JPH03214163A - Direct drawing type original plate for planographic printing - Google Patents

Abstract

PURPOSE:To improve the image receiving property of an image receiving layer and to prevent a change with the lapse of time by incorporating at least one kind of resin contg. at least one kind of polymer component having a formyl group and/or a specified functional group into a binder in the image receiving layer. CONSTITUTION:At least one kind of resin contg. at least one kind of polymer component having a formyl group and/or a functional group represented by formula I is incorporated into a binder in an image receiving layer. In the formula I, R1 and R2 are hydrocarbon groups or org. residues forming a ring by bonding to each other. The resin is preferably cross-linked beforehand because the image receiving layer has water resistance when the non-image area is treated with a desensitizing soln. An original plate for planographic printing improve the adhesive property of oily ink on the image area to the image receiving layer, keeping satisfactory hydrophilic property of the non-image area even after repeated printing, causing no ground stain and having printing resistance can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a lithographic printing original plate, and more particularly to a direct-drawing type lithographic printing original plate suitable for office printing original plates and the like.

[Conventional technology]

Currently, as printing plates for office use, direct-drawing type planographic printing plates having an image-receiving layer on a support are widely used.

In order to perform plate making, that is, image formation on such a printing original plate, generally a method is adopted, such as hand-drawing oil-based ink on the image-receiving layer, or printing using a typewriter-inkjet method or a transfer type thermal method. .

In addition, a method that uses a plain paper electrophotographic copier (PPC) to transfer and fix a toner image formed on a photoreceptor to an image-receiving layer through the steps of charging, exposure, and development has also begun to be used in recent years. In any case, the printing original plate after plate making is subjected to surface treatment with a desensitizing liquid (so-called etch liquid) to desensitize non-image areas, and then subjected to lithographic printing as a printing plate.

In the conventional direct drawing type lithographic printing original plate, surface layers are provided on both sides of a support such as paper with a back layer and an intermediate layer interposed therebetween. The back layer or intermediate layer is made of a water-soluble resin such as PVA and starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is formed from a pigment, a water-soluble resin, and a water-resistant agent.

A typical example of such a direct drawing type lithographic printing original plate is as described in U.S. Pat.
It is composed mainly of an inorganic pigment such as calcium carbonate and a water resistance agent such as an initial condensate of melamine/formaldehyde resin.

[Problem to be solved by the invention]

However, in conventional printing plates obtained in this way, if the hydrophobicity is increased by increasing the amount of water-resistant agent added or using a hydrophobic resin to improve printing durability, Although the printing durability is improved, the hydrophilicity is decreased and printing stains occur.On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is decreased. Particularly in a high-temperature operating environment of 30° C. or higher, the surface layer dissolves in the soaking water used in offset printing, resulting in major drawbacks such as reduced printing durability and printing stains.

Furthermore, in a lithographic printing plate, images are drawn on an image-receiving layer using oil-based ink or the like as an image area. Even if such printing stains do not occur, there is a problem in that oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability.

The present invention is intended to improve the above-mentioned problems of direct drawing type lithographic printing original plates.

An object of the present invention is to provide a direct-drawing type lithographic printing original plate which is used as an offset original plate and has excellent desensitization properties that do not cause not only uniform background smudges over the entire surface but also dotted background smudges.

The purpose of the present invention is to improve the adhesion between the oil-based ink in the image area and the image-receiving layer, and to maintain the hydrophilicity of the non-image area sufficiently even when the number of printing issues increases, so that scumming does not occur. An object of the present invention is to provide a lithographic printing original plate having high printing durability.

[Means to solve the problem]

The above-mentioned aspects include, in a direct-drawing lithographic printing original plate having an image-receiving layer on a support, the binder of the image-receiving layer is a formyl group and/or a functional group represented by the following general formula (I). This can be achieved by a direct-drawing lithographic printing original plate characterized by containing at least one resin containing at least one polymer component having the following.

General formula (I) [However, in the above formula (I), R,,R.

may be the same or different and each represents a hydrocarbon group, or R, and R2 represent an organic residue linked to each other to form a ring] In the present invention, formyl group and/or the above general formula (I
) At least one of the polymer components having a functional group represented by
The seed-containing resin may be crosslinked in advance, which is preferred because the image-receiving layer has water resistance when the non-image area is treated with a desensitizing (etching) treatment liquid.

The present invention also provides a formyl group and/or the above general formula (I)
The resin containing at least one kind of polymer component having a functional group represented by may be a resin containing at least one kind of functional group that causes a curing reaction with heat and/or light.

The present invention provides a resin having at least one type of formyl group or a functional group represented by the above general formula (1), preferably a partially crosslinked resin, as a binder for an image-receiving layer of a lithographic printing original plate. When treated with a treatment solution containing at least one nucleophilic hydrophilic compound, dealcoholization occurs from the formyl group or the functional group represented by the above general formula (I). A nucleophilic hydrophilic compound can be added to the formyl group generated by the reaction, and as a result, the image-receiving layer can exhibit hydrophilicity, and at the same time, when the resin has a crosslinked structure,
At this time, it has hydrophilicity but is insoluble or sparingly soluble in water.

As a result, the lithographic printing original plate according to the present invention reproduces a copy image that is faithful to the original image, and has good hydrophilicity in the non-image area, so it can be used as an offset original plate to prevent not only one-sided background smear but also dotted background smear. This has the advantage that the image-receiving layer has good smoothness and electrostatic properties, and has excellent printing durability.

Furthermore, the printing original plate for plate making of the present invention is not affected by the environment during plate making processing, has excellent preservability before processing, and has the characteristics that hydrophilic processing can be carried out quickly.

