JPH0516554A - Original plate for direct describing lithographic press - Google Patents

Abstract

PURPOSE:To provide an original plate for direct describing lithographic press excellent in desentization and having high print resistance wherein spot tinting as well as uniform tinting of entire surface is suppressed when it is employed as an offset original plate. CONSTITUTION:In an original plate for direct describing lithographic press having an image receiving layer on a support, the image receiving layer contains resin particles dispersed with nonaqueous solvent obtained through dispersion polymerization of monofunctional monomer (A) containing a functional group producing a hydroxyl group through decomposition which is soluble to nonaqueous solvent but becomes insoluble through polymerization and a monofunctional monomer (M) having repeating unit including a substituent containing silicon and/or fluorine atom and having a polymeric double bond group at one end of the main chain of polymer. Consequently, an original plate for direct describing lithographic press having high plate wear wherein fogging is well-suppressed can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lithographic printing original plate, and more particularly to a direct drawing type lithographic printing original plate suitable for office printing original plates.

[0002]

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

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

[0004]

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

The present invention solves the above-mentioned problems of the direct drawing type lithographic printing plate precursor. An object of the present invention is to provide a direct-drawing lithographic printing plate precursor that is excellent in desensitizing property and does not cause spot stains as well as uniform background stains as an offset master. Another object of the present invention is to improve the adhesiveness between the oil-based ink in the image area and the image-receiving layer, and keep the hydrophilicity of the non-image area sufficiently even if the number of printed sheets is increased during printing, thus causing scumming. No, it is to provide a direct drawing type lithographic printing plate precursor having high printing durability.

[0006]

The above object of the present invention is to provide a direct drawing type lithographic printing plate precursor having an image receiving layer on a support, in which the following non-aqueous solvent type dispersed resin particles are contained in the image receiving layer. This can be achieved by a direct drawing type lithographic printing plate precursor containing at least one kind. Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, at least one functional group that is soluble in the non-aqueous solvent but is insolubilized by polymerization and that produces at least one hydroxyl group by decomposition
The following general formula (A) is provided only at one end of the main chain of the polymer containing at least one repeating unit containing a seed-containing monofunctional monomer (A) and a substituent containing a silicon atom and / or a fluorine atom. Polymer resin particles obtained by subjecting a monofunctional polymer [M] having a polymerizable double bond group represented by I) to a dispersion polymerization reaction.

[Chemical 3] [However, in the general formula (I), V ₀ is -O-, -CO
O -, - OCO -, - (CH 2) -OCO -, - (CH
_{2) -COO -, - SO 2} -,

[Chemical 4] Represents —CONHCOO— or —CONHCONH— (R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), and a ₁ and a ₂ may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R ₂ or -COO-R ₂ (R
₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)
Furthermore, in the present invention, the non-aqueous solvent-based dispersed resin particles may form a high-order network structure.

[0007]

The present invention is characterized in that the image receiving layer of the lithographic printing plate precursor for direct drawing contains the above-mentioned non-aqueous solvent-based dispersed resin particles. Abbreviated as “), but at least one functional group capable of generating at least one hydroxyl group by decomposition is used.
A monofunctional polymer which contains a seed and which is insoluble in the non-aqueous solvent after the polymerization, and which contains a repeating unit containing a silicon atom and / or a fluorine atom as at least a substituent and is soluble in the non-aqueous solvent even after the polymerization. It is characterized in that it is chemically bonded to the volatile polymer component.

That is, the resin particles are composed of a polymer component (A) containing a protected hydroxyl group, a portion insoluble in a non-aqueous dispersion solvent, and a monofunctional polymer soluble in the solvent. A non-aqueous latex composed of [M] and the dispersion resin has a molecular weight of 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In the present invention, the resin particles are present as particles in the image receiving layer, separately from the binder resin which is the matrix of the image receiving layer. The resin particles undergo a reaction such as a hydrolysis reaction, a redox reaction, a photodecomposition reaction, etc. by a hydrophilizing treatment with a desensitizing solution and a soaking water used at the time of printing to chemically react the protected hydroxyl group portion. To produce a hydroxyl group and convert it from a hydrophobic property to a hydrophilic property.

On the other hand, the resin particles also have a polymer component containing a silicon atom and / or a fluorine atom, which is extremely lipophilic. Therefore, the direct-drawing type lithographic printing plate precursor of the present invention containing the resin particles in the image receiving layer, when the oil-based ink or the like is drawn as an image portion on the image receiving layer, the lipophilic group in the resin particles is used. By the action, the adhesion between the image receiving layer and the oil-based ink becomes good, and the printing durability is improved, while
In the non-image area, the resin particles rapidly hydrophilic to the desensitizing liquid and immersion water as described above, so it is clearly distinguished from the lipophilicity of the image area, and printing ink adheres to the non-image area during printing. It will not do.

Further, it has an image receiving layer in which such hydrophilic resin particles are dispersed in a binder resin of a matrix,
In the printing original plate of the method of making the surface hydrophilic by treating the non-image area with a desensitizing solution, known hydrophilic resin particles are uniformly dispersed in the entire surface layer. To do. Unlike this, the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the image-receiving layer, but the function of the substituent-containing polymer component having a significantly large lipophilic silicon atom and / or fluorine atom. As a result, they are concentrated and present on the surface portion of the image receiving layer which is the air interface (highly lipophilic). Therefore, the water retention in the non-image area is dramatically improved only by dispersing a smaller amount (50 to 10% of the amount used in the known technique of hydrophilic resin particles).

Further, since the resin particles are bound with a hydrophobic (lipophilic) polymer component, the hydrophobic portion interacts with the binder resin which is the matrix of the image receiving layer. Due to the anchor effect of this part, even if it shows hydrophilicity, it does not elute in the immersion water during printing, and it is possible to maintain good printing characteristics even when printing a considerably large number of sheets.

Further, in the present invention, if the resin particles form a high-order network structure, the elution property in water is further suppressed, while the water swelling property is exhibited and the water retention is further improved. Become. That is, in the case of having a network structure, in the above-mentioned non-aqueous solvent-insoluble portion, the molecules of the polymer component (A) forming the insoluble portion are bridged to form a high-order network structure. As a result, the network resin particles are hardly soluble or insoluble in water.

It is important that the resin particles are dispersed as particles in the image receiving layer separately from the binder resin which is the matrix, and are concentrated near the air interface. As a result, the direct drawing type original plate of the present invention forms a faithful image portion and a non-image portion, and provides a high-quality printed image without background stains. Moreover, since the resin particles are fixed by the binder resin, they do not peel off during various processing steps,
In addition, since the protective effect of the binder resin can be obtained,
Excellent printing durability. Further, due to the hydrophilicity of the hydroxyl group of the resin particles, there is a concern that the resin particles may flow out due to the immersion water during printing, but by crosslinking at least a part, such concern is eliminated. As described above, the direct-drawing type lithographic printing plate precursor according to the present invention has the advantages that the hydrophilicity of the non-image area is good, so that background stains do not occur and the printing durability is excellent.

