JPH04185488A - Original plate for direct drawing-type lithographic printing - Google Patents

Abstract

PURPOSE:To obtain a printing plate with superb ability to make it insensible to fat without entirely uniform background contamination and spot background contamination by adding resin particles having at least, one kind of polymer component with a specific functional group in an image-receptive layer. CONSTITUTION:An image-receptive layer laid on a support contains resin particles of resin consisting of at least, one kind of a functional group expressed by formula I and/or formula II. The resin particles are treated in a treatment liquid containing at least one kind of a hydrophilic compound containing a nucleophilic substituent group. In this case, the hydrophilic compound containing the nucleophilic substituent group is added under reaction at the terminal of a functional group generated by dehalogenated hydrogen from the functional group shown by formula I or II of the resin particles. Subsequently, the image- receptive layer demonstrates an increased hydrophilic ability and also water insolubility or retarded water solubility. In addition, the image-receptive layer becomes swollen in water so that is does not effuse when wetted. Therefore, excellent printing properties can be maintained, if a considerable number of sheets are printed.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a direct-drawing lithographic printing original plate, and more particularly, to an improvement of a composition for forming an image-receiving layer of a direct-drawing lithographic printing original plate suitable for office printing original plates, etc. It is. [Prior Art] Currently, as printing plates for office use, direct-drawing 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,
In general, a method is adopted in which the image is drawn by hand with oil-based ink on the image-receiving layer, or by printing using a typewriter, an inkjet method, or a transfer type heat-sensitive method. others,
A method of transferring and fixing a toner image formed on a photoreceptor to an image-receiving layer through charging, exposure, and development steps using a plain paper electrophotographic copier (PPC) has also begun to be used in recent years. In any case, the printing original plate after platemaking is subjected to surface treatment with a desensitizing liquid (so-called etch ll1jl) to desensitize non-image areas, and then subjected to lithographic printing as a printing plate. Conventional direct-drawing lithographic printing original plates have a back layer on one side of a support such as paper, and an image-receiving layer as a surface layer on the other side with an intermediate layer interposed therebetween. The back layer or 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 waterproofing 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. [Problems to be Solved by the Invention] However, conventional printing plates obtained in this manner do not require the addition of a large amount of water-resistant agent or the use of hydrophobic resin in order to improve printing durability. If hydrophobicity is increased by increasing hydrophobicity, printing durability will improve, but hydrophilicity will decrease, resulting in printing stains.On the other hand, if hydrophilicity is improved, water resistance will deteriorate, leading to a decrease in printing durability. there were. Particularly in high-temperature operating environments of 30°C or higher, the surface layer (image-receiving layer) dissolves in the soaking water used in offset printing, resulting in major drawbacks such as reduced printing durability and printing stains. . Furthermore, in planographic printing plates, images are drawn on the image-receiving layer using oil-based ink, etc., and if the binder properties between the image-receiving layer and the oil-based ink are not good, even if the non-image area has sufficient hydrophilicity. Even if the above-mentioned printing stains do not occur, there is a problem in that the oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability. The present invention is intended to solve 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 has excellent desensitization properties and does not cause not only uniform background smudge over the entire surface but also dotted background smear as an offset original plate. Another object 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 sufficient hydrophilicity in the non-image area even when the number of prints increases, thereby preventing the occurrence of scumming. An object of the present invention is to provide a direct-drawing type lithographic printing original plate having high printing durability. [Means for Solving the Problems] The present invention achieves the above object in a direct drawing type lithographic printing original plate having an image-receiving layer on a support, in which the image-receiving layer contains the following general formula (I) and/or This can be achieved by a direct-drawing lithographic printing original plate characterized by containing resin particles having at least one polymer component having a functional group represented by the general formula (II). General formula (I) m-1→CII x ) TTCH= CH2 General formula (I
F) -6→CHz+TrCHtCHz-1 [However, in the above formula (I) or (n), W+
, -L- are each -so, -, -co- or 10OC-
represents n + + n! represent 0 or 1, respectively, and
represents a halogen atom] In the present invention, in the resin particles, even if the polymer component having the functional group represented by the general formula (I) and/or the general formula (II) has a crosslinked structure. In this case, the resin particles are preferably water resistant when reacting with the hydrophilic treatment liquid to develop hydrophilicity. [Function] In the direct-drawing lithographic printing original plate of the present invention, the image-receiving layer provided on the support has the general formula (I) and/or the general formula (II).