[For production]

The mechanism by which the binder resin of the image-receiving layer according to the present invention is made hydrophilic by a nucleophilic hydrophilic compound is explained below, taking as a typical example the case where sulfite ion is used as the nucleophilic hydrophilic compound.
It is shown in the reaction formula (1) below. ■ is formyl group or formula (I)
Indicates a resin moiety other than the functional group.

General formula (1) Formyl group 5O5e Hydrophilicity (1) That is, the resin of the binder according to the present invention has a nucleophilic property in the processing liquid only when etching the non-image area as a lithographic printing original plate. By reacting with the compound as described above, a hydrophilic group is added to the end, thereby making it hydrophilic. There are no issues of concern at all.

Since the formyl group is a functional group that reacts very quickly with nucleophilic compounds, it is possible to quickly develop hydrophilic properties.

Furthermore, the functional group represented by the general formula (I) is a precursor of a formyl group, and as shown in reaction formula (1), a formyl group is easily formed by acid decomposition. It can be used in the same way, and it is well known that this functional group has extremely excellent storage stability.

The binder resin used in the present invention will be explained in detail below. The functional group contained in the polymer component contained in the resin is a formyl group or one represented by the following general formula (I).

General formula (I) OR.

In formula (I), L and R2 may each be the same or different and represent a hydrocarbon group, or R.

R2 represents organic residues connected to each other to form a ring.

When R,,R, each represents a hydrocarbon group, RI +R
2 is preferably an optionally substituted aliphatic group having 1 to 12 carbon atoms (for example, an optionally substituted alkyl group having 1 to 12 carbon atoms; specific examples include a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, methoxymethyl group, ethoxymethyl group, 2-hydroxyethyl group, 2-chloroethyl group, 2-bromoethyl group, 1-)tetraethyl group base, 2
-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, 3-methoxypropyl group and the like. An optionally substituted alkenyl group having 2 to 12 carbon atoms: Specific examples include propenyl group, butenyl group, hexenyl group, octenyl group, docenyl group,
Examples include dodecenyl group. An optionally substituted aralkyl group having 7 to 12 carbon atoms: Specific examples include benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, Examples include methoxybenzyl group, dimethoxybenzyl group, chlorobenzyl group, bromobenzyl group, 70lobenzyl group, and dichlorobenzyl group.

An optionally substituted alicyclic group having 3 to 12 carbon atoms (specific examples include cyclopentyl group, cyclohexyl group, cyclohebutyl group, adamantyl group, etc.).

When R+ and R2 represent organic residues that are linked to each other to form a ring, preferably a functional group represented by the following general formula (Ia>, ie, a cyclic acetal group) is mentioned.

General formula (I a) In formula (I a), R3, R, may be the same or different from each other, and represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or a -0R6 group ( R, has 1 carbon number
~12 optionally substituted hydrocarbon groups), and n represents an integer of 1 to 4.

Preferred examples of the optionally substituted hydrocarbon group in which R3, R, and R3 have 1 to 12 carbon atoms include aliphatic groups (specifically, the same content as exemplified for R, and R2);
, aromatic groups (e.g. phenyl group, tolyl group, xylyl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, dimethoxyphenyl group, chloro-methylphenyl group, naphthyl group, etc.)
etc.

More preferably, in general formulas (I) and (Ia), R
In the case of the aliphatic group represented by 1-R3, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and an aralkyl group having 7 to 9 carbon atoms are preferable.

Further, n more preferably represents an integer of 1 to 3.

Formyl group and or formula (I) used in the present invention
Examples of the copolymerization component containing the functional group represented by the above include those represented by the repeating unit of the following general formula (n).

General formula (n) a, R2 1←CH-C± z-y-w.

[In formula (n), 2 is -C00-1-OCO-1-0-1
rl rl -CO-1-CON-1-3O2N- (rl represents a hydrogen atom or a hydrocarbon group) -CONHCOD-1
-CONHCONH-1Y represents an organic residue that directly bonds or connects -Z- and -Wo. In addition, Shiz-Y
Professionals may directly connect the 2nd edition -C-+ part and -Wo.

No represents a formyl group or a functional group represented by general formula (I).

air R2 may be the same or different from each other, and each
Represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group, or an aryl group.

General formula (II) will be explained in more detail.

Preferably, Z is -C00-1-0CO-1-0-1.

However, rl is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methylbenzyl group, dibromobenzyl group 1
, an optionally substituted aryl group (e.g. phenyl group,
tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.).

Is Y a direct bond? -Z- and -W. Represents an organic residue that connects

When Y represents a linked organic residue, this linking group represents a carbon-carbon bond that may be via a petro atom, and the petro atom represents an oxygen atom, an atom atom, or a nitrogen atom) 5 3 4 +CH=CH+ , -0-1-5-1-N-1-CO
O-1-[:0NH-1-8O, -1-8O2NH-1
-NHCOO-15 NHCOO-15 NHCONH-1-3i- and other bonding units singly or in combination (provided that r 21 r
31r4+ rS+ r6 each represent the same content as rl above. ) a+ and a2 may be the same or different, and include a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group,
Hydrocarbon groups (e.g. methyl, ethyl, propyl,
Butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group,
an optionally substituted alkyl group having 1 to 12 carbon atoms such as hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group,
represents an aryl group such as a phenyl group, tolyl group, xylyl group, chlorophenyl group, etc.).

Furthermore, -E-Z-Y bond 2 in formula (n) The residue may directly link 1,000+ parts and -W0.

