JPH04216995A - Manufacture of direct drawing-type lithographic printing plate - Google Patents

Abstract

PURPOSE:To obtain an improved image-receptive layer composition of a direct drawing-type lithographic printing plate free from background contamination and with high plate wear resistance and improve its manufacturing technique by improving insensitiveness to grease and adhesiveness of oily ink to an image- receptive layer. CONSTITUTION:Resin particles having a formyl group and/or an acetal group and binder resin are added to the image-receptive layer of a direct drawing-type lithographic printing plate. Then the image-receptive layer is made insensitive to grease using a treatment liquid containing a hydrophilic chemical compound with a substitution group of Pearson's nucleophilic constant n of 5.5 or high after the formation of an image. Further the image-receptive layer becomes hydrophilic due to the addition of the mentioned hydrophilic chemical compound to the terminals of the formyl and acetal groups. In addition, the layer becomes insoluble or hardly soluble in water and swollen with water while remaining hydrophilic and further, has improved plate wear due to the structural bridging of resin particles. In addition, the layer is not hydrophilic before the formation of an image and as such, is highly resistant against environmental effect.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a method for producing a direct-drawing type lithographic printing original plate, and in particular to a method for producing a direct-drawing type lithographic printing original plate suitable for an office printing original plate. This invention relates to improvements in compositions for forming image-receiving layers. BACKGROUND OF THE INVENTION At present, as printing plates for office use, direct drawing type lithographic 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 in which a drawing is done by hand with oil-based ink on the image-receiving layer, or printing is performed using a typewriter, an 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 original printing plate after platemaking is
After the surface is treated with a desensitizing liquid (so-called etch liquid) to desensitize the non-image area, it is used as a printing plate for lithographic printing. [0003] Conventional direct-drawing type 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 disclosed in U.S. Patent No. 2
As described in No. 532,865, the image-receiving layer mainly contains a water-soluble resin binder such as PVA, an inorganic pigment such as silica, calcium carbonate, and a water-resistant agent such as a melamine-formaldehyde resin initial condensate. It is composed as a component. [Problems to be Solved by the Invention] However, conventional printing plates obtained in this manner have been modified by adding a large amount of water-resistant agent or adding a hydrophobic resin to improve printing durability. Increasing the hydrophobicity by using other materials improves the printing durability, but reduces the hydrophilicity and causes printing stains.On the other hand, increasing the hydrophilicity deteriorates the water resistance and reduces the printing durability. There was a problem. Especially in high-temperature environments of 30°C or higher,
This had major drawbacks, such as the surface layer (image-receiving layer) being dissolved in the soaking water used in offset printing, resulting in both reduced printing durability and printing stains. Furthermore, in the lithographic printing original plate, 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 becomes hydrophilic. Even if the printing properties are sufficient and the above-mentioned printing stains do not occur, there is a problem that the oil-based ink in the image area is missing during printing, resulting in a decrease in printing durability. [0006] The present invention is intended to solve the above-mentioned problems associated with 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 by providing a method for producing a direct-drawing lithographic printing original plate having an image-receiving layer on a support, in which formyl groups and/or
Or, after forming an image on a direct plate lithographic printing original plate containing at least a binder resin and resin particles having at least one polymer component having a functional group represented by the following general formula (I), A printing original plate is obtained by desensitizing a non-image area other than the image area with a treatment liquid containing a hydrophilic compound containing a substituent having at least a Parson's nucleophilic constant n of 5.5 or more. This can be achieved by a method for producing a direct-drawing lithographic printing original plate, which is characterized by the following. General formula (
I) [Chemical formula 2] [However, in the above formula (I), R 1 and R 2 may each be the same or different and represent a hydrocarbon group, or R 1 and R 2 may be connected to each other to form a ring. [0008] In the present invention, in the resin particles, a formyl group and/or an organic residue formed by the general formula (I
) may have a crosslinked structure, and in this case, when reacting with the desensitizing treatment liquid to develop hydrophilicity, the resin particles will exhibit water resistance. It is preferable because it has. [Function] The method for producing a direct drawing type lithographic printing original plate of the present invention includes:
The image-receiving layer provided on the support contains resin particles made of a resin (hereinafter referred to as resin [L]) containing at least one formyl group and/or a functional group represented by general formula (I). This is characterized by the fact that when the resin particles are treated with a treatment liquid (desensitizing liquid or soaking water during printing) containing at least one hydrophilic compound containing a nucleophilic substituent, formyl group and/or the above general formula (I
) The hydrophilic compound containing the nucleophilic substituent can be added to the end of the functional group represented by ), and as a result, the image-receiving layer can exhibit even more hydrophilicity, and at the same time, If it has a crosslinked structure, it has hydrophilicity, is insoluble or poorly soluble in water, and has water swelling properties, so it will not be eluted with soaking water during printing and can be printed in large numbers. Good printing characteristics can be maintained even when printing is performed. [0010] The size of the resin particles used in the present invention is as follows:
The maximum particle diameter of the particles is 10 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 or less. In addition,
The smaller the particle diameter of resin particles, the larger the specific surface area.