) is characterized by containing resin particles consisting of a resin (hereinafter referred to as resin [L]) containing at least one functional group represented by A processing liquid containing at least one type of chemical compound (
When treated with a desensitizing liquid or soaking water during printing, the functional group of the general formula (I) or the general formula (II) of the resin particle
The hydrophilic compound containing the nucleophilic substituent can be added to the end of the functional group of formula (D) generated by dehydrohalogenation from the functional group represented by can exhibit even more hydrophilicity, and at the same time, if the resin particles have a crosslinked structure, they have hydrophilicity but are insoluble or sparingly soluble in water, and have water-swelling properties, so printing is possible. It does not dissolve when soaked in water, and can maintain good printing characteristics even when printing a large number of sheets. Furthermore, the direct drawing type lithographic printing original plate of the present invention is not affected by the circular mound during plate-making processing, has excellent preservability before processing, and has the characteristics that hydrophilization processing can be carried out quickly. has. The mechanism by which the resin particles contained in the image-receiving layer according to the present invention are rendered hydrophilic by the hydrophilic compound containing a nucleophilic substituent is explained in the case of sulfite ion as a hydrophilic compound containing a nucleophilic substituent. As a representative example, the following reaction formula (II
Shown below. P~ represents a resin moiety other than the functional group of formula (1) or formula (II), and W represents an organic residue, more specifically represented by ←Z-Y→ in the general formula (IV) described later. Indicates a linking group. HCI Lipophilicity Lipophilicity Hydrophilicity...+1.1 In other words, the resin particles in the image-receiving layer of the present invention are treated with the processing liquid only when desensitizing the non-image area as a direct plate planographic printing original plate. A hydrophilic group is added to the terminal end by reacting with a hydrophilic compound containing a nucleophilic reactive substituent in the polymer as described above, thereby expressing hydrophilicity, that is, becoming lignophilic. Since it does not react with moisture in the atmosphere, there are no concerns regarding storage stability. Furthermore, the vinyl sulfone group, vinyl carbonyl group, and acryloxy group represented by the general formula (1) according to the present invention are functional groups that react very quickly with a hydrophilic compound containing a nucleophilic reactive substituent. Therefore, rapid development of hydrophilicity is possible. Furthermore, the functional group represented by general formula (n) can be expressed by reaction formula (1)
As shown in the following, the dehydrohalogenation reaction easily proceeds by alkali treatment and can be converted to the corresponding functional group of the general formula (I).
It can be used in the same way as the one above. Below, the resin particles used in the present invention will be explained in more detail. Specifically, the resin particles of the present invention have a maximum particle diameter of 1
It is 0 μm or less, preferably 5 μm or less. The average particle size of the particles is 1.0 μm or less, preferably 0.5 μm.
It is less than μm. Note that the smaller the particle size of the resin particles, the larger the specific surface area, which brings about good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, molecules Since the same disadvantages as in the case of dispersion occur, it is preferable to use the film at a thickness of 0.05 μm or more. In addition, in the present invention, if the resin particles are crosslinked,
It does not dissolve into the soaking water during printing, and can maintain good printing characteristics even when printing a large number of sheets. In the total amount of the composition for forming an image-receiving layer, the resin particles of the present invention are
It is preferably used in an amount of 10 to 90 parts by weight, preferably 15 to 80 parts by weight. The resin particles used in the present invention will be explained in more detail below. To explain the resin [L] forming the resin particles, the resin [L] contains at least a functional group represented by the general formula (I) and/or (n) in its molecular structure. . General formula (I) -W +-+-CHt-+rT-CII = CH2 General formula (II) % formula % In formulas (1) and (n), -W, -, -ken1- are each -3o
y +, -co- or -0OC-, nl,
nt represents 0 or 1, and X represents a halogen atom. In the above general formula (1) or (II), n, nl is more preferably 0. Moreover, the halogen atom of X specifically represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. As a more specific example of the copolymer component containing the functional group represented by formula (I) and/or (II) of the resin CL),
Examples include those represented by the following formula (III). General formula (Iff) Z-Y-W. In formula (I), Z is -coo-, -oco-, -o-. (represents a hydrocarbon group), -CONHCOO-, -CO
NHCON+(-. -CH2COO-, -CHzOCO-, or -(2〉'
represents. Y represents an organic residue that directly bonds or connects -2- and -We. Furthermore, +Z-Y+ is ←C→part and -l
110 may be directly connected. (2) -- represents a functional group represented by general formula (I) or general formula (n). al and a 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. General formula (I[) will be explained in more detail. Preferably, Z is -COO-1-0CO-1-〇-1-
Co-, -CON +, -3O2N- or -(=
)′ represents. 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 groups, phenethyl groups, 3-phenylpropyl groups, chlorobenzyl groups, bromobenzyl groups, methylbenzyl groups, methoxybenzyl groups, chloro-methylbenzyl groups, dibromobenzyl groups, etc.), optionally substituted aryl groups (e.g. phenyl groups) ,
tolyl group, xylyl group, mesityl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.). Y represents a direct bond or an organic residue connecting -2- and -111@. When Y represents a linked organic residue, this linking group represents a carbon-carbon bond that may be via a heteroatom; examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom), z - +CH=CJ-, -0-, -S-, -N-, -Coo
−. -CONH-, -3O2-2-SChNH-, -NHC
OO-. -NIC0N)f-, -51-, etc. alone or in combination (r2+r31r)
m, rl, and ri each represent the same content as rl above). al and al may be the same or different, and include a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (e.g. methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group) , an optionally substituted alkyl group having 1 to 12 carbon atoms such as ethoxycarbonyl group, proboxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, aralkyl groups such as benzyl group and phenethyl group, aryl groups such as phenyl group, tolyl group, xylyl group, and chlorophenyl group). Furthermore, the +-z -y+ bonding residue in formula (I[) may connect the ←C→ moiety and m-. Specific examples of polymer components containing functional groups represented by general formula (I) and/or formula (n) of the present invention are shown below. However, the scope of the present invention is not limited to these. In examples (ad) to (a-25), a is -H or =C
H, represents R+ CH=CHz, -CHy=
CHZ also represents CHZCHZX, where X is -Ft
C'j? lBr, representing I. (al) →CHt-C← ■ C00CHtCHzSOt-R+ CH.