Specific examples of the formyl group-containing polymer component of the present invention are shown below. However, the scope of the present invention is not limited to these.

Example (a ■) ~(a In 15) a teeth Represents H or -CH.

(a-1) →C1(, -C+ CHD (a-2) →CH, -C+ C0D(CH,), CHD m: Integer from 1 to 6 β: Integer from 1 to 4 CH3 (a 5) -← CH-CH+- COD(CH,), [:)10 (a 8) →CH2-C+ C0NH(CH2), CHom: Integer from 1 to 6 (a-9) →CH,-C+ C'0N1(COD (Cl(2), CH0(a-11) → [:H, -C+ C00(CH2),,1OCO(CH,),,,CI(
0n1: An integer from 1 to 4 2: An integer from 1 to 3 0NHCH CH,CHD Further, specific examples of the functional group represented by the general formula (I) of the present invention are shown below, but the scope of the present invention does not extend to these. It is not limited. In examples (b-1) to (b-9), R
a and L represent an alkyl group having 1 to 4 carbon atoms or CHzCJs, and Ro is an alkyl group having 1 to 4 carbon atoms.

CH2C, )l, or represents a phenyl group.

(bl) (b-2) (b-3) (b-4> (b 5) (b-6) (b-7) (b-8) (b-9) The present invention as described above Formyl group and/or - general formula (I)
A resin containing a polymer component containing a functional group represented by can be synthesized by a conventionally known synthesis method.

That is, a monomer containing a formyl group or a functional group represented by general formula (I) and a polymerizable double bond group in the molecule (for example, a monomer corresponding to a repeating unit of general formula (II)). Method of polymerization reaction and reacting a low molecular compound containing a formyl group or a functional group of general formula (I) with a high molecular compound containing a polymer component containing a functional group that chemically reacts with the low molecular compound. (ie, polymer reaction).

Furthermore, after synthesizing a resin with a functional group represented by general formula (I),
A formyl group-containing resin can also be synthesized by performing acid decomposition treatment.

The formylation reaction or acetalization reaction in the monomer synthesis or polymer reaction synthesis described above can be easily carried out by conventionally known reactions.

For example, as a method for synthesizing formyl group-containing compounds, Nippon Kagaku Complete Edition, New Experimental Chemistry Course Volume 14, 636 (197
8th year) Published by Maruzen ■, B, M711er.

rMethoden der Organischen
Chemie J p 13 (1954), G
Examples include methods described in eorg Th1ea+e Verlag, Nippon Kagaku Complete Edition, Experimental Chemistry Course, Volume 19, p231 (1957), Maruzen ■, etc.; , New Experimental Chemistry Course, Volume 14, p611 (1978),
There are methods described in Maruzen ■ and other publications.

When the binder resin of the present invention contains a formyl group and/or a functional group represented by the general formula (I), when the resin is a copolymer, the amount of the polymer component is 1 to 95 in the total copolymer.
It is preferably 10 to 85% by weight. Further, the molecular weight of the resin polymer is preferably 103 to 106, particularly 3x103 to 5x105.

The resin of the present invention can further be used in a direct drawing type lithographic printing original plate,
At least a portion thereof may be crosslinked.

As such a resin, a resin that has been crosslinked in advance during application of the image-receiving layer forming material in the plate-making process may be used, or a resin that is cured by heat and/or light together with a formyl group and/or a functional group of formula (I) may be used. A resin containing a crosslinkable functional group capable of causing a reaction may be used as a binder, and then crosslinked during the lithographic printing original manufacturing process (for example, during the drying process). Furthermore, these may be used in combination.

When using a resin in which a portion of the polymer has been crosslinked in advance (resin having a crosslinked structure in the polymer), the above-mentioned functional groups contained in the resin are desensitized to make them hydrophilic. Preferably, the resin is poorly soluble or insoluble in acidic or alkaline aqueous solutions when developed.

Specifically, the solubility in distilled water is preferably 90% by weight or less, more preferably 79% by weight or less at a temperature of 20 to 25°C.

As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used.

That is, a method of polymerizing a monomer containing a formyl group and/or a group of general formula (I) in the coexistence of a polyfunctional monomer, and a functional group that progresses a crosslinking reaction in the polymer. and then the above (I) and/or (I
This is a method of crosslinking by reacting a polymer with a compound containing a functional group (I).

The resin of the present invention has a simple manufacturing method (for example, it does not require a long reaction, the reaction is not quantitative, and there are no problems such as contamination of impurities due to the use of a reaction accelerator, etc.). The functional group that undergoes the reaction is C0NHCH,
OR'(R' is a hydrogen atom or an alkyl group) or a crosslinking reaction by polymerization is effective.

Specifically, a monomer having two or more polymerizable functional groups (polyfunctional monomer) is a monomer containing at least one formyl group and/or a functional group of general formula (I) of the present invention. or a method of polymerizing the polyfunctional monomer with a formyl group and/or a polar group capable of introducing a functional group of general formula (1) (for example, -0[1, -'' -Br, -1-NH
2, N=C=0, -CO", -3O2Cf, etc.) to form a copolymer, and then a copolymer containing a formyl group and/or a functional group of general formula (I) is formed. The resin of the present invention can be produced by a method of introducing a molecular compound through a polymer reaction.

Specifically, the polymerizable functional group is CH2=CH-CH,
=CH-C0NH-1CH2=CH-CI(2-NHC
O-1CH2=CH-3O2-C)I2=CH-CD-
1CH2=CHL-OCH, =CH-8-, etc., but monomers having two or more of the above polymerizable functional groups may have the same or different polymerizable functional groups. Any monomer having two or more may be used, and upon polymerization, it forms a polymer insoluble in non-aqueous solvents.