Colloidal particles (0.01 μm or less) are sufficient to bring about good effects in terms of the electrophotographic properties mentioned above, but if they become too small, the same disadvantages as in the case of molecular dispersion will occur, so 0.05 μm or more It is preferable to use it in [0011] To explain the resin [L] forming the resin particles of the present invention, the resin [L] contains at least a formyl group and/or a functional group represented by the general formula (I) in its molecular structure. This is what happens. General formula (I) [Chemical formula 3] In the above formula (I), R 1 and R2 may be the same or different, and represent a hydrocarbon group, or R 1 ,
R2 represents organic residues connected to each other to form a ring. When R 1 and R2 each represent a hydrocarbon group, R1 and R2 are 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). Groups: Specific examples include methyl group, ethyl group, 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-
An optionally substituted alkenyl group having 2 to 12 carbon atoms, including fluoroethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, 3-methoxypropyl group, etc. Specific examples include propenyl group, butenyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, etc., 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, methoxybenzyl group, dimethoxybenzyl group, chlorobenzyl group, bromobenzyl group, fluorobenzyl group,
Examples include dichlorobenzyl group. An optionally substituted alicyclic group having 3 to 12 carbon atoms (specific examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, etc.). When R 1 and R 2 represent organic residues that are linked to each other to form a ring, preferably the following general formula (
Examples include the functional group represented by Ia), that is, a cyclic acetal group. General formula (Ia) [Chemical formula 4] In formula (Ia), R 3 and R 4 may be the same or different, and each represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or -OR 5 groups (R 5
represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4. [0014] R 3 , R 4 and R 5 have 1 to 1 carbon atoms
Preferred examples of optionally substituted hydrocarbon groups include aliphatic groups (specifically, the same content as exemplified for R1 and R2), aromatic groups (e.g., phenyl group, tolyl group, xylyl group). group, methoxyphenyl group, chlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, dimethoxyphenyl group, chloro-methylphenyl group, naphthyl group, etc.). More preferably, formulas (I), (Ia
), when R 1 to R 5 are aliphatic groups,
Preferred are alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 3 to 6 carbon atoms, and aralkyl groups having 7 to 9 carbon atoms. Examples of the polymer component containing a formyl group and/or a functional group represented by the formula (I) used in the present invention include those represented by the repeating unit of the following general formula (II). General formula (II) [Image Omitted] In formula (II), Z is -COO-, -OCO-, -O
-, -CO-, [Formula 6] -CONHCOO-, -CONHCONH-, -CH
2 represents COO-, -CH 2 OCO-, or [Chemical formula 7]. Y represents an organic residue that directly bonds or connects -Z- and -W0. Furthermore, [Image Omitted] may be directly linked. W 0 represents a formyl group or a functional group represented by (I). [0020] a 1 and a 2 may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (II) will be explained in more detail. Preferably, Z is -COO-, -OCO-, -O-
, -CO-, represents [Chemical formula 9]. [0022] However, r 1 is a hydrogen atom, and has 1 to 8 carbon atoms.
an optionally substituted alkyl group (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) group, 2-
hydroxyethyl group, 3-bromopropyl group, etc.), optionally substituted aralkyl group 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, etc.), optionally substituted aryl groups (e.g., phenyl group, 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 -Z- and -W0. When Y represents a connecting organic residue, this linking group represents a carbon-carbon bond that may be via a heteroatom (heteroatoms include an oxygen atom,
sulfur atom, nitrogen atom), for example, consisting of a bonding unit such as
, r 6 each represent the same content as r 1 above). [0024] a 1 and a 2 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, a hydrocarbon group (for example, a methyl group,
Ethyl group, propyl group, butyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
butoxycarbonyl group, hexyloxycarbonyl group,
Alkyl groups having 1 to 12 carbon atoms which may be substituted such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, chlorophenyl group aryl group, etc.). Furthermore, the bonding residue [Image Omitted] in formula (II) may link [Image Omitted] and the -W0 moiety. Specific examples of the polymer component containing a formyl group and/or a functional group represented by the general formula (I) of the present invention are shown below. Example In (a-1) to (a-15), a
represents -H or -CH3. However, the scope of the present invention is not limited to these. (a-1) [Formula 13] (a-2) [Formula 14] (a-3) [Formula 15] (a-4) [Formula 16] (a-5) [Formula 17] (a-6) [Formula 18] (a-7) [Formula 19] (a-8) [Formula 20] (a-9) [Formula 21] (a-10) [Formula 22] (a-11) [Formula 23] ( a-12) [Formula 24] (a-13) [Formula 25] (a-14) [Formula 26] (a-15) [Formula 27] [0027] Furthermore, the compound represented by the general formula (Ia) of the present invention Examples (a'-1) to (a'-
9), R 7 and R 8 represent an alkyl group having 1 to 4 carbon atoms or -CH 2 C6 H 5 , and R
9 is an alkyl group having 1 to 4 carbon atoms, -CH 2 C
Represents 6 H 5 or a phenyl group. However, the scope of the present invention is not limited thereto. (a'-1) [Chemical formula 28] (a'-2) [Chemical formula 29] (a'-3) [Chemical formula 30] (a'-4) [Chemical formula 31] (a'-5) [Chemical formula 32] (a'-6) [Chemical 33] (a'-7) [Chemical 34] (a'-8) [Chemical 35] (a'-9) [Chemical 36] Resin of the present invention [L] When the resin [L] is a copolymer, the polymer component containing a formyl group and/or a functional group of general formula (I) is 30 to 99% by weight of the total copolymer, especially It is preferably 50 to 95% by weight. Moreover, the molecular weight of the polymer of this resin is 103
~106, particularly preferably 5 x 103 - 5 x 105. The resin containing a polymer component having a formyl group and/or a functional group represented by the general formula (I) of the present invention as described above can be synthesized by a conventionally known synthesis method. That is, a 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)) A method of polymerizing 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. (i.e. polymer reaction)
It can be synthesized by Furthermore, after synthesizing a resin having a functional group represented by the general formula (I), a formyl group-containing resin can be synthesized by subjecting the resin to 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,
Synthesis methods for formyl group-containing compounds are described in the Chemical Society of Japan, New Experimental Chemistry Course, Vol. 14, 636 (1978), published by Maruzen Co., Ltd., E. Muller, “Methoden
der Organischen Chemie” p.