The resin particles will be further described below. The dispersed resin of the resin particles of the present invention is composed of at least one kind of each of the monomer (A) and the monofunctional polymer [M]. The functional monomer (D) is allowed to coexist, and in any case, if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. it can.

The hydrophilicity of the resin particles is such that the film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent has a contact angle with distilled water (measured by a goniometer) of 50 degrees or less. Value, preferably a value of 30 degrees or less. Further, in the case of the network resin particles, the solubility of the resin in water is 80% by weight or less, preferably 50% or less.
It is less than or equal to weight%.

Resin particles of the present invention (including network resin particles)
Preferably has an average particle diameter of 0.05 to 1.0 μm. When it is larger than 1.0 μm, the smoothness of the surface layer is deteriorated, which causes a decrease in film strength or toner image strength. On the other hand, if it is smaller than 0.05 μm, it is similar to the case of molecular dispersion, and the effect of being particles for improving water retention is weakened. Since the resin particles of the present invention are synthesized by a dispersion polymerization method in a non-aqueous dispersion system, the average particle size of the polymer latex particles easily becomes 1 μm or less, and the particle size distribution is very narrow, and monodisperse particles are obtained. You can do it.

In the present invention, if the amount of resin particles (including mesh resin particles) in the image receiving layer is too small, the hydrophilicity of the non-image area will not be sufficient and the effect will be lost, causing scumming. On the other hand, if the amount is too large, the hydrophilicity of the non-image area is further improved, but the amount of water absorption of the entire image receiving layer increases, causing a decrease in adhesiveness with the support and a decrease in image strength. It is preferably used in an amount of 1 to 80% by weight based on 100 parts by weight of the matrix resin of the layer.

Next, the non-aqueous solvent-based dispersed resin particles used in the present invention will be described in more detail. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. First, a monofunctional monomer (A) containing at least one functional group that is soluble in a non-aqueous solvent but is insolubilized by polymerization and that produces a hydroxyl group by decomposition (hereinafter simply referred to as hydroxyl group formation). The functional group-containing monomer (A) may be referred to) in detail. The functional group contained in the hydroxyl group-forming functional group-containing monomer (A) of the present invention produces a hydroxyl group by decomposition, and the number of hydroxyl groups produced from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the hydroxyl group-forming functional group-containing monomer (A) contains at least one functional group represented by the general formula (II) [-O-L ₁ ]. And a monomer having one polymerizable double bond group. In the general formula (II) [-OL ₁ ], L ₁ is

[Chemical 5] Represents However, R₃, R_Four, R_Five, R₆, R₇, R₈
May be the same or different from each other, a hydrogen atom, a hydrocarbon
Group or -OR₉(R₉Represents a hydrocarbon group),
Y ₁, Y₂Represents a hydrocarbon group, Z is an oxygen atom, sulfur
Represents an atom or a -NH- group, Y₃Is a sulfur atom or oxygen
Represents an atom.

The functional group of [-O-L ₁ ] of the general formula (II) produces a hydroxyl group by decomposition, and will be described in more detail below. L ₁ is

[Chemical 6] In the case of₃, R_Four, R_FiveAre the same as each other
Or may be different, preferably a hydrogen atom or substituted
Optionally linear or branched alkyl group having 1 to 18 carbon atoms
(For example, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, decyl group, dodecyl group, octyl group
Tadecyl group, chloroethyl group, methoxyethyl group, meth
Xypropyl group, etc.), optionally substituted alicyclic group (eg,
Cyclopentyl, cyclohexyl, etc.)
An aralkyl group having 7 to 12 carbon atoms (eg benzyl)
Group, phenethyl group, fluorobenzyl group, chloroben
Zyl group, methylbenzyl group, methoxybenzyl group, 3-
Phenylpropyl group, etc.) or optionally substituted aromatic group
(For example, phenyl group, naphthyl group, chlorophenyl group,
Tolyl group, methoxyphenyl group, methoxycarbonyl group
(Phenyl group, dichlorophenyl group, etc.) or -OR₉(R
₉Represents a hydrocarbon group, specifically, the above R₃, R _Four, R_Five
Represents the same substituents as the hydrocarbon group of).

In the case where L ₁ represents --CO--Y ₁ ,
Y ₁ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted (eg, methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group,
Phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-1-propyl group, etc., optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group) , Methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group,
Methoxybenzyl group, etc.), 6 to optionally substituted carbon atoms
12 aryl groups (eg, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group,
Methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.). When L ₁ represents —CO—Z—Y ₂ , Z represents an oxygen atom, a sulfur atom or a —NH— bonding group, and Y ₂ has the same meaning as Y ₁ described above. Further L ₁
But,

[Chemical 7] In the case of representing, Y ₃ represents an oxygen atom or a sulfur atom. R ₆ , R ₇ and R ₈ may be the same as or different from each other, and specifically have the same contents as R _{3 to} R ₅ described above. i represents an integer of 3 to 5.

The general formula [-O-L ₁ ] used in the present invention
The monofunctional monomer (A) containing at least one functional group selected from the group can be easily synthesized by a conventionally known organic synthesis reaction. For example, JFWMcOmie “Prote”, “New Experimental Chemistry Course, Volume 14, Synthesis and Reaction of Organic Compounds [V]”, page 2497 (published by Maruzen Co., Ltd.) edited by The Chemical Society of Japan.
ctive groups in Organic Chemistry '' (Plenum Press
1973), TW Greene "Protective groups in
Organic Synthesis "(John Wiley and Sons Interscie
nce, published in 1981) and the like, and a synthetic method similar to the method of introducing a protecting group into a hydroxyl group.

As described above, the monofunctional monomer (A) containing a functional group represented by the general formula [-O-L ₁ ] and having a polymerizable double bond group in one molecule is more specific. For example, compounds represented by the following general formula (III) can be mentioned.

[Chemical 8] In formula (III), X ₁ is

[Chemical 9] Indicates an aromatic group or a heterocyclic group (provided that Q ₁ , Q ₂ ,
Q _3, Q ₄ are each a hydrogen atom, a hydrocarbon group or a group of the following formula (III) in the a _{(Y 4 -O-L 4)} , f 1, f 2 may be the same or different, a hydrogen atom, a hydrocarbon Hydrogen group or formula (III)
(Y ₄ —OL ₂ ), and n ₁ represents an integer of 0 to 18]. Y ₄ represents a carbon-carbon bond which may pass through a hetero atom connecting the bonding group X ₁ and the bonding group [—O—L ₄ ] (the hetero atom includes an oxygen atom, a sulfur atom or a nitrogen atom). , For example

[Chemical 10] Etc. consisting of a combination of binding units such as
(However f₃, F_Four, F _FiveAre each f₁, F₂Synonymous with
Is). L₂Is L in formula (II)₁Has the same meaning as.
a₃, A_FourMay be the same or different, a hydrogen atom,
Hydrocarbon groups (eg charcoal which may be substituted with -COOH, etc.
An alkyl group having a prime number of 1 to 12), -COOH or -CO
OW₁[W₁Is a general formula (-OL₂) Substituents containing groups
An alkyl group having 1 to 18 carbon atoms which may be substituted with
Represents a kenyl group, an aralkyl group, an alicyclic group or an aromatic group]
Represents

More specifically, the following compound examples can be given as the monomer containing a functional group of the general formula [-O-L ₃ ]. In each of the examples (a-1) to (a-25), Me represents a methyl group.