Specific examples of monomers having two or more polymerizable functional groups include monomers having the same polymerizable functional groups, styrene derivatives such as divinylbenzene and trivinylbenzene, polyhydric alcohols (e.g. , ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200. #400, #600.1.3
-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenol (
Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid (e.g. hydroquinone, resolucin, catechol and their derivatives); dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, leic acid, phthalic acid,
Itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or triamides of polyamines (e.g. ethylenediamine, 1,3-propylenediamine,
1,4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, examples of monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpyropionic acid, acryloylpropionic acid, itaconylyl acetic acid, itaconyl [Roylpropionic acid, reactants of carboxylic acid anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.)]
Ester derivatives or amide derivatives containing vinyl groups (e.g. vinyl methacrylate, vinyl acrylate, vinyl itaconate, aryl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylpropionate, methacryloylpropion) allyl acid, vinyloxycarbonyl methyl methacrylate, vinyloxycarponyl methyloxycarponyl ethyl acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, methacryloylpropionic acid torylamide, etc.), or , condensates of amino alcohols (e.g. aminoethanol, 1-aminopropanol, ■-aminobutanol, 1-aminobutanol, 2-T minobutanol, etc.) and carboxylic acids containing vinyl groups, etc. Can be mentioned.

The monomer having two or more polymerizable functional groups that can be used in the present invention is polymerized in an amount of 10 mol% or less, preferably 5 mol% or less of the total monomers, to form a pre-crosslinked resin. can do.

However, in the case of a polymer containing a functional group represented by general formula (I), among the above-mentioned polymerizable functional groups,
CH2=CH-[:00113 C11,=C-COO-1CH,=CH-CONH-,
It is preferable not to use CH2=CH-3O□-CH, -CH-CD-.

On the other hand, in the method of crosslinking a polymer containing a functional group (curable functional group) that promotes a crosslinking reaction by a polymer reaction, the curable functional group causes a chemical reaction between molecules to form a chemical bond. Whatever you can get is fine. That is, condensation reaction,
It is possible to use a reaction mode in which bonding between molecules by addition reaction or the like or crosslinking by polymerization is caused by heat and/or light.

Specifically, the curable functional group includes a functional group having a dissociable hydrogen atom (for example, -COOH group, -PO:+tb group, -F'-R, group [R represents an aliphatic group, CH 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, Butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3
-chloropropyl group, etc.) or -0Rs'(Rs' represents the same content as the group of R1) -CH group, -3H group,
-NH-R,. (R, 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, a butyl group)], an -NCO group, and a cyclic dicarboxylic acid anhydride. each having at least one combination of selected functional groups, or -CONHCH2
0R1, (R,, is a hydrogen atom or a methyl group, an ethyl group,
(representing an alkyl group having 1 to 6 carbon atoms such as a propyl group, a butyl group, a hexyl group, etc.) or a polymerizable double bond group.

Specific examples of the polymerizable double bond group include those listed as specific examples of the polymerizable functional group described above.

Furthermore, for example, Tsuyoshi Endo ``Refinement of thermosetting polymers (C
, M, C■, published in 1986), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter ■-1 (Sogo Technological Center, published in 1985), Yoshiyuki Otsu, "Synthesis and design of acrylic resin and development of new applications" (Chubu Management Development Center Publishing Department, published in 1985)
, Eizo Omori, “Functional Acrylic Resin” (Technosystem, 1985), Hideo Inui, Gentabe Nagamatsu, “Photosensitive Polymer” (Kodansha, 1977), Takahiro Tsunoda, “New Photosensitive Resin” (Printing Society of Japan) Publishing Department, 1981), G, B
, Green and B, P, 5tar R, J.

Macro, Sci Revs, Macro, Ch.
e+n,, C21(2), 187-273 (198
1-82), C, G, Roffey.

”Photopoly+nerization of
5 surface coatings (A, Wiley
Interscience Pub, 1982)
Functional groups, compounds, etc. cited in, etc. can be used.

These curable functional groups are formyl groups and/or general formulas (
It may be contained in one copolymer component together with a functional group represented by formula (I), or a formyl group and/or a functional group of formula (I
) may be contained in a separate copolymer component from the copolymer component containing the functional group.

Specific monomers corresponding to the copolymer component containing these curable functional groups include, for example, general formula (n)
Any vinyl compound containing the functional group that can be copolymerized with the polymer component may be used.

Such vinyl compounds are described, for example, in Polymer Data "Polymer Data Handbook [Basic Edition]" (Baifukan 1988).
6th edition) etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-chocetoxymethyl form, α-(2-aminomethyl) form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
cyano body, β-chloro body, β-proshen body, α-chloro body
β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-chlorokenylcarboxylic acid (
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, Vinyl sulfonic acid, vinyl phosphoric acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, ester derivatives of these carboxylic acids or sulfonic acids, compounds containing the curable functional group in the substituent of amide derivatives, etc. Can be mentioned.

The proportion of the "curable functional group-containing polymer component" in the resin of the present invention is preferably 1 to 80% of the total amount of the binder resin.
Weight%. More preferably, it is 5 to 50% by weight.

If necessary, a reaction accelerator may be added to such a resin in order to promote the crosslinking reaction. For example, acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), peroxides, azobis compounds,
Examples include crosslinking agents, sensitizers, photopolymerizable monomers, and the like.