13 (1954) Georg Thieme Ver.
lag, edited by the Chemical Society of Japan, Experimental Chemistry Course, Volume 19,
p. 231 (1957) published by Maruzen Co., Ltd., etc., and methods for synthesizing acetal group-containing compounds include the Chemical Society of Japan, New Experimental Chemistry Course, Vol. 14, p.
．． 611 (1978), published by Maruzen Co., Ltd., and the like. Examples of the polymerizable functional group used in the above-mentioned monomer synthesis include common polymerizable double bond groups, specifically, the following. When the resin [L] is a copolymer, examples of other monomers that can be copolymerized with the above monomer having a formyl group and/or a functional group of formula (I) include, for example, α-olefin vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, (vinylpyrazole, vinyldioxane, vinylfuran, vinylquinoline, vinylthiazole, vinyloxazine, etc.). Furthermore, in the present invention, at least a portion of the above 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 formyl group and/or the functional group of formula (I) contained in the resin undergoes a nucleophilic reaction. It is preferable to use a resin that is sparingly soluble or insoluble in acidic and alkaline aqueous solutions when reacting with a treatment solution containing a hydrophilic compound having a substituent group to form a hydrophilic group. Specifically, the solubility in distilled water is preferably 90% by weight or less, more preferably 7% by weight at a temperature of 20 to 25°C.
It shows a solubility of 0% by weight or less. [0034] As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used. That is, in the polymerization reaction of a monomer containing a formyl group and/or a functional group of the above formula (I), a polyfunctional monomer (a monomer containing two or more polymerizable functional groups) or a polyfunctional (1) A method of crosslinking between molecules by polymerizing in the coexistence of a functional oligomer; Is it a method of crosslinking with a curing agent?
This method includes a method in which a crosslinkable functional group-containing polymer is reacted with a compound containing a formyl group and/or a functional group of the above formula (I). [0035] More specifically, in the method (2) using a polymer reaction, a polyfunctional monomer or a polyfunctional oligomer is
A formyl group or a polar group into which a functional group of general formula (I) can be introduced (e.g. -OH, -Cl, -Br, -I, -N
H2, -COOH, -SH, [Chemical 38] -N=C=O, -COCl, -SO2Cl, etc.)