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

According to another preferred embodiment of the present invention, a monofunctional monomer (A) containing a hydroxyl group-forming functional group.
Is a monofunctional monomer containing at least one functional group having a form in which at least two hydroxyl groups sterically close to each other are simultaneously protected by one protecting group. Examples of the functional group having in a protected form at least two hydroxyl groups sterically close to each other include, for example, the following general formulas (IV), (V), (VI), (VI
Examples include those represented by I).

[Chemical 36] In formula (IV), R ₁₀ and R ₁₁ may be the same or different and each represents a hydrogen atom, a hydrocarbon group or —O—O—R ₁₂ (R ₁₂ represents a hydrocarbon group), and U is hetero. Represents a carbon-carbon bond which may pass through an atom (provided that the number of atoms between oxygen atoms is within 5).

[Chemical 37] In formula (V), U is as defined above.

[Chemical 38] In formula (VI), R ₁₀ , R ₁₁ and U are as defined above.

[Chemical Formula 39] In formula (VII), R ₁₀ and R ₁₁ are as defined above. R ₁₃
Is a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms (eg, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, a chlorobenzyl group) Represents an aralkyl group and the like).

The functional group will be described in more detail below. In formula (IV), R ₁₀ and R ₁₁ may be the same as or different from each other, preferably a hydrogen atom and a carbon number of 1 to 1.
12 optionally substituted alkyl groups (eg, methyl, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, octyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms ( For example, benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic group having 5 to 7 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), optionally substituted aryl group (eg, Phenyl group, chlorophenyl group,
A methoxyphenyl group, a methylphenyl group, a cyanophenyl group) or —O—R ₁₄ (R ₁₄ has the same meaning as the hydrocarbon group for R ₁₀ and R ₁₁ ). U represents a carbon-carbon bond which may pass through a hetero atom, and the number of atoms between oxygen atoms is 5 or less.

As described above, the monofunctional monomer (A) having at least two hydroxyl groups protected by one protecting group is the same as the one cited in the above-mentioned synthesis method [-O-L ₁ ]. Can be synthesized by the method described in the publicly known technical literature.

More specifically, examples of the monomer containing the functional group are as follows. Example (a-2
In 6) ~ (a-37) , a represents -H or -CH _3.

[Chemical 40]

[Chemical 41]

[Chemical 42]

[Chemical 43]

[Chemical 44]

[Chemical formula 45]

[Chemical formula 46]

[Chemical 47]

[Chemical 48]

[Chemical 49]

[Chemical 50]

[Chemical 51]

As the insoluble polymer component in the resin particles of the present invention, a monomer copolymerizable with the above-mentioned monofunctional monomer (A) may coexist. Examples of such a monomer include methacrylic acid esters, acrylic acid esters, and crotonic acid esters, as well as α-olefins, vinyl carboxylates, and acrylic acid esters (for example, carboxylic acids such as acetic acid and propionic acid. , Butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.) acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg dimethyl ester,
Diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), Vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (for example, vinylpyrrolidone,
Vinyl pyridine, vinyl imidazole, vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.).

As the polymerization component in the resin particles of the present invention, the proportion of the monomer (A) present is 30% by weight or more, preferably 5%.
It is 0% by weight or more, and particularly preferably, the resin particles are composed only of the monomer (A) and the monofunctional polymer [M]. When the other copolymerizable monomer is contained, the proportion of the other monomer present is at most 20% by weight or less. When the resin particles are a copolymer, the polymer component containing a hydroxyl group-forming functional group in the resin particles of the present invention is 10 to 95% by weight, particularly 20% by weight based on the total amount of the copolymer.
It is preferably about 90% by weight. What is important as the polymerization component that is insoluble in the non-aqueous solvent is that it has a hydrophilicity represented by a contact angle to distilled water of 50 ° or less as a substance after generation of a hydroxyl group.

Next, the monofunctional polymer [M] will be described. At least one repeating unit containing a substituent containing a silicon atom and / or a fluorine atom is contained, and the polymerizable double bond group represented by the general formula (I) is bonded to only one end of the polymer main chain. It is important that the polymer characterized in that it is copolymerized with the monomer A and solvated and soluble in the non-aqueous solvent, and functions as a dispersion stabilizing resin in so-called non-aqueous dispersion polymerization. To do. The monofunctional polymer liquid of the present invention may be soluble in the non-aqueous solvent, specifically, it may be dissolved in 100 parts by weight of the solvent at a temperature of 25 ° C. of at least 5% by weight. The weight average molecular weight of the polymer [M] is 1 × 10 ³ to 1 × 1.
It is 0 ⁵ , preferably 2 × 10 ^{3 to} 5 × 10 ⁴ , and particularly preferably 3 × 10 ³ to 2 × 10 ⁴ . The weight average molecular weight of the polymer [M] is less than 1 × 10 ³ or 1 ×
If it exceeds 10 ⁵ , the generated dispersed resin particles agglomerate, and it becomes impossible to obtain fine particles having a uniform average particle diameter.

In the monofunctional polymer [M], the polymerizable double bond group component represented by the general formula (I) which is bonded to only one end of the polymer main chain will be described below.

[Chemical 52] In the general formula (I), V₀Is -O-, -COO-,-
OCO-,-(CH ₂) -OCO-,-(CH₂) -C
OO-, -SO₂-,

[Chemical 53] Represents -CONHCOO- or -CONHCONH-.

Here, R ₁ is not only a hydrogen atom but also a preferable hydrocarbon group is a C 1-18 optionally substituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) Or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl Group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group Group, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

V ₀ is

[Chemical 54] When represented by, the benzene ring may have a substituent.
As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group,
Propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

A₁And a₂Are the same or different from each other
Yes, but preferably a hydrogen atom or a halogen atom (for example,
For example, chlorine atom, bromine atom, etc.), cyano group, C1-C4
Alkyl groups (eg methyl, ethyl, propyl
Group, butyl group, etc.)-COO-R ₂Or via hydrocarbon
COOR₂(R₂Is a hydrogen atom or an atom having 1 to 18 carbon atoms.
Alkyl group, alkenyl group, aralkyl group, alicyclic group or
Represents an aryl group, which may be substituted,
Specifically, the above R₁Similar to that described for
Represents). -COO via the above hydrocarbon
R₂Hydrocarbons in the group include methylene group and ethylen
Group, propylene group and the like.

More preferably, in the general formula (I),
V ₀ is -COO-, -OCO-, -CH ₂ OCO-,
_{-CH 2 COO -, - O -} , - CONH -, - SO 2 N
H-, -CONHCOO- or

[Chemical 55] And a ₁ and a ₂ may be the same or different from each other, and are a hydrogen atom, a methyl group, —COOR ₂ ′ or —C.
H ₂ COOR ₂ ′ and (R ₂ ′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). One of a ₁ and a ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group-containing moiety represented by the general formula (I), specifically,

[Chemical 56] Etc.

