. The density of the image area of the obtained original plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This is offset printing machine (Oliver 52 type made by Sakurai Seisakusho Co., Ltd.)
And printed on wood free paper. Even if the number of sheets exceeds 5,000, there is no problem in the background stain of the non-image area of the printed matter and in the image quality of the image area. Furthermore, using the original plate, the environmental conditions are 30 ° C,
When 80% RH was used to make a plate with a commercially available PPC, each printing plate had a contact angle with water in the non-image area of 10 ° or less and was sufficiently hydrophilized. Even when the printing plate number was 5000, the print quality of the printed matter was good with a clear image without fog.

Example 27 In place of 40 g of resin [A-1] in Example 1, 33 g of resin [A-14] and resin [B-1 of the following structure:
7] An original plate was prepared in the same manner as in Example 1 except that 7 g was used. Resin [B-17]

[Chemical 41]

This material is 30 cm with a 400 W high pressure mercury lamp.
After irradiating light from the place for 3 minutes, in the dark at 20 ℃, 65% R
A lithographic printing plate was prepared by leaving it under H condition for 24 hours. A plate was prepared in the same manner as in Example 1,
The density of the obtained printing plate was 1.2 or more, and the image quality was clear. Furthermore, when an etching treatment was performed and printing was performed by a printing machine, the printed matter after printing 5000 sheets had fog in the non-image area and the image was clear.

Examples 28 to 39 0.5 mol of the nucleophilic compound shown in Table 9 below, 100 organic solvents
g and Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.)
Distilled water was added to 3 g to make 1 liter, and then the pH of each mixture was adjusted to 13.0 to prepare a treatment liquid. Example 1
Each of the printing original plates prepared in No. 21 to No. 21 was immersed in the above processing solution at a temperature of 40 ° C. for 1 minute to be desensitized, and then, in Example 1.
Printing was performed under the same printing conditions as.

[0080]

[Table 15]

The density of the obtained printing plate was 1.0 or more, and the image quality was clear. Further, the image quality of the printed matter after printing 5000 sheets was a clear image without background fog.

[0082]

As described above, according to the present invention, a direct drawing type lithographic printing plate precursor and a printing plate which are excellent in image acceptability and do not change with time can be obtained. Further, a printing original plate having very good printing characteristics can be obtained.

Claims (4)

[Claims] 1. A resin having an image-receiving layer on a support, wherein the binder resin of the image-receiving layer is a resin containing at least one polymer component having a functional group represented by the following general formula (I). A direct drawing type lithographic printing plate precursor containing at least one kind. General formula (I): [However, in the above formula (I), at least one of -X and -X 'is an electron-withdrawing group, and Ha of -X and -X' is
If the sum of the values of mmet σ _P is 0.45 or more,
R ₀ may be the same or different, and R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms] 2. The direct drawing type lithographic printing according to claim 1, wherein the resin containing at least one polymer component having a functional group represented by the general formula (I) is pre-crosslinked. Original edition. 3. A resin containing at least one kind of the polymer component having a functional group represented by the general formula (I) further contains at least one kind of functional group which causes a curing reaction by heat and / or light. A resin as claimed in claim 1.
Alternatively, the lithographic printing plate precursor for direct drawing according to claim 2. 4. A resin having an image receiving layer on a support, wherein the binder resin of the image receiving layer is a resin containing at least one polymer component having a functional group represented by the following general formula (I). A direct-drawing type lithographic printing plate precursor containing at least one kind is used to form an image, and then the non-image part of the image-receiving layer contains at least a nucleophilic constant n of a person having a substituent group having a value of 5.5 or more. A method for producing a direct-drawing type lithographic printing plate, which comprises forming a printing plate by desensitizing with a processing liquid containing the hydrophilic compound. General formula (I) [However, in the above formula (I), at least one of -X and -X 'is an electron-withdrawing group, and Ha of -X and -X' is
If the sum of the values of mmet σ _P is 0.45 or more,
R ₀ may be the same or different, and R ₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]