After polymerizing with a monomer containing to form a copolymer,
A compound containing a formyl group and/or a functional group of general formula (I) is introduced 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, monomers having the same polymerizable functional group include 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 methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives): dibasic 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 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.). Further, polyfunctional monomers or oligomers having different polymerizable functional groups include, for example, vinyl group-containing carboxylic acids [for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropion] Reactants of acids, itaconiroyl acetic acid, itaconiroyl propionic acid, carboxylic acid anhydrides, etc. and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) ) and other vinyl group-containing ester derivatives or amide derivatives (e.g. vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylpropionate, methacryloylpropion) Allyl acid, vinyloxycarbonyl methacrylate methyl ester, vinyloxycarbonyl acrylate methyloxycarbonyl ethylene ester, N-allylacrylamide, N-
allyl methacrylamide, N-allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.) or amino alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a vinyl group. Examples include condensates with carboxylic acids containing . The monomer or oligomer having two or more polymerizable functional groups that can be used in the present invention is polymerized in an amount of 10% by weight or less, preferably 5% by weight or less of the total monomers, to form a resin. can be formed. However, in the case of a polymer containing a functional group represented by formula (I), among the polymerizable functional groups mentioned above, CH 2 =CH-COO-, CH 2 =CH-
CONH-, CH2=CH-SO2-, CH2=
It is preferable not to use CH-CO- [Image Omitted]. In the present invention, as the functional group for proceeding with the crosslinking reaction in the method (1) or (2) above, ordinary 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 books such as Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers," Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals", Kodansha (published in 1976), etc. For example, in Table 1 below, a polymer reaction using a combination of a group A functional group (a functional group having a dissociable hydrogen atom) and a group B functional group is listed as a commonly known method. In addition, R and R' in Table 1 are hydrocarbon groups, and represent the same contents as r 5 and r 6 described above. [Table 1] In addition, -CONHCH as a reactive functional group
2 OR10 (R10 is a hydrogen atom or a methyl group,
(representing an alkyl group having 1 to 6 carbon atoms such as ethyl group, propyl group, butyl group, hexyl group, etc.), and this reactive group is known as a group that condenses in a self-condensation type reaction,
This can also be used. Furthermore, for example, Tsuyoshi Endo, "Refinement of Thermosetting Polymers", C. M. C Co., Ltd. (published in 1986)
, Yuji Harasaki "Latest Binder Technology Handbook" Chapter II-1,
General Technology Center (published in 1985), Takayuki Otsu "Synthesis, design and development of new applications of acrylic resin" Chubu Business Development Center Publishing Department (published in 1985), Eizo Omori "Functional Acrylic Resin" Techno System (published in 1985), Hideo Inui,
Gentaro Nagamatsu "Photosensitive Polymer" Kodansha (1977), Takahiro Tsunoda "New Photosensitive Resin" Printing Society Publishing Department (1988)
1 year), G. E. Green and B. P. St
ar, R. J. Macro. Sci. Revs
．． Macro. Chem. , C21(2), 187
~273 pages (1981-82), C. G. Roffe
y “Photopolymerization of
"Surface Cortings", A. Will
ey Interscience Pub. (198
It is possible to use functional groups, compounds, etc. cited in reviews such as 2010). These crosslinkable functional groups may be contained in one copolymer component together with the formyl group and/or the functional group represented by general formula (I), or the formyl group and/or the functional group represented by the general formula (I) may be contained in one copolymer component.
Alternatively, it has already been explained that it may be contained in a copolymer component separate from the copolymer component containing the functional groups of formulas (I) and (II). Specific monomers corresponding to the copolymers containing these crosslinkable functional groups include, for example, monomers containing the functional groups that can be copolymerized with the polymer component of the general formula (II). Any vinyl compound that can be used may be used. Such vinyl compounds are described, for example, in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (published in 1986). 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) body, β-chloro body, β-bromo body,
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, vinyl benzenesulfonic acid,
Half-ester derivatives of vinyl or allyl groups of vinyl sulfonic acid, vinylphosphonic acid, and dicarboxylic acid salts, and compounds containing the crosslinkable functional group in the substituent of these carboxylic acids or sulfonic acids, ester derivatives, amide derivatives, etc. etc. A reaction accelerator may be added to the resin [L] of the present invention, if necessary, 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,
Compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Society of Polymer Science, Baifukan (1986), etc. can be used. . For example, organic silane compounds (such as vinyltrimethoxysilane, vinyltributoxysilane,
Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.)
, polyisocyanate compounds (e.g. toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.),
Polyol compounds (e.g. 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (e.g. ethylenediamine, γ-hydroxypropylated ethylenediamine, 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), Kuniyuki Hashimoto Compounds described in "Epoxy Resin" edited by Nikkan Kogyo Shinbunsha (1969), etc.), melamine resin (for example, described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shinbunsha (1969), etc.) compounds), poly(meth)acrylate compounds (e.g., Shin Okawara, Takeo Saegusa, Toshinobu Higashimura, “Oligomer”, Kodansha (1)
(published in 1976), Eizo Omori "Functional Acrylic Resin" Technosystem (published in 1985), etc. Specific examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1
, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof. [0049] By treatment with a treatment liquid containing a hydrophilic compound having a nucleophilic reactive substituent, synthesized as described above,
In the present invention, the resin [L] containing at least one functional group that generates at least one hydrophilic group exhibits a particle state with a maximum particle size of 5 μm or less and an average particle size of 1.0 μm or less. [0050] The resin particles of the present invention having such a fine particle size can be made into a desired particle size by allowing resin powder to coexist as is and dispersing it when preparing a composition for forming an image-receiving layer. can. Alternatively, conventionally known dry and wet microparticulation methods or a method of forming polymer gel latex can be used. That is, a method in which resin powder is directly pulverized into fine particles using a conventionally known pulverizer or disperser (for example, a ball mill,
A paint shaker, sound mill, hammer mill, jet mill, kedimir, etc.) and a conventionally known method for producing latex particles of a paint or an electrostatic photographic liquid developer can be used. The latter method of producing polymer latex is a method of dispersing resin powder together with a dispersing polymer.The resin powder and dispersion-assisting polymer are kneaded in advance to form a kneaded product, 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), Kyoritsu Shuppan (1971), ``Solomon, Chemistry of Paint'', ``Paint and Surfac''
e Coating theory and practice
is”, Yuji Harasaki “Coating Engineering” Asakura Shoten (1
971), Yuji Harasaki, "Basic Science of Coatings", Maki Shoten (published in 1977), JP-A-62-96954, 62
-115171, 62-75651, etc. [0053] Furthermore, methods for easily obtaining latex particles by conventionally known polymerization reactions such as suspension polymerization and dispersion polymerization can also be used. Specifically, Souichi Muroi, “Chemistry of Polymer Latex”, Kobunshi Kankakai (published in 1970), Okuda
Taira, Hiroshi Inagaki, “Synthetic Resin Emulsion”, Kobunshi Kankankai (published in 1978), Soichi Muroi, “Introduction to Polymer Latex”
It is described in Kobunsha (1983), etc. [0054] In the present invention, a method of forming polymer latex particles is preferred, and by this method resin particles having an average particle size of 1.0 μm or less can be easily formed. As a method for producing latex particles having such a small particle size and a narrow particle size distribution, a non-aqueous dispersion polymerization method is cited as a preferable 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 less, and it may be used alone or in combination of two or more. Specific examples of this organic solvent include alcohols such as methanol, ethanol, propanol, 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, etc., 6 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, etc.