Next, the repeating unit having a substituent containing a silicon atom and / or a fluorine atom in the monofunctional polymer [M] will be described. Examples of the chemical structure of the repeating unit include those obtained from radical addition-polymerizable monomers, those consisting of a polyester structure, those consisting of a polyether structure, etc., and the side chains in the repeating units of these polymer structures include Any one containing a silicon atom and / or a fluorine atom may be used. Examples of the fluorine atom-containing substituent include —C _h F _{2h + 1} (h
Represents an integer of _{1~12), - (CF 2)} j CF 2 H
(J represents an integer of 1 to 11),

[Chemical 57] Is mentioned.

Examples of the substituent containing a silicon atom include, for example,

[Chemical 58] Examples thereof include a polysiloxane structure. However, R ₁₅ ,
R _16, R _17, which may be the same or different, optionally substituted hydrocarbon group or -OR ₂₁ group (R ₂₁ represents the same meaning as the hydrocarbon group of R ₁₅₎ represents an. R ₁₅ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2,2,2-
Trifluoroethyl group, 2-cyanoethyl group, 3,3
3-trifluoropropyl group, 2-methoxyethyl group,
3-bromopropyl group, 2-methoxycarbonylethyl group, 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl group, etc., and an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, , 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc., C7-12 optionally substituted aralkyl group (for example, benzyl group) , Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), Carbon number 5
To 8 optionally substituted alicyclic groups (eg, cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic groups having 6 to 12 carbon atoms (eg, Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, didecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) . In the —OR ₂₁ group, R ₂₁ has the same meaning as the hydrocarbon group for R ₁₅ above. R ₁₈ , R ₁₉ and R ₂₀ may be the same or different and have the same meaning as R ₁₅ , R ₁₆ and R ₁₇ .

Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. However, the scope of the present invention is not limited to these.

[Chemical 59]

[Chemical 60]

[Chemical formula 61]

[Chemical formula 62]

[Chemical formula 63]

[Chemical 64]

[Chemical 65]

[Chemical formula 66]

[Chemical formula 67]

[Chemical 68]

[Chemical 69]

[Chemical 70]

[Chemical 71]

[Chemical 72]

[Chemical formula 73]

[Chemical 74]

[Chemical 75]

[Chemical 76]

[Chemical 77]

[Chemical 78]

[Chemical 79]

[Chemical 80]

[Chemical 81]

[Chemical formula 82]

[Chemical 83]

[Chemical 84]

[Chemical 85]

[Chemical 86]

[Chemical 87]

[Chemical 88]

The monofunctional polymer [M] of the present invention comprises a repeating unit having a polymerizable double bond group represented by the above formula (I) and a substituent containing a silicon atom and / or a fluorine atom. At least one end of the main chain of the polymer to be contained is directly bonded or is bonded with an arbitrary linking group. Specifically as the linking group is a divalent organic residue,

[Chemical 89] A binding group selected from the group may be interposed. It represents an organic residue composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues. Where g ₁
To g ₅ have the same meaning as R ₁ in formula (I).

As the divalent aliphatic group, for example,

[Chemical 90] {E ₃ and e ₄ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group). , Ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q
Represents —O—, —S— or —NR ₂₂ —, R ₂₂ represents an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂ Br.
Represents}.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be given as examples of the substituent.
Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-
An oxazoline ring etc. are mentioned.

The general formula (II) of the above monofunctional polymer [M]
Specific examples of the polymerizable double bond group-containing portion represented by and the portion composed of the organic residue linked thereto include, but are not limited to, the following.
However, in each of the following examples, P ₁ is —H, —CH ₃ , —
CH ₂ COOCH _3, -Cl, shows -Br or -CN, P ₂ represents -H or -CH _3, X ₂ represents a -Cl or -Br, n is an integer of 2 to 12, m Is 1 to 4
Indicates an integer.

[Chemical Formula 91]

[Chemical Formula 92]

[Chemical formula 93]

[Chemical 94]

[Chemical 95]

[Chemical 96]

[Chemical 97]

[Chemical 98]

[Chemical 99]

[Chemical 100]

[Chemical 101]

[Chemical 102]

[Chemical 103]

[Chemical 104]

[Chemical 105]

[Chemical formula 106]

[Chemical formula 107]

[Chemical 108]

[Chemical 109]

[Chemical 110]

[Chemical 111]

[Chemical 112]

[Chemical 113]

[Chemical 114]

[Chemical 115]

[Chemical formula 116]

[Chemical 117]

[Chemical 118]

[Chemical formula 119]

[Chemical 120]

In the total sum of repeating units of the monofunctional polymer [M] of the present invention, the repeating units having a substituent containing a silicon atom and / or a fluorine atom account for 40% of the total.
It is preferably contained in an amount of not less than wt%, more preferably 60 to 100 wt%. When the amount of the above components of the present invention is less than 40% by weight of the whole, the effect of concentrating the resin particles dispersed in the image receiving layer, particularly on the surface portion, decreases, and as a result, the effect of improving water retention as a printing original plate is weakened. Will end up.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthetic method. For example,
A) a method by ionic polymerization, in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to obtain a monofunctional polymer [M],
(B) A polymer having a terminal reactive group bond obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxyl group and an amino group in the molecule. A method by a radical polymerization method in which various reagents are reacted to obtain a monofunctional polymer [M], and c) a polymer obtained by a polyaddition or polycondensation reaction is treated with a polymerizable diamine in the same manner as in the above radical polymerization method. Examples thereof include a method by a polyaddition condensation method of introducing a heavy bond group.

Specifically, P. Dreyfuss & RP Quirk
, Encycl. Polym. Sci. Eng., 7 , 551 (198
7), PF Rempp, E. Franta, Adv. Polym. Sci., 5
8 , 1 (1984), V. Percec, Appl. Poly. Sci., 2
85 , 95 (1984), R. Asami, M. Takari, Macro.
mol. Chem. Suppl., 12 , 163 (1985), P. Rem
pp., et al, Macromol. Chem. Suppl., 8 , 3 (198
4), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987),
Yuya Yamashita, Kobunshi, 31 , 988 (1982), Shiro Kobayashi, Kobunshi, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesive Society, 18 , 536 (1982), Koichi Ito,
Polymerization, 35 , 262 (1986), Takashiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5 and the like, and the methods described in the literature and patents cited therein.

More specifically, as the method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radical-polymerizable monomer is described in JP-A No. 2/1990.
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application Nos. 1-206989 and 1-69011, and the like, and also contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] is prepared according to Japanese Patent Application Nos. 1-56379 and 1-58989.
It can be obtained in the same manner as the methods described in the specification of the application, etc., as Nos. 1-56380.

As described above, the dispersed resin particles of the present invention are obtained by adding the functional group-containing monofunctional monomer (A) which decomposes to produce at least one hydroxyl group to the monofunctional resin [M]. It is a copolymer resin particle obtained by dispersion polymerization in the presence.