[ (a -7) -+CH2-CH→-〇〇〇(C
Hi) is (h-R+ (1; U-K I (m: an integer of 1 to 4) and υ to n(t, n2) ``''ha blind tree in the resin [L] which is the resin particle of the present invention General formula (I
) and/or (II) in a bottle base in which the resin CL) is a copolymer, the polymer component containing functional groups (CL) is 30 to 99% by weight, especially 50 to 95% by weight of the total copolymer. % is preferable. Further, the molecular weight of the polymer of the resin (L) is preferably 1O'' to 106, particularly 5X10'' to 5X10''. A resin containing a polymer component having a functional group represented by
It can be synthesized by conventionally known synthesis methods. That is, a monomer containing a functional group represented by general formula (I) and/or (n) and a polymerizable functional group in the molecule (for example, a monomer corresponding to a repeating unit of general formula (I[[)) mer) and the general formula CI) and/or (II
) and a polymer compound containing a polymer component containing a functional group that chemically reacts with the low-molecular compound (i.e., polymer reaction). It is possible to do this. Furthermore, after synthesizing a resin having a functional group represented by general formula (II), a dehydrohalogenation reaction is performed by an alkali treatment to synthesize a resin containing a functional group represented by general formula (I). be able to. As the polymerizable functional group in the monomer synthesis described above, ordinary polymerizable double bond groups, specifically, l CH2=CH-CHl O-C-, CH2=CH-NH
CO-. CHz=CH-CHz-NHCO-, CHz=CH-S
Ch-. CH2=CH-CO-, CH2=CH-0-, CH2"
CH-S-. etc. can be mentioned. The sulfonylation, carbonylation, or carboxylic acid esterification reactions in the monomer synthesis or polymer reaction-based synthesis described above are described, for example, in Nippon Kagaku Complete Edition, New Experimental Chemistry Course, Volume 14, "Synthesis and Reactions of Organic Compounds" 751 pages, 1
000 pages. 1759 pages (1978) Published by Maruzen ■, S, Patai
. Z + Rappoport and C, Stirlin
g, 'The CheIIltstryor 5ul
fones and 5 ulfoxides” l
65 pages (1988), John Willey
It can be carried out according to the method described in the review article published by & 5ons. When the resin [L] is a copolymer, examples of other monomers that can be copolymerized with the monomer having a functional group of formula (I) and/or (n) include, for example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile,
methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacyline, vinylpyrazole, vinyldioxane, vinylfuran, vinyl quinoline, vinylthiazole, vinyloxazine, etc.). In the present invention, at least a portion of the resin particles may be crosslinked. In a resin in which at least a portion of the polymer has been crosslinked in advance (a polymer having a crosslinked structure in the polymer), the functional group of the formula (I) or (II) contained in the resin is made hydrophilic by treatment. Preferably, the resin is sparingly soluble or insoluble in acidic and alkaline aqueous solutions when the group is formed. Specifically, the solubility in distilled water at a temperature of 20 to 25°C is preferably 90% by weight or less, more preferably 70% by weight or less. As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used. That is, in the polymerization reaction of monomers containing the functional groups of formulas (1) and/or (II) above, polyfunctional monomers (monomers containing two or more polymerizable functional groups) or polyfunctional monomers A method of crosslinking between molecules by polymerizing in the coexistence of a functional oligomer; Alternatively, there is a method of crosslinking with a curing agent, or ■
The crosslinkable functional group-containing polymer has the above formula (I) and/or (n
) is a method of reacting a polymer with a compound containing a functional group. More specifically, in the method (2) using a polymer reaction, a polyfunctional monomer or a polyfunctional oligomer of the general formula (I) is used.
or a polar group (e.g. -OH) that can introduce the functional group (n)
, -Cll, -Br, -I. -N=C=O, -COCj! , -5ChCIl, etc.)
After polymerizing with a monomer containing to form a copolymer,
- Introducing a compound containing a functional group of general formula (I) and/or (n) by a polymer reaction. The polyfunctional monomer or oligomer used in the method (2) above may be one having two or more of the same or different polymerizable functional groups. Specifically, examples of monomers having the same polymerizable functional group include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol). #400゜#600.1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenol (such as hydroquinone, resorcinol, catechol, etc.) methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers (derivatives thereof), tribasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid) , itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or allylamides: polyamines (e.g. ethylenediamine, 1.3-propylenediamine, ], 4
-butylene diamine, etc.) and carboxylic acids containing vinyl groups (e.g., methacrylic acid, acrylic acid, crotonic acid,
Examples include condensates with allyl acetic acid, etc.). In addition, polyfunctional monomers or oligomers having different polymerizable functional groups include, for example, vinyl group-containing carboxylic acids [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid,
Reactants of acryloylpropionic acid, itaconilloylacetic acid, itaconiroylpropionic acid, carboxylic acid anhydride, etc. and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) ester derivatives or amide derivatives containing vinyl groups such as vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate,
allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl acrylate ester, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, allylmethacryloylpropionate, etc.) or amino Alcohols (e.g. aminoethanol, 1-aminopropatol, 1-aminobutanol, l-aminehexanol, 2
-aminobutanol, etc.) and a carboxylic acid containing a vinyl group. The monomer or oligomer having a polymerizable functional group of 2M or more used in the present invention is used in an amount of 10% by weight or less, preferably 5% by weight or less of the total monomers, and is polymerized to form a resin. However, in the case of a polymer containing a functional group represented by formula (I), among the above-mentioned polymerizable functional groups, CH2=CH-Coo-, CH2=C-COO-, C
H2: CH-CONH-. It is preferable not to use CH2=C)I-3o-, CH2=CH-C0-. In the present invention, as the functional group that proceeds with the crosslinking reaction in the method (1) or (2) above, the usual polymerizable double bond groups, such as those described above as polymerizable double bond groups, can be used. In the case of forming a chemical bond and bridging the polymers by the reaction of the reactive groups between the polymers in method (2), it can be carried out in the same manner as the reaction of ordinary organic low-molecular compounds. Specifically, it is described in detail in the bottom pages of Giyu Iwakura, Keisuke Kurita, "Reactive Polymers", Ikudansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals", Kodansha (published in 1976), etc. For example, a commonly known method is a polymer reaction using a combination of group A (functional group having a dissociable hydrogen atom) and group B functional group shown in Table 1 below. In addition, R and R' in Table 1 are hydrocarbon groups, and the formula (I
%') represents the same content as r g pr s. Table 1 In addition, -CONHCHiORz(R
z represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, hexyl group), and this reactive group is a group that condenses in a self-circular table type reaction. This is known as, and can also be used. Furthermore, for example, Tsuyoshi Endo [Refinement of Thermosetting Polymers J.
, C, M, C■ (published in 1986), Yuji Harasaki [Latest Binder Technology Handbook] Chapter 1 [-1. General Technology Center (published in 1985), Takayuki Otsu [Synthesis, design and development of new applications of acrylic resins] Chubu Business Development Center Publishing Department (published in 1985), Eizo Omori [Functional Acrylic Resins] Chikunon Stem (published in 1985), Inui Hideo, Gentabu Nagamatsu, "Photosensitive Polymer" Kodansha (1977), Takahiro Tsunoda, "New Photosensitive Resin", Printing Society Publishing Department (1981), G, E, Green and B, P,
5tar, R. J, Macro, Sci, Revs, Macr
o+CheII1. , (: 21(2), 187-2
73 pages (1981-82), C, G, Roffey
rPhotopolymerization of
5ur-face Cortings”, A, Wi
ley Interscience Pub. (published in 1982) and the like can be used. These crosslinkable functional groups have general formula (1) and/or (I
may be contained in one copolymer component together with the functional group represented by f) or in a separate copolymer component from the copolymer component containing the functional group of formula (I) and/or (II). It has already been explained that it may be contained in the combined component. Specific monomers corresponding to the copolymers containing these crosslinkable functional groups include, for example, the general formula (I[
) may be any vinyl compound containing the functional group that can be copolymerized with the polymer component. Such vinyl compounds are described, for example, in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Engineers, Baifukan (1988).
6th edition) etc. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-aminomethyl) form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl -2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-
(ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl or allyl group of dicarboxylic acid salts Compounds containing the crosslinkable functional group in a substituent such as half ester derivatives of , ester derivatives of these carboxylic acids or sulfonic acids, and amide derivatives are included. If necessary, a reaction accelerator may be added to the resin CL) of the present invention in order to promote the crosslinking reaction. Examples include acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), peroxides, azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like. As the crosslinking agent, compounds commonly used as crosslinking agents can be used. in particular, . Use the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Kobaken Single Child Data Handbook Basic Edition J Baifukan (1986)" edited by The Society of Polymer Science, etc. For example, organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.) silane coupling agents, etc.), polyisocyanate compounds (e.g. toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate) ), polyol compounds (e.g., 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1.1.1-trimethylolpropane, etc.), polyamine compounds (e.g., ethylenediamine, γ- hydroxyprobylated ethylene diamine, phenylene diamine, hexamethylene diamine, N-aminoethyl piperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo ( (published in 1985), compounds described in "Epoxy Resin" edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (published in 1969), etc.), melamine resin (for example, "Uria Melamine Resin", edited by Miwa-bu, Hideo Matsunaga, Nikkan Kogyo Shimbun) (1969), etc.), poly(
meth)acrylate compounds (for example, those described in Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, eds., "Oligomer", Ikudansha (1976), Eizo Omori, "Functional Acrylic Resin", Technosystem (1985), etc. Compounds are mentioned,
Specifically, polyethylene glycol diacrylate,
Examples include neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof. Resin CL containing at least one functional group that generates at least one hydrophilic group by treatment with a treatment liquid containing a hydrophilic compound having a nucleophilic reactive substituent synthesized as described above, In the present invention, particles exhibit a maximum particle size of 5 μm or less and an average particle size of 1.0 μm or less. The resin particles of the present invention having such a microparticle size can be made into a desired particle size by allowing the resin powder to coexist as is and dispersing it when preparing the composition for forming a surface layer. Alternatively, conventionally known dry and wet atomization methods,
Alternatively, a method of using polymer gel latex can be used. That is, a method of directly pulverizing resin powder into fine particles using a conventionally known pulverizer or dispersing machine (for example, a ball mill, paint shaker, sound mill, hammer mill, jet mill,
(Kedimir, etc.) and a conventionally known method for producing latex particles of paint or electrostatic photographic liquid developer. The latter method of producing polymer latex involves dispersing resin powder in combination with a dispersion polymer.The resin powder and dispersion-assisting polymer are kneaded in advance to form a mixed material, which is then crushed and then There are mechanical methods such as a method of dispersing in the coexistence of a dispersed polymer. Specifically, for example, "Paint Flow and Pigment Dispersion" translated by Kenji Ueki J Kyoritsu Shuppan (1971), "Solomon!!! Chemistry of Materials", rPaint and SurfaceCoa
ting theory and practice”,
Yuji Harasaki "Coating Engineering" Breakfast Bookstore (1971)
, Yuji Harasaki, “Basic Science of Coatings,” Maki Shoten (197
(published in 1987), JP-A-62-96954, JP-A-62-1151
71. It is described in 62-75651 publications. Alternatively, a method for easily obtaining latex particles by a conventionally known polymerization reaction such as a suspension polymerization method or a dispersion polymerization method can also be used. Specifically, the chemistry of So Muroi-r polymer latex.