~14 aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, trichloroethane, etc. Can be mentioned. However, it is not limited to the compound examples described above. By synthesizing polymer latex using a dispersion polymerization method in these non-aqueous solvent systems, the average particle size of the resin particles can easily be reduced to 1 μm or less, and the particle size distribution is very narrow and monodisperse particles can be formed. It can be done. Specifically, K. E. J. Barrett “Dispers
ion Polymerization in Org
anic Media” John Wiley (19
1975), Koichiro Murata, Polymer Processing, 23, 20 (
Tsunetaka Matsumoto, Toyokichi Tange, Journal of Japan Adhesive Association 9, 183 (1973), Toyokichi Tange, Journal of Japan Adhesive Association 23, 26 (1987), D. J. Walbr
idge, NATO. Adv. Sturdy. Ins
t. Ser. E. No. 67, 40 (1983),
British Patent Nos. 893429 and 934038,
U.S. Patent No. 1122397, U.S. Patent No. 3900412, U.S. Patent No. 46
The method is disclosed in the specifications of JP-A No. 06989, JP-A Nos. 60-179751 and JP-A No. 60-185963, and the like. The resin particles contained in the image-receiving layer of the present invention have a hydrophilic group formed by reacting with a hydrophilic compound containing a nucleophilic substituent by treatment with a desensitizing solution or soaking water during printing. generate. The mechanism of this hydrophilization is shown in the following reaction formula (1), with a representative example of a sulfite ion as a nucleophilic hydrophilic compound. Poly~ represents a resin moiety containing a formyl group and/or a functional group of formula (I), and W 1 represents an organic residue, more specifically represented by the following general formula (III): Indicates a linking group. ##STR41## That is, the resin particles of the present invention have a Parson's nucleophilic constant n of 5.5 in the processing solution only when the non-image area is desensitized as a direct plate lithographic printing original plate. It is characterized by adding a hydrophilic group to the terminal by reacting with the above-mentioned substituent-containing nucleophilic hydrophilic compound, thereby expressing hydrophilicity, that is, becoming hydrophilic. Since it does not react with moisture in the atmosphere, there are no concerns regarding storage stability. Since the formyl group is a functional group that reacts very quickly with nucleophilic compounds, it is possible to quickly develop hydrophilicity. Furthermore, the functional group represented by general formula (I) can be expressed by reaction formula (1
) As shown in the following, the deacetal reaction easily proceeds by acid treatment and it can be converted into a formyl group, and therefore it can be used in the same manner as a formyl group. 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 due to the hydrophilic groups generated by the resin particles. Since the hydrophilicity is further increased, 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. Further, in the case of the above-mentioned resin particles that are partially crosslinked, the solubility in water is significantly reduced while maintaining hydrophilicity, and the resin particles become poorly soluble or insoluble and swellable in water. 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. [0061] As a result, the direct-drawing lithographic printing original plate manufactured according to the present invention can reproduce a faithful copy image to the original image even if the environmental conditions change, and the hydrophilicity of the non-image area is good. Therefore, it has the advantage that background smudge does not occur, the image-receiving layer has good smoothness and electrostatic properties, and furthermore, printing durability is excellent. Furthermore, the direct drawing type lithographic printing original plate according to the present invention is not affected by the environment during manufacturing processing, has excellent storage stability before processing, and has the characteristics that hydrophilization processing can be performed very quickly. has. 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 are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer,
Methacrylate copolymers, acrylate copolymers, vinyl acetate copolymers, polyvinyl butyral, alkyd resins, silicone resins, epoxy resins, epoxy ester resins, polyester resins, and water-soluble polymer compounds such as polyvinyl alcohol, modified polyvinyl alcohol,
Examples include starch, oxidized starch, carboxymethyl cellulose, hydroxyethyl cellulose, gelatin, polyacrylic acid, polyvinylpyrrolidone, polyvinyl ether-maleic anhydride copolymer, polyamide, polyacrylamide, and the like. The molecular weight of the binder resin is preferably 103
~106, more preferably 5x103 ~5x105
It is. Further, the glass transition point of this resin is preferably -10°C to 125°C, more preferably 0°C to 85°C. Inorganic pigments are used as other components of the image-receiving layer of the present invention, and examples of the inorganic pigments include kaolin clay, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, and alumina. . The binder resin/pigment ratio in the image-receiving layer varies depending on the type of material and, in the case of pigments, the particle size, but generally the weight ratio is 1.