The resin particles of the present invention may have at least a part thereof crosslinked. The resin particles in which at least a part of the polymer is pre-crosslinked (resin having a crosslinked structure in the polymer) has a structure in which the above-mentioned hydroxyl group-forming functional group contained in the resin produces a hydroxyl group by decomposition. Resin particles that are hardly soluble or insoluble in acidic and alkaline aqueous solutions are preferred.

Further, when the dispersed resin particles of the present invention have a network structure, a polymer component containing the above-mentioned hydroxyl group-forming functional group-containing monofunctional monomer (A) as a main component [polymer component (A Abbreviated as []] is cross-linked between polymers to form a high-order network structure.

That is, the dispersed resin particles of the present invention are composed of a non-aqueous dispersion solvent composed of the polymer component (A) and a polymer soluble in the non-aqueous dispersion solvent. When it is a latex and has a network structure, the molecules of the polymer component (A) forming the portion insoluble in the solvent are bridged. As a result, the network resin particles after the formation of hydroxyl groups are hardly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight.
It is the following.

The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, (a) a method of crosslinking a polymer containing the polymer component (A) with various crosslinking agents or curing agents, and (b) containing at least a monomer corresponding to the polymer component (A). When a polymerization reaction is carried out by using a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, a network structure is formed between the molecules, and (c) the polymer. It can be carried out by a method such as a method of crosslinking the combined component (A) and the polymers containing the component containing a reactive group by a polymerization reaction or a polymer reaction.

Examples of the cross-linking agent in the above method (a) include compounds that are usually used as cross-linking agents.
Specifically, compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei Corporation (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), etc. Can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and other silane coupling agents), polyisocyanate compounds (eg, toluylene diisocyanate, o-toluy) Diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), polyol compounds (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (for example, ethylenediamine, γ-hydroxypropyl) Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
Kakiuchi Hiroshi "New Epoxy Resins" Shokoido (1985), Kuniyuki Hashimoto "Epoxy Resins" compounds published in Nikkan Kogyo Shimbun (1969), melamine resins (for example, Ichiro Miwa, Hideo Matsunaga) Edited by "Uria Melamine Resin", compounds described in Nikkan Kogyo Shimbun (published in 1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976) Annually), Eizo Omori "Functional acrylic resin" Techno System (published in 1985) and the like, and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6- Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacryle Door, bisphenol A-
Examples include diglycidyl ether diacrylate, oligoester acrylate, and their methacrylates.

Further, polymerization of a polyfunctional monomer (also referred to as a polyfunctional monomer (D)) or a polyfunctional oligomer having two or more polymerizable functional groups coexisting in the above method (b). As the sexual functional group, specifically,

[Chemical 121] Etc. can be mentioned. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a monomer or oligomer having the same polymerizable functional group, a styrene derivative such as divinylbenzene or trivinylbenzene: polyvalent. Alcohol (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg methacrylic acid, acryl) Acid, crotonic acid, allyl acetic acid, etc.) and the like.

The monomers or oligomers having different polymerizable functional groups include, for example, vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, arylloyl). Propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants (for example, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropione) Ester derivatives or amide derivatives containing vinyl groups such as acids) (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl) Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene ester, N- allyl acrylamide, N-
Allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group And a condensate with a carboxylic acid containing

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is a monomer (A).
And 10 with respect to the total amount of other monomers coexisting with (A).
Polymerization is carried out using less than mol%, preferably less than 5 mol% to form a resin.

Further, in the case of the above method (c), when a chemical bond is formed by the reaction between the reactive groups between the polymers to form a bridge between the polymers, the reaction with a usual organic low molecular compound is performed. You can do the same. Specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (Published in 1977), Ryohei Oda "Polymer Fine Chemical" Kodansha (Published in 1976),
JP-A-61-43757, Japanese Patent Application No. 1-149030
It is described in detail in the specification etc. filed as No. 5.

For example, a polymer reaction resulting from the combination of the functional group of group A and the functional group of group B in Table 1 below is a well known method. Note that R ₂₃ and R _{24 in} Table-1
It is a hydrocarbon group, supra _{-Si (g 4) (g 5} ) - represents a g _4, g ₅ same contents as in.

[Table 1] In dispersion polymerization, monodisperse particles having a uniform particle size can be obtained, and fine particles of 0.5 μm or less can be easily obtained. Therefore, as a method for forming a network structure, a polyfunctional monomer is used. The method (b) using is preferred.

As described above, the network-dispersed resin particles of the present invention contain a repeating unit containing a protected carboxyl group and a polymer component soluble in the non-aqueous solvent, and have a high degree of intermolecular chain linkage. It is a polymer particle having a bridged structure.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, which may be used alone or in admixture of two or more. Good. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, and benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether, and the like.
Tetrahydrofuran, dioxane, and other ethers, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and other carboxylic acid esters, hexane, octane, decane, dodecane, tridecane, cyclohexane, cyclooctane, and other fatty acids having 6 to 14 carbon atoms Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene, xylene, chlorobenzene, and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle diameter of the resin particles easily becomes 0.8 μm or less, and the distribution of the particle diameter is very narrow and monodispersed. Can be particles. Specifically, KEJ Barrett "Dispersion Polymerization
in Organic Media "John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto, Toyokichi Tange, Japan Adhesion Society Magazine 9 , 183 (197).
3), Toyokichi Tange, The Japan Adhesive Society magazine 23 , 26 (198).
7), DJ Walbridge, NATO. Adv. Study. Inst. Se
r. E. No. 67, 40 (1983), British Patent No. 893.
429, 934038, U.S. Pat. No. 112.
2397, 394012, 4606989, JP-A-60-179751, and 60-18596.
The method is disclosed in each of the three gazettes.

The dispersion resin of the present invention comprises at least one type of each of the monomer (A) and the monofunctional polymer [M],
In the case of forming a network structure, a polyfunctional monomer (D) is allowed to coexist as necessary, and in any case, it is important that the resin synthesized from these monomers is used in the non-aqueous solvent. If insoluble, desired dispersed resin particles can be obtained.
More specifically, the amount of the monomer (A) is 30% by weight or more, preferably 50% by weight or more, and the insoluble monomer (A) is used.
It is preferable to use 1 to 50% by weight of the monofunctional polymer [M], more preferably 2 to 30% by weight,
It is particularly preferably 5 to 25% by weight. When another copolymerizable monomer is used, the content of the other monomer is 20% by weight or less. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ -10.
⁶ and preferably 10 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersed resin particles used in the present invention as described above, generally, a monomer (A), a monofunctional polymer [M], and further a polyfunctional monomer (D) are used. Benzoyl peroxide, azobisisobutyronitrile in a non-aqueous solvent,
The heat polymerization may be carried out in the presence of a polymerization initiator such as butyl lithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of a monomer (A), a monofunctional polymer [M] and a polyfunctional monomer (D), There is a method in which a mixture of the above-mentioned polymerizable compound and a polymerization initiator is added dropwise or arbitrarily added to a water solvent, and the method is not limited to these, and any method can be used for production.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 30
It is about 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles having a uniform particle size distribution.