Polymer Publishing Association (1970), Oku 1) Taira, Hiroshi Inagaki [
"Synthetic Resin Emulsion" Kobunshi Publishing Association (published in 1978)
, So Muroi - [Introduction to polymer latex] Kobunsha (1983)
year) etc. In the present invention, a method of forming polymer latex particles is preferred, and by this method, the average particle size can be easily reduced to 1. Oa
It can be made into resin particles of not more than m. These fine latex particles with uniform particle size are
This can be easily achieved by manufacturing by a non-aqueous dispersion polymerization method. The non-aqueous solvent used in the non-aqueous latex may be any organic solvent as long as it has a boiling point of 200° C. or lower, and may be used alone or in combination of two or more. Specific examples of this organic solvent include alcohols such as methanol, ethanol, propatool, butanol, fluorinated alcohol, and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, and ethers such as diethyl ether, tetrahydrofuran, and dioxane. carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, benzene , aromatic hydrocarbons such as toluene, xylene, and chlorobenzene, methylene chloride,
dichloroethane, tetrachloroethane, chloroform,
Examples include halogenated hydrocarbons such as methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the compound examples described above. By synthesizing polymer latex using dispersion polymerization in these non-aqueous solvent systems, the average particle diameter of resin particles can be easily reduced to 1.
It is possible to obtain monodisperse particles with a particle size distribution of .mu.m or less and a very narrow particle size distribution. Specifically, K, E, J, Barrett rD
ispersion Polymerization
in Organic Media J Jo
hn Will-1! V (published in 1975), Koichi Murata, Polymer Processing. l, 20 (published in 1974), Tsunetaka Matsumoto, Toyokichi Tange 1 Journal of the Japan Adhesive Association, 183 (1973), Toyokichi Tange 1 Journal of the Japan Adhesive Association, IL, 26 (19g7)
, D., J., Walbridge, NATO,A.
dv, 5turdy. In5t, Ser, E, Na67,40 (198
3) , British Patent Nos. 893429 and 934038, US Patent Nos. 1122397 and 3900412
, 4606989, Japanese Patent Application Laid-Open No. 1797-1797
51. The method is disclosed in Publications No. 60-185963 and the like. The resin particles of the present invention described above generate hydrophilic groups by reaction with a hydrophilic compound containing a nucleophilic substituent by treatment with a desensitizing solution or soaking water during printing. Therefore, in the original plate of the present invention containing the resin particles in the image-receiving layer, the hydrophilicity of the non-image area that is made hydrophilic by the desensitizing treatment liquid is further enhanced by the hydrophilic groups generated by the resin particles. Therefore, the hydrophilicity of the image area and the hydrophilicity of the non-image area become clear, and it is possible to prevent ink from adhering to the non-image area during printing. As a result, it becomes possible to print a large number of prints with clear image quality and no background smear. In addition, in the case of the above-mentioned resin particles that are partially cross-linked, the solubility in water is significantly reduced while maintaining hydrophilicity.
Becomes poorly soluble or insoluble. Therefore, the effect that the hydrophilicity of the non-image area is further enhanced by the hydrophilic groups generated by the resin particles is improved, and the durability is improved. In terms of more specific effects, even if the amount of the above-mentioned functional groups in the above-mentioned resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or the increase in the size of the printing machine or the fluctuation of printing pressure. Even when printing conditions become severe, it is possible to print a large number of sheets with clear image quality and no background smudges. As the matrix resin (binder resin) provided for the image-receiving layer of the present invention, any of the various binder resins conventionally known can be used. Typical examples include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl butyral, alkyd resin, Silicone resin, epoxy resin, epoxy ester resin, polyester resin, etc., and water-soluble polymer compounds such as polyvinyl alcohol, modified polyvinyl alcohol, starch, oxidized starch, carboxymethyl cellulose, hydroxyethyl cellulose, gelatin, polyacrylic acid, polyvinyl pyrrolidone, polyvinyl ether -Maleic anhydride copolymers, polyamides, polyacrylamide, etc. The molecular weight of the binder resin is preferably 101 to 10@1.