/(0.5-5), preferably 1/(0.8-2.
5) The degree 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. in particular,
It is described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981). [0066] 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 is provided on the support surface opposite to the image-receiving layer for the purpose of preventing curling. (back layer) can be provided. Here, the intermediate layer is made of acrylic resin, emulsion type resin such as ethylene-butadiene copolymer, methacrylate ester-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer, epoxy resin, polyvinyl butyral. , a solvent type resin such as polyvinyl chloride and polyvinyl acetate, and at least one kind of water-soluble resin as mentioned above, but an inorganic pigment or a waterproofing agent can be added as necessary. . 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 volume resistivity of the printing original plate is 1010 to 1013 Ωcm.
A dielectric agent may also be added to the image-receiving layer, interlayer and/or backcoat layer so as to achieve the following. The dielectric agent may be inorganic or organic. Inorganic agents include salts of monovalent or polyvalent metals such as Na, K, Li, Mg, Zn, Co, and Ni; Examples include polymeric cation conductive agents such as polyvinylbenzyltrimethylammonium chloride and acrylic resin-modified quaternary ammonium salts, and polymeric anionic dielectric agents such as polymeric sulfonate salts. 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 in each layer. [0069] Generally, in order to produce the direct-drawing lithographic printing original plate of the present invention, an aqueous solution containing an intermediate layer component is coated on one side of the support, if necessary, and dried to form an intermediate layer, and then an image-receiving layer is formed. An aqueous solution containing the ingredients is applied and dried to form an image-receiving layer.
Furthermore, if necessary, 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/m 2 and 5 to 20 g/m 2 , respectively.
is appropriate. [0070] 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 and making the plate, the plate is made into a plate. After the surface is treated with a fattening liquid to desensitize the non-image area, it is used as a printing plate for lithographic printing. [0071] The desensitization treatment to be subjected to the present invention is carried out on the formyl group-containing resin particles of the present invention using a solution (aqueous solution or water-soluble This is achieved by treatment with a mixed solution containing organic solvents. As a hydrophilic compound that causes a nucleophilic substitution reaction on a formyl group, the nucleophilic constant n [R. G. Pearson, H. Sobel,
J. Songstad, J. Amer. Chem
．． Soc. , 90, 319 (1968)] is 5.5
Examples include hydrophilic compounds that contain a substituent having the above value and 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 salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and also contains at least one polar group selected from hydroxyl group, carboxyl group, sulfo group, phosphono group, and amino group in the molecule. mercapto compound,
Examples include hydrazide compounds, sulfinic acid compounds, primary amine compounds, and secondary amine compounds. 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, mercapto Benzene sulfonic 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, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, dicarboxybenzenesulfinic acid, etc., as a hydrazide compound As a primary or secondary amine compound, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid, etc. As,
For example, N-(2-hydroxyethyl)amine, N,N-
Di(2-hydroxyethyl)amine, N,N-di(2-
hydroxyethyl)ethylenediamine, tri(2-hydroxyethyl)ethylenediamine, N-(2,3-dihydroxypropyl)amine, N,N-di(2,3-dihydroxypropyl)amine, 2-aminopropionic acid,
Examples include aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2-carboxyethylmorpholine, and 3-carboxypiperazine. [0075] These nucleophilic compounds are used by being incorporated into the desensitizing treatment liquid 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. Further, the pH of the treatment liquid is preferably 4 or more. The processing conditions are
The temperature is preferably 15°C to 60°C and the immersion time is preferably 10 seconds to 5 minutes. The treatment liquid contains the above-mentioned nucleophilic compound and p
Other compounds may be contained in addition to the H regulator. For example, add 1 to 50 parts of a water-soluble organic solvent to 100 parts by weight of water.
It may be contained in parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), and ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.),
Examples include 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. [0077] Also, the surfactant was added in 100 parts by weight of water.
．． It may be contained in an amount of 1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants. For example, the compounds described in Hiroshi Horiguchi, "New Surfactants", Sankyo Publishing Co., Ltd. (published in 1975), Ryohei Oda, Kazuhiro Teramura, "Synthesis of Surfactants and Their Applications", Maki Shoten (published in 1980), etc. 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. [Examples] The present invention will be specifically explained below 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.