As the matrix resin (binder resin) used in the image-receiving layer of the present invention, all of the conventionally known binder resins can be used. Typical examples are 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 polyvinyl alcohol as a water-soluble polymer compound, modified polyvinyl alcohol, Examples thereof include starch, oxidized starch, carboxymethyl cellulose, hydroxyethyl cellulose, gelatin, polyacrylic acid, polyvinylpyrrolidone, polyvinyl ether-maleic anhydride copolymer, polyamide and polyacrylamide.

The molecular weight of the matrix resin used in the image receiving layer of the present invention is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . The glass transition point of this resin is preferably -10 ° C to 120 ° C.
C, more preferably 0 to 85 ° C. The proportion of resin particles present in the image receiving layer is about 1 to 80 parts by weight of resin particles with respect to 100 parts by weight of the matrix resin. If it is less than 1% by weight, scumming will occur, and if it exceeds 80% by weight, the image strength will decrease, which is not preferable.

An inorganic pigment is used as another component of the image receiving layer of the present invention, and examples of the inorganic pigment include kaolin clay, calcium carbonate, silica, titanium oxide, and the like.
Examples thereof include zinc oxide, barium sulfate, and alumina. The ratio of the binder resin / pigment in the image receiving layer varies depending on the type of material and the particle size of the pigment. Generally, the weight ratio is 1 / (0.5 to 5), preferably 1 / (0.8 to 2.5). Is appropriate.

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

The support used in the present invention includes high quality paper, wet reinforced paper, plastic film such as polyester film, metal plate such as aluminum plate and the like.

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

When it is used as a PPC plate-making, in order to further reduce the background stain of the printing original plate of the present invention, an image receiving layer is further added so that the volume resistivity of the printing original plate becomes 10 ¹⁰ to 10 ¹³ Ωcm. A dielectric agent can be added to the intermediate layer and / or the back coat layer. The dielectric agent may be an inorganic type or an organic type, and as the dielectric type, salts of monovalent or polyvalent metals such as Na, K, Li, Mg, Zn, Co, and Ni may be used. Examples thereof include polymeric cation conductive agents such as polyvinylbenzyltrimethylammonium chloride and acrylic resin-modified quaternary ammonium salts, and polymeric anionic dielectric agents such as polymeric sulfonates. The amount of these conductive agents added is 3 to 40% by weight, preferably 5 to 20% by weight of the amount of binder used in each layer.
% By weight.

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

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

The method for desensitizing the resin particles used in the present invention, that is, the method for decomposing the protected hydroxyl group, is arbitrarily selected depending on the decomposition reactivity of the protected hydroxyl group as one of the methods. acidic conditions of pH 1-6,
A method of hydrolyzing with an aqueous solution of pH 8 to 12 under alkaline conditions can be mentioned. The adjustment of these pHs can be easily performed with known compounds. Alternatively, a method by a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and known compounds can be used as these compounds, for example, hydrazine hydrate, sulfite, lipoic acid, hydroquinones, formic acid, Examples thereof include thiosulfate, hydrogen peroxide, persulfate and quinones.

The treatment liquid may contain other compounds in order to accelerate the reaction or improve the storage stability of the treatment liquid. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.),
Ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.) ), Esters (methyl acetate, ethyl acetate, ethyl formate, etc.) and the like, and these may be used alone or in combination of two or more kinds.

Further, the surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, 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.

The scope of the present invention is not limited to the above specific compound examples. The processing condition is a temperature of 15 ° C.
The immersion time at -60 ° C is preferably 10 seconds to 5 minutes.

[0083]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this. First, a production example of a monofunctional polymer [M] for resin particles and resin particles will be shown. Production Example 1: Monofunctional Polymer [M] 1: [M-1] 2
A mixed solution of 95 g of 2,2,2 ′, 2 ′, 2′-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.0 g of azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and t were added to the reaction solution.
-Butyl hydroquinone 0.5g was added and the temperature was 100 ° C.
The mixture was stirred for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight of the polymer [M-1] was 4000. Monofunctional polymer [M-1]

[Chemical formula 122]

Production Example 2 of monofunctional polymer [M]: [M-
2] A mixed solution of 96 g of the monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to 70 ° C under a nitrogen stream. A. I. B. N.
1.0g was added and it reacted for 8 hours. Then, the reaction solution was cooled in a water bath to a temperature of 25 ° C., and 10 g of 2-hydroxyethyl methacrylate was added thereto. Dicyclohexyl carbonamide (abbreviated as D.C.C.) 15 g, 4
A mixed solution of 0.2 g of-(N, N-dimethylamino) pyridine and 50 g of methylene chloride was added dropwise with stirring over 30 minutes, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added and after stirring for 1 hour, the precipitated insoluble material was filtered off, and the filtrate was reprecipitated in 1 liter of n-hexane. The viscous material that precipitated was collected by decantation, dissolved in 100 ml of tetrahydrofuran, the insoluble material was filtered off again, and reprecipitated in 1 liter of n-hexane. The polymer [M-2] obtained by drying the precipitated viscous material had a yield of 60 g and a weight average molecular weight of 5.2 × 10 5.
^{Was 3} . Monomer (MA-1)

[Chemical 123] Monofunctional polymer [M-2]

[Chemical formula 124]

Production Example 3 of Monofunctional Polymer [M]: [M-
3] A mixed solution of 95 g of a monomer (MA-2) having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. 2 g of 4,4′-azobis (4-cyanovaleric acid) (abbreviation ACV)
Was added and reacted for 8 hours. After cooling, it was reprecipitated in 1 liter of methanol, and the obtained polymer was dried. Then 50 g of this polymer and 2-hydroxyethyl methacrylate 11
g, dissolved in 150 g of benzotrifluoride, temperature 25 ° C
And This mixture was stirred under a D.I. C. C. 15g, 4
A mixed solution of 0.1 g of-(N, N-dimethylamino) pyridine and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was stirred as it was for 4 hours. After that, 3 g of formic acid was added and stirred for 1 hour. Then, the precipitated insoluble matter was filtered off, and the filtrate was reprecipitated in 800 ml of methanol. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again,
30 g of a viscous material was obtained. The weight average molecular weight of the polymer [M-3] was 3.3 × 10 ⁴ . Monomer (MA-2)

[Chemical 125] Monofunctional polymer [M-3]

[Chemical formula 126]

Production Examples 4 to 22 of Monofunctional Polymer [M]:
[M-4] to [M-22] Another monomer (a monomer corresponding to the polymer component shown in Table 2) instead of the monomer (MA-1) in Production Example 2.
Each monofunctional polymer [M] was produced in the same manner as in Production Example 2 except that was used. Each weight average molecular weight is 4 × 10 ³ ~
It was 6 × 10 ³ .