Jl*L, or 5xl Qs ~ 5Xl O'. Further, the glass transition point of this resin is preferably -10°C.
-125°C, more preferably 0°C - 85°C. 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 aluminum. The ratio of binder resin/pigment in the image-receiving layer varies depending on the type of material and, in the case of pigment, the particle size, but is generally 1/(0.5 to 5) by weight, preferably 1/(0.8). ~2.
5) The level 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 crosslinking agent, commonly used ammonium chloride, organic peroxide, metal soap, organic silane, polyurethane crosslinking agent, epoxy resin curing agent, etc. can be used. Specifically, it is described in Shinzo Yamashita and Tosuke Kaneko, eds. [Crosslinking Agent Handbook], published by Taiseisha (1981). Examples of the support used in the present invention include wood-free 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 (back layer) is provided on the support surface opposite to the image-receiving layer for the purpose of preventing curling. ) can be provided. Here, the intermediate layer is an emulsion type resin such as acrylic resin, ethylene-butadiene copolymer, methacrylate ester-butadiene copolymer, 3-acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer; epoxy resin, polyvinyl Solvent-type resins such as butyral, polyvinyl chloride, and polyvinyl acetate; mainly composed of at least one of the aforementioned water-soluble resins, but inorganic pigments and waterproofing agents may be added as necessary. can. The structure of the back coat layer is also almost the same as that of the intermediate layer. When used as PPC plate-making, in order to further reduce background staining of the printing original plate of the present invention, the printing original plate should have a volume resistivity of 10′@~10”Qas.
Additionally, dielectric agents can be added to the image-receiving layer, interlayer and/or backcoat layer. The dielectric agent may be inorganic or organic.
, K, Li, Mg, Zn, Co, Ni, etc., monovalent or polyvalent metal salts, organic ones such as polyvinylbenzyltrimethylammonium chloride, acrylic resin-modified quaternary ammonium salts, and other polymeric cation conductive agents. and polymeric anionic dielectric agents such as polymeric sulfonates and polymeric sulfonates. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 40% by weight of the amount of binder used in each layer.
It is 20% by weight. In general, to make the direct drawing type lithographic printing original plate of the present invention, an aqueous solution containing an intermediate layer component, if necessary, is coated on one side of a support, dried to form an intermediate layer, and then an intermediate layer containing an image-receiving layer component is formed. An aqueous solution may be applied and dried to form an image-receiving layer, and if necessary, an aqueous solution containing backcoat layer components may be applied and dried to the other side to form a backcoat layer. The amount of each of the image-receiving layer, intermediate layer, and back coat layer is 1
~30g/l&, 5~20g/d 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 includes a hydrophilic group-containing compound that easily reacts nucleophilically with the double bond in the resin particles of the present invention containing a functional group represented by the general formula (I). This is achieved by treatment with a solution (aqueous solution or mixed solution containing a water-soluble organic solvent). As a hydrophilic compound that causes a nucleophilic substitution reaction on the double bond of the functional group represented by general formula (I), parts: / Paa
The nucleophilic constant n[:R2O, Paarson,
H, 5obel, J, Songstad, J,
Acer, Chew. Soc, , , JLL, 319 (1968)
Examples include hydrophilic compounds which contain a substituent having a value of 5.5 or more and which dissolve in 1 part by weight or more in 100 parts by weight of distilled water. Specific compounds include, for example, hydrazine, hydroxylamine, sulfites (ammonium salts, sodium salts, potassium salts, zinc salts, etc.), thiosulfates, etc.
In addition, at least one group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group is present in the molecule.
Examples include mercapto compounds, hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds containing two polar 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, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercaptobenzenesulfonic acid , 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1゜2-dimercaptopropionylaminoacetic acid, 2゜3-dihydroxypropylmercaptan, 2
-Methyl-2-mercapto-1-aminoacetic acid etc. as a sulfinic acid compound such as 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, dicarboxybenzenesulfinic acid, etc. 2-hydrazinoethanesulfonic acid, 4 as a hydrazide compound
-Hydrazibutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid, etc., as a 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-dihydroxy propyl)amine, N,N-di(2,3-dihydroxypropyl)amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2
-hydroxyethylmorpholine, 2-carboxyethylmorpholine, 3-carboxypiperazine and the like. These nucleophilic compounds are used by being included in the desensitizing treatment solution described above. The amount of the nucleophilic compound present in these treatment solutions is 0.05 mol/l to 10 mol/l, preferably 0.1 mol/l to 5 mol/l. In addition, p)( of the treatment liquid is preferably 4 or more. The treatment conditions are preferably a temperature of 15°C to 60°C and an immersion time of 10 seconds to 5 minutes. The treatment liquid contains the above-mentioned nucleophilic compound and I ) Other compounds may be contained in addition to the H regulator. For example, add 1 part by weight of a water-soluble organic solvent to 100 parts by weight of water.