It was heated to Add 1.5 g of 2,2-azobis(isobutyronitrile) (abbreviated as A.I.B.N.) to this and add 8
Time reacted. To this reaction mixture solution, 12 g of glycidyl methacrylate, 1 g of t-butylhydroquinone and N
, N-dimethyldodecylamine 0.8g was added, and 10
The reaction was carried out at 0°C for 15 hours to obtain a dispersed resin [P-1]. Next, a mixed solution of 7.5 g (solid content) of the dispersion resin [P-1], 50 g of monomer [M-1] having the following structure, and 200 g of methyl ethyl ketone was heated to 65° C. with stirring under a nitrogen stream. It was warm. To this, 2,2-azobis(isovaleronitrile) (abbreviated as A.I.V.N.) 0.7
g was added and reacted for 6 hours. Initiator (A.I.V.N.)
20 minutes after addition, the homogeneous solution started to become cloudy and the reaction temperature was 90°C.
The temperature rose to ℃. After cooling, it was passed through a 200 mesh nylon cloth to obtain a white dispersion. It was latex [L-1] with an average particle diameter of 0.45 μm. Dispersion resin [P-1] [Chemical formula 42] Monomer [M-1] [Chemical formula 43] Production example 2 of resin particles: [L-2] 20 g of monomer [M-2] having the following structure , Dispersion resin [P-1] 8g (
A mixed solution of 150 g of ethyl acetate and 150 g of n-hexane (in terms of solid content) was heated to 55 ml with stirring under a nitrogen stream.
Warmed to ℃. A. I. V. N. Add 0.5g, 4
After reacting for some time, a white dispersion was obtained. After cooling, the resulting dispersion was passed through a 200 mesh nylon cloth with an average particle size of 0.
．． It was 30 μm latex [L-2]. Monomer [M-2] [Chemical formula 44] Production example 3 of resin particles: [L-3] 20 g of acrolein, 5 g of macromonomer [P-2] having the following structure
The reaction was carried out in the same manner as in Example 1 for the production of resin particles, except that a mixed solution of 150 g of methyl ethyl ketone was used.
．． A 30 μm white latex [L-3] was obtained. Macromonomer [P-2] [Chemical formula 45] Production example 4 of resin particles: [L-4] 20 g of acrolein, 2.0 g of divinylbenzene, 5 g of macromonomer [P-3] with the following structure, 1 methyl ethyl ketone
The reaction was carried out in the same manner as in Resin Particle Production Example 1 except that 80 g of a mixed solution was used to obtain white latex [L-4] with an average particle size of 0.25 μm. Macromonomer [P-3] [Chemical formula 46] Production examples 5 to 16 of resin particles: [L-5] to [L-16]
Same as Resin Particle Production Example 3 except for using a mixed solution of 20 g of monomer [M] shown in Table 2 below, a predetermined amount of crosslinking monomer, 5 g of macromonomer [P-4] having the following structure, and 200 g of methyl ethyl ketone. Each latex [L-5
] to [L-16] were obtained. Macromonomer [P-4] [Chemical formula 47] [Table 2] Example 1 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 On top, a resin with the following structure [S-1
] 25 g, resin particles [L-1] 10 g (as solid content), zinc oxide 50 g, and toluene 150 g were dispersed in a ball mill for 2 hours, and then glutaric anhydride 4
g was added and dispersed for 10 minutes. The obtained dispersion was applied with a wire bar so that the dry adhesion amount was 18 g/m 2 , dried at 100° C. for 30 seconds, and further heated at 120° C. for 1 hour and 30 minutes to prepare a lithographic printing original plate. Resin [S-1] [Chemical formula 48] This original plate was immersed for 3 minutes in a desensitizing solution (E-1) prepared according to the following formulation, and then washed with water. Desensitizing liquid treatment liquid (E-1) Ammonium sulfite
85g methyl ethyl ketone
80
gELP-FS (manufactured by Fuji Photo Film Co., Ltd.) 83
More than 5g 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. 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 degree of oxidation needs to be less than 20° in terms of contact angle with water). Next, a plate was made using commercially available PPC, and the obtained original plate was subjected to a desensitization treatment under the same conditions as above to obtain a printing original plate. The density of the image area of the obtained original plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This was printed on high-quality paper using an offset printing machine (Oliver 52 model manufactured by Sakurai Seisakusho Co., Ltd.). 30
Even after printing more than 00 sheets, no problem occurred in the background stains in the non-image areas and the image quality in the image areas of the printed matter. [0088] Further, using the above original plate, the environmental condition was adjusted to 30°C.
, 80% RH was used for plate making using commercially available PPC, and the image of the original plate obtained had a density of 1.0 or more in the image area, no background fog 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. 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 A resin having the following structure [S-2
] 34g, resin particles [L-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 4 g of 1,3-xylylene diisocyanate was added thereto and dispersed in a ball mill for 10 g.
Dispersed for minutes. The resulting dispersion has a dry coating weight of 18 g/
Coat with a wire bar so that the thickness is 110°C.