Specifically, as the crosslinking agent, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, Taiseisha (19SI), etc. can be used. For example, commonly used crosslinking agents such as organic silanes, polyurethanes, and polyisocyanates, and curing agents such as epoxy resins and melamine resins can be used.

When containing a photocurable functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used. Examples include compounds having an allyl ester group, a cinnamoyl ester group, a dimethylmaleimide ring group, and the like.

When a resin containing a curable functional group is used, crosslinking in at least a portion of the polymer can be carried out during the process of forming the image-receiving layer or during the process of heating and/or light irradiation. Usually, it is preferable to perform a thermosetting treatment. This heat curing treatment is performed at, for example, 60°C to 120°C for 5 minutes to 120°C.
Just process it for a minute. When a reaction accelerator is used in combination, it becomes possible to perform the treatment under milder conditions.

In addition, when a photocurable resin is used, it is crosslinked by irradiation with electron beams, The reaction is further accelerated by heating.

Also in this case, if a reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

Conventionally known resins can also be used together with the resins used in the present invention. For example, silicone resin, alkyd resin, vinyl acetate resin, polyester resin, styrene-butadiene resin, acrylic resin, polybutyral resin, polyolefin resin, ethylene vinyl acetate copolymer, styrene resin, acrylate-butadiene resin, vinyl alkanoate resin, etc. Can be mentioned.

The resin of the present invention may be dissolved or dispersed in an organic solvent,
Furthermore, an aqueous emulsion can also be used. Therefore, any water-soluble resin can be used in combination with the resin of the present invention, such as PVA.

Modified PVA such as carboxyPVA, starch and its derivatives CMC, hydroxyethylcellulose, casein,
Water-soluble resins such as gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, and styrene-maleic acid copolymer can be used.

When these water-soluble resins are used together, it is preferable to use a water-resistant agent. Examples of the water-resistant agent include glyoxal, melamine formaldehyde resin, urea formaldehyde resin and other amine blast initial condensates, and methylolated polyamide resins. Examples include modified polyamide resins such as polyamide-polyamine-epichlorohydrin adducts, polyamide epichlorohydrin resins, modified polyamide polyimide resins, and the like.

The resin of the present invention and known resins can be mixed in any ratio, but the functional groups [formyl group and/or formula (I) The amount of the copolymer component having a functional group] needs to be at least 30% by weight, preferably at least 40% by weight.

If the content of the functional group component that reacts with a nucleophilic compound to form a hydrophilic group is less than 30% by weight, the resulting direct plate printing original plate will be insensitive to desensitizing liquid and soaking water. The hydrophilicity produced by the fat treatment is not sufficient and stains occur during printing.

Inorganic pigments are used as other components of the image-receiving layer of the present invention, such as kaolin clay,
Examples include calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, and alumina.

The ratio of binder resin/pigment in the image-receiving layer varies depending on the type of material and particle size in the case of pigment, but is generally 1/(0.5 to 5), preferably 1/(0.5) by weight. ~2.
5) The level is appropriate.

Other crosslinking agents may be added to the image-receiving layer in order to further improve the film strength. As the crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap, organic silane, polyurethane crosslinking agent, epoxy resin curing agent, etc. can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko (eds.), “Crosslinking Agent Handbook”, Taiseisha (1981)
You can use the ones listed in the annual publication) etc.

Supports used in the present invention include wood-free paper, wet reinforced paper, plastic films such as polyester films, metal plates such as aluminum plates, and the like.

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 support surface opposite to the image-receiving layer for the purpose of preventing curling. I can do it.

Here, the intermediate layer is an emulsion type resin such as acrylic resin, styrene-butadiene copolymer, methacrylic acid ester butadiene copolymer, T-crylonitrile-butadiene copolymer, ethylene vinyl acetate copolymer; epoxy resin, Solvent-type resins such as polyvinyl butyral, polyvinyl chloride, and polyvinyl acetate; mainly composed of at least one of the water-soluble resins mentioned above, but inorganic pigments and waterproofing agents may be added as necessary. be able to.

When used as PPC plate-making, in order to further reduce scumming of the printing original plate of the present invention, an image-receiving layer, an intermediate layer and/or a backing layer are further added so that the volume resistivity of the printing original plate is 1010 to 10I3Ωcm. A dielectric agent can be added to the coating layer. The dielectric agent may be inorganic or organic, and inorganic ones include Na, K, Lx, M gs Z n, CO, N 1
Salts of monovalent or polyvalent metals such as polyvinylbenzyltrimethylammonium chloride and organic salts such as polyvinylbenzyltrimethylammonium chloride,
Examples include polymeric cationic conductive agents such as acrylic resin-modified quaternary ammonium salts and polymeric anionic conductive agents such as polymeric sulfonates.

The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 20% by weight of the amount of binder used for each member.

In general, in order to create the direct drawing type lithographic printing original plate of the present invention,
If necessary, an aqueous solution containing an intermediate layer component is coated on one side of the support and dried to form an intermediate layer, and then an aqueous solution containing an image-receiving layer component is coated and dried to form an image-receiving layer. For example, a backcoat layer may be formed by applying an aqueous solution containing backcoat layer components to the other surface and drying it.

The adhesion amounts of the image-receiving layer, intermediate layer, and back coat layer are 1 to 30 g/m2.5 to 20 g/m', and 5 to 20 g/m', respectively.
20g/[112 is suitable.

In order to create a printing plate using the direct plate lithographic printing original plate of the present invention, after forming and fixing an image on the direct plate lithographic printing plate having the above-mentioned structure using a known technique, a desensitizing solution is applied. After surface treatment to desensitize the non-image areas, the plate is used as a printing plate for lithographic printing.