It may contain up to 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol,
ethanol, propatool, propargyl 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, tetrahydrobilane, etc.) amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate,
ethyl formate, etc.), and these may be used alone or in combination of two or more. Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants. For example, Hiroshi Horiguchi [New Surfactant J Sankyo Publishing ■, (197
Compounds described in Ryohei Oda and Hiroshi Teramura, "Synthesis of Surfactants and Their Applications" Maki Shoten (published in 1980) can be used. Furthermore, a material containing an antifoaming agent and other various additives may be used as required. Note that the scope of the present invention is not limited to the specific compound examples described above. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Production Example 1 of Resin Particles: (L-1 A mixed solution of 95 g of dodecyl methacrylate, 5 g of acrylic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. butyronitrile) (abbreviation A, engineering, B, N,) 1.5 g
was added and reacted for 8 hours. Add 12 g of glycidyl methacrylate to this reaction mixture solution.
5 1 g of t-butylhydroquinone and 0.8 g of N,N-dimethyldodecylamine were added and reacted at 100°C for 15 hours to obtain a dispersion resin CP-11 having the following structure. Dispersion resin CP-1) CH) [H Next, the dispersion resin CP-1] 7.5 g (as solid content)
A mixed solution of 50 g of monomer CM-1) having the following structure and 200 g of methyl ethyl ketone was heated to 65° C. with stirring under a nitrogen stream. To this, 2,2-azobis(isobutyronitrile) (abbreviation A, engineering, V, N,) 0.7
g was added and reacted for 6 hours. Twenty minutes after the addition of the initiators (A, T, V, N, ), the homogeneous solution began to become cloudy and the reaction temperature rose to 90°C. After cooling, it was passed through a 200 mesh nylon cloth to obtain a white dispersion. Latex CL-1 with an average particle size of 0.45 μm
〕Met. Monomer CM-1] CH3 CH,=C Coo (CHz) 20CO(CH2)之5OzC
) I = CH2 Resin particle production example 2 [L-2] 20 g of monomer CM-2 having the following structure, dispersion resin [P-i
] 8g (as solid content), ethyl acetate 150g 5n-
A mixed solution of 150 g of hexane was heated to 55° C. with stirring under a nitrogen stream. A.1. 0.5 g of V and N were added and reacted for 4 hours to obtain a white dispersion. After cooling 20
The resulting dispersion was latex CL-2) with an average particle size of 0.30 μm. Monomer CM-23 CH3 ■ CH2=C C00CH2COCH= CH2 Resin particle production example 3: CL-33 Monomer CM-3 with the following structure] 20 g, Macromonomer CP-2 with the following structure] 5 g, Methyl ethyl ketone 150
The reaction was carried out in the same manner as in Production Example I of Resin Particles, except that a mixed solution of CM-3 was used, and a white latex (L-3) with an average particle diameter of 0.30 μm was obtained. CH2-C Coo(CH7hOCO(CH2)rs+1,000CH,-C
H) - Example 4 of producing resin particles: CL-4) 20 g of monomer [M-4] with the following structure, 2.0 g of divinylbenzene, 336 g of macromonomer CP-3 with the following structure, 150 g of methyl isobutyl ketone. The reaction was carried out in the same manner as in Resin Particle Production Example 1 except that a mixed solution was used to obtain white latex CL-4 with an average particle size of 025 μm. Monomer CM-4] CHl CHl ■ Production example 5 of resin particles: [L-5] Monomer [M-5] with the following structure 20 g, ethylene glycol diacrylate 2.5 g, acrylic acid 5 g, macromonomer CP-2] 6g and methyl ethyl ketone 2
The reaction was carried out in the same manner as in Resin Particle Production Example 1 except that a mixed solution of 0.00 g was used to obtain white latex I:L-5,1 with an average particle size of 0.20 tlm. Monomer CM-5] Production Example 6 of Resin Particles ~l3:l:I,-6)~
[L-13] Resin particles [L-63] were produced in the same manner as in Production Example 4, except that the monomers shown in Table 2 below were used instead of monomer CM-4. ~(L-13: l was obtained. Production examples 14 to 20 of resin particles: (L-14) ~[
L-201 Manufacturing of resin particles except for making a mixed solution of 20 g of monomer CM in Table 3 below, a predetermined amount of crosslinking monomer, 5 g of macromonomer [P-4) with the following structure, and 200 g of methyl ethyl ketone. The reaction was carried out in the same manner as in Example 1, and each latex CL
-14) to CL-20] were obtained. Macromonomer CP-4] COOCaHs (n) Example 1 A resin [33-
1) A mixture of 35, 5 g (as solid content) of resin particles [L-1], 50 g of zinc oxide, and 150 g of toluene was dispersed in a ball mill for 2 hours, and then glutaric anhydride 4
g was added and dispersed for 10 minutes. The resulting dispersion was applied with a wire bar to a dry coating weight of 18 g/m'', dried at 100°C for 30 seconds, and further dried at 120°C for 1 hour.