The mixture was dried for 1.5 hours to prepare a lithographic printing original plate. Resin [S-1] embedded image This original plate was subjected to plate making and printing in the same manner as in Example 1. The density of the image area of the obtained original plate is 1
．． 0 or more, there was no background fog in non-image areas, and the image quality in image areas was clear. This was printed on high-quality paper using an offset printing machine (Oliver 52 model manufactured by Sakurai Seisakusho Co., Ltd.). 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. [0091] Furthermore, using the above original plate, the environmental condition was adjusted to 30°C.
, 80% RH was used for plate making using commercially available PPC, and the image of the original plate obtained had a density of 1.0 or more in the image area, no background fog 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. 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. Examples 3 to 10 34 g of Example [S-3] with the following structure, 6 g of resin particles [L] shown in Table 3 below (as solid content), 70 g of zinc oxide, 10 g of silica gel, 1,5-(N- A mixture of 5 g of imidazolyl)carbamoylnaphthalene and 150 g of toluene was dispersed in a ball mill for 2 hours. The obtained dispersion was applied with a wire bar to a dry adhesion amount of 18 g/m 2 and dried at 120° C. for 2 hours to prepare a lithographic printing original plate. Resin [S-3] [Chemical formula 50] [0094] These original plates were subjected to the following procedures except that a desensitizing treatment liquid (E-2) prepared according to the following formulation was used as the desensitizing treatment liquid. Plate making and printing were performed in the same manner as in Example 1. Desensitizing treatment liquid (E-2) Sodium sulfite
52
g Nucor B4SN [manufactured by Nippon Nyukazai Co., Ltd.] 10g Benzyl alcohol
Dissolve 80g of these in distilled water to make a total volume of 1L, and then add sodium hydroxide to pH 11.0.
Adjusted to. The density of the image area of the obtained original plate was 1.0 or more, there was no background fog in the non-image area, and the image quality of the image area was clear. This is offset printing machine (Sakurai Seisakusho)
Oliver Co., Ltd. Model 52) 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 condition was adjusted to 30°C.
, 80% RH was used for plate making using commercially available PPC, and the obtained original plate image had a density of 1.0 or more in the image area, no background fog in the non-image area, and the image quality in the image area was clear. . When I printed this in the same way as above, I got 3000
There was no problem when printing sheets. Examples 11 to 14 34 g of Example [S-4] with the following structure, 6 g each of resin particles [L] shown in Table 4 below (as solid content), 10 g of silica gel
, a mixture of 5 g of alumina and 80 g of toluene was dispersed in a ball mill for 2 hours, and 5 g of phthalic anhydride was added to give 1.
Dispersed for 0 minutes. The dry adhesion amount of the obtained dispersion was 18 g.
/m 2 with a wire bar, 120
It was dried at ℃ for 20 hours to prepare a lithographic printing original plate. Resin [S-4] [Chemical formula 51] This was made into a plate in the same manner as in Example 3, and then printed using a printing machine. The density of the obtained printing original plate is as follows: 1.
0 or more, the image quality was clear. Furthermore, the image quality of the printed matter after printing 3000 sheets was a clear image without background fog. Examples 15 to 26 Using each printing original plate prepared in Examples 2 to 14, 0.5 mol of the nucleophilic compound shown in Table 5 below, 100 g of an organic solvent, and Nucor B4SN [manufactured by Nippon Nyukazai Co., Ltd.] were used. ] Distilled water was added to 10 g to make 1 liter, and the pH of each mixture was adjusted to 11.
Adjusted to 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 10° or less, and the original plate was sufficiently hydrophilized. In addition, the number of printed sheets is 3000
The print quality of the printed matter was good, with no background fog and clear images. [Table 5] [Effects of the Invention] According to the present invention, an image with excellent image receptivity,
A direct-drawing lithographic printing original plate that does not change over time can be obtained. Moreover, a printing original plate with very good printing properties can be obtained. [Table 2] [Table 2] [Table 2]

Claims (2)

[Claims] Claim 1. A method for producing a direct-drawing lithographic printing original plate having an image-receiving layer on a support, wherein the image-receiving layer has a formyl group and/or a functional group represented by the following general formula (I). After forming an image on a direct drawing type lithographic printing original plate containing at least resin particles having at least one kind of polymer component and a binder resin, the non-image area other than the image area is subjected to at least Persson's nucleophilic determination. A method for producing a direct plate lithographic printing original plate, characterized in that the printing original plate is prepared by desensitizing it with a treatment liquid containing a hydrophilic compound containing a substituent having a number n of 5.5 or more. . General formula (I) [Formula 1] [However, in the above formula (I), R 1 and R 2 may be the same or different, and represent a hydrocarbon group, or R 1 and R 2 may be connected to each other. represents an organic residue that forms a ring with 2. The electrophotographic lithographic plate according to claim 1, wherein in the resin particles, the polymer component having a formyl group and/or a functional group represented by the general formula (I) has a crosslinked structure. A method of manufacturing a printing plate.