The desensitization treatment provided in the present invention is carried out in a formyl group-containing bonding resin of the present invention with a solution (aqueous solution or a mixture containing a water-soluble organic solvent) containing a hydrophilic compound that easily undergoes a nucleophilic reaction with the formyl group. solution).

As a hydrophilic compound that causes a nucleophilic substitution reaction on a formyl group, the nucleophilic constant n[R,G of Pearson et al.

Pearson, tt, 5obe1. J, So
ngstsd, J, Amer.

Chem, Soc, 90 319 (1968
) contains a substituent having a value of 5.5 or more, and a hydrophilic compound that dissolves 1 weight or more in 100 parts by weight of distilled water.

Specific compounds include hydrazine, hydroxylamine, sulfites (ammonium salts, sodium salts, potassium salts, zinc salts, etc.), thiosulfates, etc., and also contain hydroxyl groups, carboxyl groups, and sulfo groups in the molecule. Examples include mercapto compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds containing at least one polar group selected from , phosphono groups, and amino groups.

For example, mercapto compounds include 2-mercaptoethanol, 2-mercaptoethylamine, N-methyl-2-
Mercaptoethylamine, N(2-hydroxyethyl)
2-Mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenesulfonic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercaptobenzenesulfonic acid, 2
-Mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2 dimercaptopropionylamine vinegar 1! !
', 2,3-dihydroxypropyl mercaptan, 2-
Methyl-2-mercapto-1-aminoacetic acid, etc., and 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, dicarboxybenzenesulfinic acid, etc. as sulfinic acid compounds. , 2-hydrazinoethanesulfonic acid, 4- as a hydrazide compound
hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid, etc.
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-aminobrobionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2
-hydroxyethylmorpholine, 2-carboxyethylmorpholine, 3-carboxypiperazine and the like.

These nucleophilic compounds are used by being included in the desensitizing solution described above. The amount of the nucleophilic compound present in these treatment solutions is 0.1 mol/l to 10 mol/l, preferably 0.1 mol/l to 10 mol/l.
5 mol/l-5 mol/β.

Further, the pH of the treatment liquid is preferably 4 or more.

The conditions for the treatment are preferably a temperature of 15°C to 60°C and an immersion time of 10 seconds to 5 minutes.

The treatment liquid may contain other compounds in addition to the above-mentioned nucleophilic compound and pH adjuster. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Such water-soluble organic solvents include:
For example, alcohols (methanol, ethanol, propatool, propargyl alcohol, benzyl alcohol,
phenethyl alcohol, etc.), aromatic alcohols, ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydrobilane, etc.), amides (dimethylformamide, dimethylacetamide, etc.), amino alcohols (monoethanolamine, jetanolamine, triethanolamine, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination. A mixture of the above may be used.

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, cationic, and nonionic surfactants.

For example, Hiroshi Horiguchi, “New Surfactants,” Sankyo Publishing ■, (197
Compounds described in Ryohei Oda and Hiroshi Teramura, "Synthesis of Surfactants and Their Applications" Yoko Shoten (published in 1980), etc. can be used.

Furthermore, a material containing an antifoaming agent and other various additives is used as required.

The scope of the present invention is not limited to the specific compound examples described above.

The method of etching the binding resin of the present invention containing a functional group represented by the general formula (1) is to carry out a dealcoholization reaction by acid decomposition as shown in the reaction formula (1), and then formyl groups generated. It is characterized by being made hydrophilic by a nucleophilic reaction of a nucleophilic compound.

Since the dealcoholization reaction easily proceeds in a treatment solution with a pH of 5 or less, by setting the pH of the etching treatment solution containing at least the above-mentioned nucleophilic compound to 5 or less, the dealcoholization and nucleophilic reaction can be accelerated. hydrophilicity is achieved.

Furthermore, after the dealcoholization reaction has proceeded with a solution having a pH of 5 or lower, there is no problem in etching with a treatment solution containing nucleophilic properties.

〔Example〕

Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Resin synthesis example 1: Resin [P-1] Benzyl methacrylate 39g1 Monomer CM with the following structure
-1160g, acrylic acid 1.0g and toluene 200g
The mixed solution of g was heated to a temperature of 75° C. under a nitrogen stream. While stirring, add azobisisobutyronitrile (hereinafter referred to as A) 1.
(abbreviated as B, N) was added and reacted for 4 hours,
Furthermore, 0.4 g of ^, I, B, and N were added and reacted for 3 hours. The weight average molecular weight of the obtained polymer CA-1) (
~) was 4.3 x 10'.

Monomer CM-1) C84 CH2=C C00CH,CHo Resin [P-] C)+3 -tCL-Css-11- C00CH2C,)Is C)Is -CH, -C dimension T mark +C11, -C8 →l-1C00
CH,CHOC00N Resin Synthesis Example 2 = Resin [P-2] A mixed solution of 90 g of monomer CM-2 with the following structure, 10 g of 2-hydroxyethyl methacrylate, and 200 g of toluene was added to a temperature of 70°C under a nitrogen stream. It was warm. While stirring, 1.5g of ^, I, B, and N were added and reacted for 5 hours, and further ^, 1. 0.5 g of B and N were added and reacted for 3 hours. ~ of the obtained polymer CP-2) is 3.5
It was XIO'.