A lithographic printing original plate was prepared by heating for 0 minutes. Resin [S-13 7H)CHx ■ This original plate was treated with a desensitizing treatment liquid (E-1
) for 3 minutes and then washed with water. Desensitization treatment liquid (E-1) The above was dissolved. A droplet of 2 μl of distilled water was placed on this, and the contact angle with the water formed was measured with a goniometer and was found to be 10″ or less.The contact angle before 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 degree of oxidation needs to be 20° or less in terms of contact angle with water.) Next, a plate is made using commercially available PPC, and the obtained master plate is desensitized under the same conditions as above. An original plate for printing 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. (Sakurai Seisakusho ■Oliver 5'
2) and printed on high-quality paper. Even after 3,000 sheets were printed, there were no problems 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, 180% R.
) (When the plate was made using commercially available PPC, the image of the obtained original plate had a density of 1.0 or more in the image area, no blurring in the non-image area, and the image quality in the image area was clear. When this was printed in the same manner as above, there was no problem even after printing 3,000 sheets. As mentioned above, the original plate did not deteriorate in image quality even under high temperature and humidity conditions by PPC plate making. Example 2 High-quality paper A resin having the following structure (S-2
) 34g, resin particles CL-3] 6g (as solid content)
A mixture of 50 g of zinc oxide and 150 g of toluene was dispersed in a ball mill for 2 hours, and further, 4 g of 1,3-xylylene isocyanate was added thereto and dispersed in the ball mill for 10 minutes. The resulting dispersion has a dry coverage of 18 g/m
” and dried at 110°C for 1.5 hours to prepare a lithographic printing original plate. Resin [S-2] This original plate was operated in the same manner as in Example 1 to make a plate. The density of the image area of the obtained master 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. ■Made by Oliver 52
(type) and printed on high-quality paper. Even after 3,000 sheets were printed, there were no problems 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 the image of the obtained original plate was made with a commercially available PPC, the density of the fR area was 10 or more, there was no ground blur in the non-image area, and the image quality of the image area was clear. When printing was carried out in the same manner as above, there was no problem even after printing 3000 sheets.As mentioned above, the image quality of this original plate did not deteriorate in PPC plate making even under high temperature and high humidity conditions.Example 3 ~ IO With the following structure Example C3-3] 34 g, 6 g of resin particles (L) in Table 4 below, 70 g of zinc oxide, 10 g of silica gel,
A mixture of 5 g of 1.5-(N-imidazolyl)carbamoylnaphthalene and 150 g of toluene was dispersed in a ball mill for 2 hours. The dry adhesion amount of the obtained dispersion was 18 g.
/m2 using a wire bar, and dried at 120° C. for 2 hours to prepare a lithographic printing original plate. Resin [S-3] OH Go CH3-f-CH2-
C7cho1CHI-CH←"+CH2-C→Ryogo1
[] C00C)l z C00CH2CHz OHC
0OH Ani: 5x+O" (weight ratio) Table 4 Each original plate was treated with the same method as in Example 1 except that a desensitizing solution (E-2) prepared according to the following formulation was used as the desensitizing solution.
Plate making and printing were performed in the same manner as above. Desensitization treatment liquid (E-2) These were dissolved in distilled water to bring the total amount to 11, and then the pH was adjusted to 11.0 with sodium hydroxide. The density of the image area of the 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 in the image area was clear. When this was printed in the same manner as above, there was no problem even after printing 3000 sheets. Examples 11 to 14 34 g of Example [S-4] with lower 1-layer structure, 6 g each of resin particles [L] of Table 5 below (as solid content), silica gel
A mixture of 5 g of alumina, 5 g of alumina, and 80 g of toluene was dispersed in a ball mill for 2 hours, and then 5 g of phthalic anhydride was added and dispersed for 10 minutes. The resulting dispersion has a dry coverage of 1
Apply with a wire bar so that it is 8g/m',
It was dried at ℃ for 20 hours to prepare a lithographic printing original plate. Resin CG-4] CH) CH3i: 5.5xl O' (weight ratio) Table 5 This was plate-made in the same manner as in Example 3, and then printed using a printing machine. The density of the obtained printing original plate was 1.0 or more, and the image quality was clear. Further, the image quality of the printed matter after printing 3000 sheets was a clear image without blurring. Examples 15 to 26 Using each of the original printing plates prepared in Examples 2 to 14, distilled water was added to 05 mol of the nucleophilic compound shown in Table 6 below, 100 g of an organic solvent, and 10 g of Nucol B4SN (manufactured by Nippon Nyukazai ■). After addition, the pH of each mixture was adjusted to 11.0. Each original plate was immersed in the above treatment liquid for 3 minutes 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 less than lo0, and the plate was sufficiently hydrophilized. Furthermore, even after printing 3000 sheets, the print image quality of the printed matter was good with no blurring and clear images. [Effects 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 (2)

[Claims] (1) In a direct-drawing lithographic printing original plate having an image-receiving layer on a support, the following general formula (I) is present in the image-receiving layer:
and/or a direct-drawing lithographic printing original plate characterized by containing resin particles having at least one polymer component having a functional group represented by the general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula (I) or (II), -W_1-, -W_2 - is respectively -SO_2-, -C
Represents O- or -OOC-, n_1 and n_2 each represent 0 or 1, and X represents a halogen atom] (2) Claim (I) characterized in that, in the resin particles, the polymer component having a functional group represented by the general formula (I) and/or the general formula (II) has a crosslinked structure.
The original plate for electrophotographic lithographic printing described above.