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Production Examples 23 to 3 of Monofunctional Polymer [M]
0: [M-23] to [M-30] monofunctional polymer [M]
In Production Example 2 of Example 1, except that the monomer (MA-1) and 2-hydroxyethyl methacrylate were replaced with the compounds corresponding to the polymers in Table 3 below, respectively, and the other monofunctional polyamines were produced by the same method. A combined product [M] was produced. Each weight average molecular weight was 5 × 10 ^{3 to} 6 × 10 ³ .

[Table 6]

[Table 7]

[Table 8]

Production Example 31 of Monofunctional Polymer [M]: [M
-31] Octyl methacrylate 30 g, monomer (MA-3) 70 g having the following structure, glycidyl methacrylate 3
A mixed solution of g and 200 g of benzotrifluoride was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A.
I. B. N. 1.0 g was added and reacted for 4 hours.
I. B. N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110 ° C. for 8 hours. After cooling, reprecipitation was carried out in 2 liters of methanol, and a slightly brownish oily substance was collected and then dried. The yield was 73 g and the weight average molecular weight was 3.6 × 10 ⁴ . Monomer (MA-3)

[Chemical 127] Monofunctional polymer [M-31]

[Chemical 128]

Production Example 32 of Monofunctional Polymer [M]: [M
-32] A mixed solution of 80 g of the following monomer (MA-4), 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was heated to 60 ° C while stirring under a nitrogen stream. To this, 2,2'-azobis (isovaleronitrile) (abbreviation: AIV.
N. ) 0.8 g, and reacted for 4 hours. I.
V. N. 0.4 g was added and reacted for 4 hours. After cooling the reaction product to a temperature of 25 ° C., 4 g of methacrylic acid was added, and the mixture was added with D. C. C. 6 g, 4- (N, N-dimethylamino) pyridine 0.1 g and methylene chloride 15 g
The mixed solution of was added dropwise over 1 hour, and the mixture was stirred as it was for 3 hours. Next, 10 g of water was added, the mixture was stirred for 1 hour, the precipitated insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol to collect an oily substance. Furthermore, this oily matter was converted to benzene 1
It was dissolved in 50 g, the insoluble matter was filtered off, and then reprecipitated again in 1 liter of methanol, and an oily matter was collected and dried. Yield is 5
The weight average molecular weight of 6 g was 8 × 10 ³ .

Monomer (MA-4)

[Chemical formula 129] Monofunctional polymer [M-32]

[Chemical 130]

Production Examples 33 to 3 of Monofunctional Polymer [M]
9: [M-33] to [M-39] The monofunctional polymers [M] shown in Table 4 below were synthesized by carrying out the reactions shown in Production Example 32. The weight average molecular weight of each polymer [M] was in the range of 6 × 10 ^{3 to} 9 × 10 ³ .

[Table 9]

[Table 10]

Production Example of Resin Particles 1: [L-1] 10 g of monofunctional polymer [M-32] and n-octane 2
While stirring the mixed solution of 00g under nitrogen stream, the temperature is 60 ° C.
Warmed to. To this, 50 g of the following monomer (A-1), 5 g of ethylene glycol dimethacrylate, A. I. V.
N. A mixed solution of 0.5 g and 240 g of n-octane was added dropwise over 2 hours, and the reaction was continued for 2 hours. In addition, A.
I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a 200 mesh nylon cloth was passed through to obtain a white dispersion. It was a latex having an average particle size of 0.20 μm {C
Particle size measurement by APA-500 [manufactured by Horiba, Ltd.]. Monomer (A-1)

[Chemical 131]

Production Examples 2-11 of Resin Particles: [L-2]
[L-11] Resin particles except that the monomer (A-1) and the monofunctional polymer [M-32] were replaced with the respective compounds shown in Table 5 below in Production Example 1 of resin particles. Resin particles [L] were produced in the same manner as in Production Example 1. The average particle size of each particle is 0.15
It was in the range of μm to 0.30 μm.

[Table 11]

[Table 12]

Production Example 12 of Resin Particles: [L-12] Dispersion stabilizing resin AK-5 as a monofunctional polymer [manufactured by Toa Gosei Co., Ltd. Macromonomer: dimethylsiloxane Macromonomer having repeating unit: weight] Average molecular weight 1.
5 × 10 ⁴ ] 7.5 g and methyl ethyl ketone 133 g
The mixed solution of 1 was heated to 60 ° C. with stirring under a nitrogen stream. To this, 50 g of the following monomer (A-12), 5 g of diethylene glycol dimethacrylate, A. I. V. N.
A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour, and A. I. V. N. 0.25g
Was added and reacted for 2 hours. After cooling, the average particle size of the dispersion obtained through a 200 mesh nylon cloth was 0.18.
was μm. Monomer (A-12)

[Chemical 132]

Production Example 13 of Resin Particles: [L-13] A mixed solution of 7.5 g of the monofunctional polymer [M-35] and 230 g of methyl ethyl ketone was heated to 60 ° C. with stirring under a nitrogen stream. 35 g of the monomer (A-13),
15 g of acrylamide, A. I. V. N. A mixed solution of 0.5 g and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. In addition, A. I.
V. N. After adding 0.25 g and reacting for 2 hours, the mixture was cooled and passed through a nylon cloth of 200 mesh, and the average particle size of the obtained dispersion was 0.20 μm. Monomer (A-13)

[Chemical 133]

Production Example 14 of resin particles: [L-14] 50 g of the monomer (A-14), 2 g of ethylene glycol diacrylate, 8 g of the monofunctional polymer [M-33] and 230 g of dipropyl ketone were added to a nitrogen stream. It was added dropwise to a solution of 200 g of dipropyl ketone heated to a lower temperature of 60 ° C. over 2 hours while stirring. After reacting for 1 hour as it is, A.
I. V. N. 0.3 g was added and reacted for 2 hours. The average particle size of the dispersion obtained after passing through a 200-mesh nylon cloth after cooling was 0.28 μm. Monomer (A-14)

[Chemical 134]

Production Examples 15-25 of Resin Particles: [L-1
5] to [L-25] In the same manner as in Production Example 14, except that the polyfunctional compound of Table 6 below was used in place of 2 g of ethylene glycol diacrylate in Production Example 14 of resin particles, resin particles [ L
-15] to [L-25] were produced. Each particle has a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.
Met.

[Table 13]

Production Examples 26-31 of resin particles: [L-2
6] to [L-31] In Production Example 12 of resin particles, the dispersion stabilizing resin AK-
Each resin particle [L] was produced in the same manner as in Production Example 12 except that each monofunctional polymer [M] in Table 7 below was used in place of 6. The average particle size of each particle is 0.20 to 0.25 μm
Was in the range.

[Table 14]

Production Examples of Resin Particles 32-35: [L-3
2] to [L-35] In Production Example 13 of resin particles, the monomer (A-13),
Each resin particle [L] was produced in the same manner as in Production Example 13 except that each compound shown in Table 8 below was used instead of acrylamide and reaction solvent methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 to 0.30 μm.