Monomer CM-2] CHl CH,=C Con(CH2)2CHO Resin [P-2] Resin synthesis example 3: Resin CP-31 Monomer CM-3 with the following structure] 92 g, 2.3- 8g of dihydroxypropyl methacrylate and 2g of toluene
00 g of the mixed solution was heated to a temperature of 75° C. under a nitrogen stream. Under stirring 1. B, N, 1. Added Og and reacted for 4 hours, and further ^, 1. 0.4g of B and N were added and reacted for 3 hours. ~ of the obtained polymer CP-3) is 5.
It was 0x10'.

Monomer CM-33 CH.

Resin [P-3] CH3 CH3 Resin Synthesis Example 4: Resin CP-4] After cooling the polymer mixture obtained in Resin Synthesis Example 3 to room temperature, a methanol solution L containing 10% IN hydrochloric acid was added to the mixture.
After stirring at room temperature for 30 minutes, methanol 2
It re-sedimented in 1.

The precipitated white crystals were filtered and dried under reduced pressure at room temperature. yield? 5g was 5.5X10'.

Resin [P-4] Synthesis example 5 of leaf resin: Resin CP-5) 18 g of ethyl methacrylate, monomer CM- with the following structure
4] 80g, divinylbenzene 2.0g and toluene 2
00 g of the mixed solution was heated to a temperature of 70° C. under a nitrogen stream. Add azobisisovaleronitrile (hereinafter ^, B,
1.5 g (abbreviated as V, N) were added and reacted for 4 hours. Furthermore, 0.5 g of ^, B, V, and N were added and reacted for 3 hours. ~ of the obtained polymer [' = 5) is 1.5X
It was 105.

Monomer CM-4] C1l.

Resin [P-5] (Estimated partial structure) CH3 CH3 Resin synthesis example 6: Resin [P-6] Monomer CM-4385 g, 2-hydroxyethyl methacrylate 10 g, acrylic acid 5 g, and toluene 200 g
The mixed solution was heated to a temperature of 90° C. under a nitrogen stream. A,
1. 6g of B and N were added and reacted for 4 hours. The resulting polymer [P-63] was 8.5 x 103.

Resin [P-6’] CH.

CH3 -tCH, -C→Ryoding-÷CH2-CH→]--C00
((1:)12) Synthesis example 7 of 2DHCDDH resin: Resin CP-7] Monomer CM-5378g with the following structure, allyl methacrylate 20g, 2[2-carboxyethylcarbonyloxy]ethyl methacrylate 2g, and toluene 300g
The mixed solution was heated to 60°C under a nitrogen stream. ^、B、
Add 1.5g of V and N, react for 4 hours, and then add A and B.
, V, N, 0.5 g were added and reacted for 3 hours. ~ of the obtained polymer CP-71 was 6.8xlO'.

monomer CM-5) CH.

Resin [P-7] C8゜ fcL-C → completed a-- C00CH-CH2C11O CH, CHo COOCH, C11=C)l.

Resin synthesis example 8: Resin CP-8] Monomer [M-5) 95g, methacrylic acid 5g.

3 g of divinylbenzene, 1 n-dodecyl mercaptan
．． A mixed solution of 5 g and 200 g of toluene was heated to 75° C. under a nitrogen stream. 1 g of ^, r, B, N was added and reacted for 4 hours. Furthermore, A.1. B, N, 0.5
Add g for 3 hours, then add 0.5 g of A, I, B, N.
The mixture was added and reacted for 3 hours. ~ of the obtained polymer [P-8] was 7.3XlO'.

Resin CP-8:l (estimated partial structure) CH, C00H 0-C)I　　　　　Me N-1　CH( CH.

Synthesis Example 9 of CH3I-\--N Resin: Resin [P-9] After cooling the polymer mixture obtained according to the synthesis example of Resin [P-8], an ethanol solution containing 10% by weight of IN hydrochloric acid was added to the mixture. After adding 10 g of the mixture and stirring at a temperature of 30° C. for 30 minutes, it was reprecipitated in 1.5 g of methanol, filtered, and dried under reduced pressure at room temperature. ~ of the obtained polymer [P-9]
was 7.5X10'.

Resin [P9] (Estimated partial structure) C) l-CL-1\-1 Example 1 On the intermediate layer of a support provided with a back layer on one side of high-quality paper and an intermediate layer on the other side. 40g of resin CP-1)
(as solid content), 50g of zinc oxide and 15g of toluene
0g of the mixture was dispersed in a ball mill for 2 hours, and the resulting dispersion was coated with a wire bar so that the dry adhesion amount was 18g/m2, and dried at 100°C for 30 seconds to prepare a lithographic printing original plate. did. This original plate was immersed for 20 seconds in a desensitizing treatment liquid (E-1) adjusted to the following formulation, and then washed with water.

Desensitizing treatment liquid (E-1) The above was dissolved.

A 2μβ water droplet of distilled water was placed on this, and the contact angle with the water formed was measured with a coniometer, and it was found to be 10° or less. Note that the contact angle before the desensitization treatment was 98°. This indicates that the non-image area of the image-receiving layer of the original plate of the present invention has changed from lipophilic to hydrophilic. (The contact angle with water must be 20° or less.) Next, a plate is made using commercially available PPC, and the obtained master plate is desensitized under the same conditions as above. , an original printing plate was obtained.

The density of the image area of the obtained original plate was 1.0 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear.

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problems occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no ground blur 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 after printing 5000 sheets.

As described above, the image quality of this original plate did not deteriorate during PPC plate making even under high temperature and high humidity conditions.

Example 2 Resin CP-6140g (
(as solid content), 50 g of zinc oxide and 150 g of toluene
The mixture of g was dispersed in a ball mill for 2 hours, and further, 4 g of 1,3-xylylene diisocyanate was added thereto and dispersed in a ball mill for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m' and dried at 110° C. for 1.5 hours to prepare a lithographic printing original plate. This original plate was operated in the same manner as in Example 1 to perform plate making and
I printed it.

The density of the image area of the obtained original plate was 1.0 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear.

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problems occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no ground blur 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 after printing 5000 sheets.

As mentioned above, the image quality of this original plate did not deteriorate during PPC plate making even under high temperature and high humidity conditions.

Example 2 40 g of resin ['-6] (
(as solid content), 50 g of zinc oxide and 150 g of toluene
The mixture of g was dispersed in a ball mill for 2 hours, and further, 4 g of 1,3-xylylene diisocyanate was added thereto and dispersed in a ball mill for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m 2 and dried at 110° C. for 1.5 hours to prepare a lithographic printing original plate. This original plate was operated in the same manner as in Example 1 to perform plate making and
I printed it.

The density of the image area of the obtained original plate was 1.0 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear.

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problem occurred with background stains in non-image areas or image quality in image areas of the printed matter.

Furthermore, using the above original plate, the environmental conditions were adjusted to 30°C and 80% RH.
When a plate was made using a commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no ground blur 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 after printing 5000 sheets.

Examples 3 to 14 40 g each of resins CP-10 to [P-21] shown in Table-1 below
(Solid content > 1.5-(N-imidazolyl)carbamoylnaphthalene zinc oxide 10g and toluene 80g
The mixture of g was dispersed in a ball mill for 2 hours. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m' and dried at 120° C. for 20 hours to prepare a lithographic printing original plate. ~ for each resin CP) is 3X10'~5
It was X10'.

Table Example 1 except that a desensitizing treatment liquid (E-2) prepared according to the following formulation was used as a desensitizing treatment liquid for this original plate.
Plate making and printing were performed in the same manner as above.

Desensitizing treatment liquid (E-2) These were dissolved with distilled water to bring the total amount to 11, and then hydroxylated.) The pH was adjusted to 11.0 with IJum.

The density of the image area of the obtained original plate was 1.0 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear.

This is an offset printing machine (Oliver 52 manufactured by Sakurai Seisakusho).
(type) and printed on high-quality paper. Even after printing more than 5,000 sheets, no problems occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter.

Furthermore, using the above original plate, the groove boundary conditions were set to 30°C and 80%RH.
When a plate was made using a commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no ground blur 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 after printing 5000 sheets.

Examples 15-25 40g each of resins [P-22] to [P-32] shown in Table-2 below
1 A mixture of 5 g of silica gel, 5 g of alumina, and 80 g of toluene was dispersed in a ball mill for 2 hours, and further, the following table--
5 g of the crosslinking compound No. 2 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' and dried at 120° C. for 20 hours to prepare a lithographic printing original plate. In addition, each resin in Table 2 [Pl ~ was 3X10' to 6X10'.

This was made into a plate in the same manner as in Example 3, and then printed using a printing press. The density of the obtained printing original plate was 1.0 or more, and the image quality was clear. Furthermore, the image quality of the printed matter after printing 5,000 sheets was a clear image without any blurring.

Examples 26 to 37 Using each printing master plate prepared in Examples 2 to 25, 0.5 mol of the nucleophilic compound shown in Table 3 below, 100 g of an organic solvent, and 10 g of Nucol B4SN (manufactured by Nippon Nyukazai ■) were distilled. After adding water to bring the mixture to 1β, the pH of each mixture was adjusted to 11.0. Each original plate was immersed in the above treatment liquid for 30 seconds to perform a desensitization treatment, and then printed under the same printing conditions as in Example 1.

In each original plate, the contact angle with water in the non-image area was 10° or less, making it sufficiently hydrophilic. Furthermore, even though the number of prints was 5,000, the print image quality of the printed matter was good with no blurring and clear images.

Examples 38 to 39 Original plates were prepared in the same manner as in Example 1, except that 40 g of resin [P] shown in Table 4 below was used instead of 40 g of resin [P-1] in Example 1.

Measure each of these materials from a distance of 30cm using a 400W high-pressure mercury lamp.
After irradiating with light for a minute, the plate was left in a dark place at 20° C. and 65% RH for 24 hours to prepare a lithographic printing original plate.

When this plate was made in the same manner as in Example 1, the printing original plate obtained had a density of 1.2 or more and a clear image quality. Further, when etching was performed and printed using a printing press, the printed matter after printing 5,000 sheets had no fog in the non-image area and the image was clear.

〔Effect of the invention〕

According to the present invention, a direct drawing type lithographic printing original plate which has excellent image receptivity and does not change over time can be obtained.

Moreover, a printing original plate with very good printing properties can be obtained.

Claims (3)

[Claims] (1) In a direct-drawing lithographic printing original plate having an image-receiving layer on a support, the binder of the image-receiving layer is a polymer having a formyl group and/or a functional group represented by the following general formula (I). A direct drawing type lithographic printing original plate, characterized in that it contains at least one resin containing at least one component. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula (I), R_1 and R_2 may be the same or different, and may represent a hydrocarbon group,
Or R_1 and R_2 represent organic residues linked to each other to form a ring] (2) The resin containing at least one of the above formyl groups and/or a polymer component having a functional group represented by general formula (I) is crosslinked in advance. An original plate for direct-drawing planographic printing. (3) The resin containing at least one polymer component having a formyl group and/or a functional group represented by general formula (I) further contains at least one functional group that causes a curing reaction with heat and/or light. The original plate for direct drawing type lithographic printing according to claim 1 or 2, characterized in that the resin contains seeds.