[Table 15]

Example 1 10 g of resin particles [L-1] (as solid content) and resin [B-1]: methyl methacrylate / acrylic acid (99
/ 1, weight ratio) copolymer (weight average molecular weight 4500
0): 20 g, zinc oxide 100 g and toluene 300 g
The mixture was dispersed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 × 10 ³ rpm for 10 minutes. Next, this dispersion was applied onto a middle layer of a support having a back layer on one side of high-quality paper and an intermediate layer on the other side with a wire bar so that the dry adhesion amount was 18 g / m ^2. Then 1
It was dried at 00 ° C. for 1 minute to prepare a lithographic printing plate precursor. Next, the plate was made with a commercially available PPC, and the obtained original plate was etched once with an aqueous solution prepared by diluting the desensitizing treatment liquid ELP-EX manufactured by Fuji Photo Film Co., Ltd. 5 times with distilled water. I passed it. Furthermore, a liquid obtained by diluting 0.5 mol monoethanolamine in 1 liter of distilled water [treatment liquid (E
-1)] for 3 minutes. The density of the image portion of the obtained original plate was 1.0 or more, there was no background fog in the non-image portion, and the image quality of the image portion was clear. This was applied to an offset printing machine (Oliver 52 type, manufactured by Sakurai Seisakusho Co., Ltd.) to print on high-quality paper. Even if the number of sheets exceeds 3,000, there is no problem in the background stain of the non-image area of the printed matter and in the image quality of the image area.

Examples 2 to 15 The procedure of Example 1 was repeated, except that the copolymers shown in Table 9 were used instead of the resin particles [L-1] of the present invention. Thus, each lithographic printing plate precursor was produced.

[Table 16] This was operated in the same manner as in Example 1 to prepare an original plate, and the obtained master plate for offset printing had a density of 1.
At 2 or more, the image quality was clear. Further, when etching was performed and printing was performed by a printing machine, the printed matter after printing 3000 sheets had no fog in the non-image area and the image was clear.

Example 16 A mixture of 4 g of resin particles [L-12] (as solid content) and 29 g of a binder resin [B-2] having the following structure, 50 g of zinc oxide and 200 g of toluene was added in a homogenizer at 6 × 1.
Disperse at 0 ³ rpm for 10 minutes, and add phthalic anhydride 0.5
g and 0.02 g of o-chlorophenol and added 1 ×
The dispersion was carried out at 10 ³ rpm for 1 minute. The dispersion thus obtained was coated on a support under the same conditions as in Example 1, and then 1
It was dried at 00 ° C. for 30 seconds and further heated at 110 ° C. for 1 hour to prepare a lithographic printing plate precursor. Binder resin [B-2]

[Chemical 135] This was subjected to plate making with the same device as in Example 1, then etching treatment and printing with a printing machine. The density of the master plate for offset printing obtained after plate making was 1.0 or more, and the image quality was clear. Further, the image quality of the printed matter after printing 5000 sheets was a clear image without background fog.

Example 17 A mixture of 15 g of resin particles [L-3] (as solid content), 20 g of resin [B-3] having the following structure, 80 g of zinc oxide and 150 g of toluene was dispersed in a ball mill for 1.5 hours. . Next, 4 g of hexamethylene diisocyanate was added to this dispersion, which was further dispersed in a ball mill for 10 minutes to prepare a backing layer on one side of the high-quality paper and an intermediate layer of a support having an intermediate layer on the other side. 25 g / m ² of dry adhesion on top
And a wire bar for 90 minutes and dried at 100 ° C. to prepare a lithographic printing plate precursor. Resin [B-3]

[Chemical 136] This original plate is used as a desensitizing solution [Fuji Photo Film Co., Ltd.
ELP-EX] to pass through the etching processor once, and then add 3 times in the following desensitizing solution (E-2).
Immerse at 5 ° C. for 3 minutes. Desensitizing treatment liquid (E-2): Diethanolamine 75 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 6 g Benzyl alcohol 100 g was dissolved in distilled water to a total amount of 1 liter. A drop of distilled water (2 μl) was placed on the printing plate thus obtained, and the contact angle with the formed water was measured by a goniometer to be 10 ° or less. It was 98 ° before the desensitizing treatment. This indicates that the non-image area of the image-receiving layer of the original plate of the present invention changed from lipophilicity to hydrophilicity (usually, the non-image area is hydrophilized so that print background stains and dot-like stains do not occur during printing). The contact angle with water is 20 °
Must be below). Next, after plate making in the same manner as in Example 1, the above desensitizing treatment was performed and printing was performed.
Even if the number of sheets exceeds 000, there is no problem with the background stain of the non-image area of the printed matter and the image quality of the image area.

Resins 18 to 22, except that the compounds of Table 10 below were used instead of the hexamethylene diisocyanate used in Example 17,
A lithographic printing plate precursor was prepared in the same manner as in Example 1.

[Table 17] This was subjected to plate making with the same device as in Example 1, then etching treatment and printing with a printing machine. The density of the master plate for offset printing obtained after plate making is 1.0 or more,
The image quality was clear. Further, the image quality of the printed matter after printing 5000 sheets was a clear image without background fog.

Examples 23 to 36 In the same manner as in Example 17, except that 15 g of resin particles [L-3] shown in Table 11 below was used instead of 15 g of resin particles [L-3] in Example 17, An original plate was made.

[Table 18] After each original plate was prepared as in Example 17, the original plate was passed through an etching machine once using ELP-EX, and then 3 times in a resin particle desensitizing solution (E-3) having the following formulation. It was desensitized by immersion for a minute. Resin particle desensitizing solution (E-3): Boric acid 65 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 6 g Benzyl alcohol 80 g was dissolved in distilled water to a total volume of 1 liter, and then pH was adjusted to 10 with potassium hydroxide. Aqueous solutions adjusted to 5 were printed in the same manner as in Example 1, and as a result, 300 prints of clear image quality with no scumming were produced on each original plate.
0 or more sheets were obtained.

[0106]

According to the present invention, it is possible to obtain a direct-drawing type lithographic printing plate precursor in which the occurrence of background fog is satisfactorily suppressed and which has good printing durability.

Claims (2)

[Claims] 1. A direct drawing type lithographic printing plate precursor having an image receiving layer on a support, wherein the image receiving layer contains at least one of the following non-aqueous solvent type dispersed resin particles. Original plate for lithographic printing. Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, at least one functional group that is soluble in the non-aqueous solvent but is insolubilized by polymerization and that produces at least one hydroxyl group by decomposition
The following general formula (A) is provided only at one end of the main chain of the polymer containing at least one repeating unit containing a seed-containing monofunctional monomer (A) and a substituent containing a silicon atom and / or a fluorine atom. Polymer resin particles obtained by subjecting a monofunctional polymer [M] having a polymerizable double bond group represented by I) to a dispersion polymerization reaction. [Chemical 1] [However, in the general formula (I), V ₀ is -O-,-
COO -, - OCO -, - (CH 2) -OCO -, -
(CH ₂ ) -COO-, -SO _2- , Represents —CONHCOO— or —CONHCONH— (R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), and a ₁ and a ₂ may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R ₂ or -COO-R ₂ (R
₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)
Represents] 2. The direct drawing type lithographic printing plate precursor as claimed in claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure.