JP2781086B2 - Original plate for direct drawing type lithographic printing - Google Patents

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 plate precursor, and more particularly to a direct drawing type lithographic printing plate suitable for an office printing plate.

[0002]

2. Description of the Related Art At present, a direct-drawing lithographic printing original plate having an image receiving layer on a support is widely used as an office printing original plate. In order to perform plate making, that is, image formation on such a printing original plate, a method of drawing oil-based ink by hand on an image receiving layer, or printing by a typewriter, an ink jet system, or a transfer type thermal system is generally adopted. In addition, a method of transferring and fixing a toner image formed on a photoreceptor to an image receiving layer through a charging, exposing, and developing process using a plain paper electrophotographic copying machine (PPC) has begun to be used in recent years. In any case, the printing original plate after plate making,
After the surface of the non-image portion is desensitized by surface treatment with a desensitizing solution (so-called etchant), the non-image portion is subjected to lithographic printing as a printing plate.

[0003] A conventional direct drawing type lithographic printing plate precursor is provided with a back surface layer on one side of a support such as paper, and an image receiving layer as a surface layer on the other side via an intermediate layer. The back layer or the intermediate layer is formed of a water-soluble resin such as PVA or starch, a water-dispersible resin such as a synthetic resin emulsion, and a waterproofing agent. A typical example of such a lithographic printing plate precursor is U.S. Pat.
As described in JP-A-532865, a water-soluble resin binder such as PVA, an inorganic pigment such as silica, calcium carbonate and the like, and a water-proofing agent such as a melamine-formaldehyde resin precondensate are mainly used. It is configured as a component.

[0004]

However, in the conventional printing plate thus obtained, in order to improve the printing durability, a large amount of a water-proofing agent is added or a hydrophobic resin is used. When the hydrophobicity is increased to increase the printing durability, the printing durability is improved, but the hydrophilicity is reduced, and printing stains are generated. On the other hand, when the hydrophilicity is improved, the water resistance is deteriorated and the printing durability is reduced. there were. Especially in a high temperature use environment of 30 ° C or more,
The surface layer (image receiving layer) was dissolved in the immersion water used for offset printing, and there were major drawbacks such as a reduction in printing durability and the occurrence of printing stains. Further, the lithographic printing plate precursor draws an oily 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 oily ink is not good, even if the non-image portion has sufficient hydrophilicity. Even if the printing stains do not occur as described above, there is also a problem that the oily ink in the image area is lost during printing, and as a result, the printing durability is reduced.

The present invention solves the above-mentioned problems of the direct drawing type lithographic printing plate precursor. SUMMARY OF THE INVENTION An object of the present invention is to provide a direct drawing type lithographic printing plate precursor which is excellent in desensitizing property and does not generate not only a uniform background stain but also a dot-like background stain as an offset master 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, maintain the hydrophilicity of the non-image area sufficiently even when the number of printed sheets increases, and generate background stains. The object of the present invention is to provide a direct drawing type lithographic printing plate precursor having high printing durability.

[0006]

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

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

Embedded image 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 a hydrocarbon group of over a -COO-R ₂ (R
₂ represents a hydrogen atom or a hydrocarbon group which may be substituted)
Further, in the present invention, the non-aqueous solvent-based dispersed resin particles may form a higher-order network structure.

[0007]

The present invention is characterized in that the image receiving layer of the direct drawing type lithographic printing plate precursor contains the non-aqueous solvent-based dispersed resin particles, and the non-aqueous solvent-based dispersed resin particles (hereinafter simply referred to as resin particles). May be abbreviated to at least one functional group capable of generating at least one hydroxyl group by decomposition.
A polymer component containing a species and becoming insoluble in the non-aqueous solvent after polymerization, and a monofunctional polymer containing a repeating unit containing at least a silicon atom and / or a fluorine atom as a substituent and being soluble in the non-aqueous solvent after polymerization. And a chemically bonded polymer component.

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

In the present invention, the resin particles are present in the image receiving layer separately and as particles from the binder resin which is a matrix of the image receiving layer. The resin particles undergo a reaction such as a hydrolysis reaction, a redox reaction, and a photodecomposition reaction by a hydrophilization treatment using a desensitizing liquid and immersion water used during printing, whereby a protected hydroxyl group portion chemically reacts. To generate a hydroxyl group, and convert from a hydrophobic property to a hydrophilic property.

[0010] On the other hand, the resin particles also have a polymer component containing silicon atoms and / or fluorine atoms having extremely large lipophilicity. Therefore, the direct-lithographic lithographic printing plate precursor of the present invention containing the resin particles in the image receiving layer has a lipophilic group in the resin particles when the image receiving layer is drawn with an oil-based ink or the like as an image portion. , The adhesion between the image receiving layer and the oil-based ink is improved, and the printing durability is improved.
In the non-image area, as described above, the resin particles quickly show hydrophilicity to the desensitizing liquid and immersion water, so that they are clearly distinguished from the lipophilicity of the image area, and the printing ink adheres to the non-image area during printing. It will not be.

And an image receiving layer in which such hydrophilic resin particles are dispersed in a binder resin of a matrix.
In a printing original plate in which a non-image portion is treated with a desensitizing liquid to make the surface hydrophilic to form a direct drawing type lithographic printing original plate, known hydrophilic resin particles are uniformly dispersed throughout the surface layer. I do. On the contrary, although the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the image receiving layer, the function of the substituent-containing polymer component having significantly large lipophilic silicon and / or fluorine atoms is exerted. As a result, it is concentrated and present on the surface of the image receiving layer which is an air interface (having a high lipophilicity). Therefore, the water retention of the non-image area is remarkably improved only by dispersing a smaller amount (the amount of use is 50 to 10% as compared with the known technique of hydrophilic resin particles).

Further, the resin particles have a hydrophobic (lipophilic) polymer component bonded thereto, and the hydrophobic portion interacts with a binder resin which is a matrix of the image receiving layer. Due to the anchor effect of this portion, even if it shows hydrophilicity, it does not elute with soaking water at the time of 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 higher-order network structure, the dissolution property in water can be further suppressed, and on the other hand, the water swelling property can be expressed and the water retention property can be further improved. Become. That is, in the case of having a network structure, the portions of the polymer component (A) forming the insoluble portion are bridged between the molecules insoluble in the non-aqueous solvent to form a higher-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 separately and as particles from the binder resin as a matrix in the image receiving layer, and that they are concentrated near the air interface. As a result, the direct-printing original plate of the present invention forms a faithful image portion and a non-image portion, and provides a high-quality printed image free from background smear. Moreover, since the resin particles are fixed by the binder resin, they are not separated during various processing steps,
In addition, by obtaining the protective effect of the binder resin,
Excellent printing durability. In addition, 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 immersion water or the like at the time of printing. However, such a concern is solved by crosslinking at least a part of the resin particles. As described above, the original plate for direct drawing type lithographic printing according to the present invention has the advantage that the non-image portion has good hydrophilicity, so that no background smear occurs and the printing durability is excellent.

Hereinafter, the resin particles will be further described. The resin dispersion of the resin particles of the present invention comprises at least one of each of the monomer (A) and the monofunctional polymer [M]. What is important in any case is that if a 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 a film of the resin formed by applying a solution of the resin particles in an arbitrary soluble solvent is applied and the contact angle with distilled water (measured with a goniometer) is 50 ° or less. , Preferably 30 degrees or less. In the case of network resin particles, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.
% By weight or less.

The resin particles of the present invention (including network resin particles)
Preferably has an average particle diameter of 0.05 to 1.0 μm. If it is larger than 1.0 μm, the smoothness of the surface layer is reduced, which causes a reduction 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 is easily reduced to 1 μm or less, and the particle size distribution is very narrow, and monodisperse particles. You can do it.

In the present invention, if the amount of the resin particles (including the network resin particles) in the image receiving layer is too small, the hydrophilicity of the non-image portion is not sufficient and the effect is lost, and the background is stained. Conversely, if the amount is too large, the hydrophilicity of the non-image area can be further improved, but the water absorption of the entire image receiving layer increases, causing a decrease in adhesion to 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) that is soluble in a non-aqueous solvent but is insolubilized by polymerization and contains at least one functional group that generates a hydroxyl group by decomposition (hereinafter simply referred to as a hydroxyl group-forming monomer). 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 generates a hydroxyl group by decomposition, but the number of hydroxyl groups generated 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) [-OL ₁ ]. And a monomer having one polymerizable double bond group. In the general formula (II) [-OL ₁ ], L ₁ is

Embedded imageRepresents Where R_Three, R_Four, R_Five, R₆, R₇, R₈
May be the same or different from each other, and may be a hydrogen atom, a hydrocarbon
Group or -OR₉(R₉Represents a hydrocarbon group),
Y ₁, Y_TwoRepresents a hydrocarbon group, Z represents an oxygen atom, sulfur
An atom or a -NH- group,_ThreeIs sulfur atom or oxygen
Represents an atom.

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

Embedded imageIn the case where_Three, R_Four, R_FiveAre the same as each other
Or different, preferably a hydrogen atom or a substituted
A straight-chain or branched alkyl group having 1 to 18 carbon atoms
(E.g., methyl, ethyl, propyl, butyl,
Hexyl, octyl, decyl, dodecyl, octyl
Tadecyl group, chloroethyl group, methoxyethyl group, meth
An alicyclic group which may be substituted (eg, a xypropyl group)
For example, cyclopentyl group, cyclohexyl group, etc.)
Aralkyl groups having 7 to 12 carbon atoms (for example, benzyl
Group, phenethyl group, fluorobenzyl group, chloroben
Jyl group, methylbenzyl group, methoxybenzyl group, 3-
Phenylpropyl group) or an aromatic group which may be substituted
(For example, phenyl, naphthyl, chlorophenyl,
Tolyl group, methoxyphenyl group, methoxycarbonyl group
Enyl group, dichlorophenyl group, etc.) or -OR₉(R
₉Represents a hydrocarbon group, and specifically R_Three, R _Four, R_Five
Represents the same substituents as the hydrocarbon group of the above).

When 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 (for example, a methyl group, a trichloromethyl group, a trifluoromethyl group, a methoxymethyl group,
A phenoxymethyl group, a 2,2,2-trifluoroethyl group, a t-butyl group, a hexafluoro-1-propyl group and the like, an optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, a benzyl group, a phenethyl group) , Methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group,
Methoxybenzyl group), which may have 6 to 6 carbon atoms
12 aryl groups (for example, phenyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl,
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. Furthermore, L ₁
But,

Embedded image In the formula, Y ₃ represents an oxygen atom or a sulfur atom. R ₆ , R ₇ , and R ₈ may be the same or different from each other, and specifically represent the same contents as R _{3 to} R ₅ described above. i represents an integer of 3 to 5.

The general formula [-OL ₁ ] used in the present invention.
The synthesis of the monofunctional monomer (A) containing at least one functional group selected from the group of can be easily performed by a conventionally known organic synthesis reaction. For example, the Chemical Society of Japan, “New Experimental Chemistry Course, Vol. 14, Synthesis and Reaction of Organic Compounds [V]”, page 2497 (published by Maruzen Co., Ltd.), JFW McOmie “Prote
ctive groups in Organic Chemistry '' (Plenum Press
1973), TWGreene "Protective groups in
Organic Synthesis ”(John Wiley and Sons Interscie
nce, 1981) and the like, and can be produced by a synthesis 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 [-OL ₁ ] and having a polymerizable double bond group in one molecule is more specifically described. For example, compounds represented by the following general formula (III) can be mentioned.

Embedded image In the formula (III), X ₁ is

Embedded image Represents 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 be connected via a hetero atom connecting the bonding group X ₁ and the bonding group [—O─L ₄ ] (hetero atoms include an oxygen atom, a sulfur atom and a nitrogen atom). For example

Embedded imageEtc. consisting of a single unit or a combination of units
(But f_Three, F_Four, F _FiveIs the f₁, F_TwoSynonymous with
Is). L_TwoIs L of the formula (II)₁Has the same meaning as
a_Three, A_FourMay be the same or different, a hydrogen atom,
Hydrocarbon group (for example, a carbon group which may be
An alkyl group having a prime number of 1 to 12, etc.), -COOH or -CO
O-W₁[W₁Is the general formula (-OL_Two) Substituents containing groups
An alkyl group having 1 to 18 carbon atoms which may be substituted
Represents a kenyl group, an aralkyl group, an alicyclic group, or an aromatic group]
Represents

More specifically, examples of the monomer having a functional group of the general formula [-OL ₃ ] include the following compound examples. In each of Examples (a-1) to (a-25), Me represents a methyl group.

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According to another preferred embodiment of the present invention, the 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 located sterically close to each other are simultaneously protected by one protective group. Examples of the functional group having at least two hydroxyl groups which are sterically close to each other in one protected form include, for example, the following general formulas (IV), (V), (VI) and (VI)
Those represented by I) can be mentioned.

Embedded image In the 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 represents a hetero atom. Represents a carbon-carbon bond which may be via an atom (provided that the number of atoms between oxygen atoms is within 5).

Embedded image In the formula (V), U is as defined above.

Embedded image In the formula (VI), R ₁₀ , R ₁₁ and U are as defined above.

Embedded image In the 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, etc.).

The functional groups will be described in more detail as follows. In the formula (IV), R ₁₀ and R ₁₁ may be the same or different from each other, and are preferably a hydrogen atom and a carbon number of 1 to 1.
12 optionally substituted alkyl groups (e.g., methyl, ethyl, propyl, butyl, hexyl, 2-methoxyethyl, octyl, etc.), and optionally substituted aralkyl groups having 7 to 9 carbon atoms ( For example, a benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, a chlorobenzyl group, etc., an alicyclic group having 5 to 7 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, etc.), and an optionally substituted aryl group (eg, Phenyl group, chlorophenyl group,
A methoxyphenyl group, a methylphenyl group, a cyanophenyl group) or -OR ₁₄ (where R ₁₄ has the same meaning as the hydrocarbon group for R ₁₀ and R ₁₁ ). U represents a carbon-carbon bond which may be via 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 quoted in the above-mentioned synthesis method of [-OL ₁ ]. Can be synthesized by the method described in the publicly known technical literature.

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

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

The proportion of the monomer (A) as a polymerization component in the resin particles of the present invention is at least 30% by weight, preferably 5% by weight.
0% by weight or more, and particularly preferably, the resin particles are composed of only the monomer (A) and the monofunctional polymer [M]. When the composition contains another copolymerizable monomer, the content of the other monomer is at most 20% by weight or less. When the resin particles are copolymers, the polymer component containing a hydroxyl group-forming functional group in the resin particles of the present invention is 10 to 95% by weight, preferably 20% by weight, based on the total copolymer.
It is preferably about 90% by weight. What is important as the polymerization component that becomes insoluble in the non-aqueous solvent is that the material after the formation of the hydroxyl group can satisfy a hydrophilicity represented by a contact angle with distilled water of 50 ° or less.

Next, the monofunctional polymer [M] will be described. A polymerizable double-bonding group represented by the general formula (I) is bonded to only one terminal of the polymer main chain at least including a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. It is important that the polymer characterized by being copolymerized with the monomer A and solvated with the non-aqueous solvent to be soluble, and functions as a dispersion stabilizing resin in so-called non-aqueous dispersion polymerization. Is what you do. The monofunctional polymer solution of the present invention may be soluble in the non-aqueous solvent, specifically, at least 5% by weight at 25 ° C with respect to 100 parts by weight of the solvent. The weight average molecular weight of the polymer [M] is 1 × 10 ³ to 1 × 1.
0 is ^5, preferably ^{2 × 10 3 ~5 × 10 4} , particularly preferably ^{3 × 10 3 ~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 , agglomeration of the generated dispersed resin particles occurs, and fine particles having a uniform average particle size cannot be obtained.

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

Embedded imageIn the general formula (I), V₀Is -O-, -COO-,-
OCO-,-(CH _Two) -OCO-,-(CH_Two) -C
OO-, -SO_Two−,

Embedded image Represents -CONHCOO- or -CONHCONH-.

Here, R ₁ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 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-
A methoxyethyl group, a 3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 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 (e.g., benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (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, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, 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, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

V ₀ is

Embedded image In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group,
A propyl group, a butyl group, a chloromethyl group, a methoxymethyl group and the like; an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group and a butoxy group).

A₁And a_TwoAre the same but different
And preferably a hydrogen atom, a halogen atom (eg,
Chlorine atom, bromine atom, etc.), cyano group,
Alkyl group (for example, methyl group, ethyl group, propyl
Group, butyl group, etc.) -COO-R _TwoOr through hydrocarbons
COOR_Two(R_TwoRepresents 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 the one described for
). -COO via the above hydrocarbon
R_TwoExamples of the hydrocarbon in the group include a methylene group and an ethylene group.
And a propylene group.

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

Embedded image A ₁ and a ₂ may be the same or different from each other, and represent a hydrogen atom, a methyl group, —COOR ₂ ′ or —C
H ₂ COOR ₂ ′, wherein R ₂ ′ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.), still more preferably represents one is always a hydrogen atom in the a ₁ and a _2.

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

Embedded image And the like.

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 a radical addition polymerizable monomer, those formed of a polyester structure, those formed of a polyether structure, and the like. And any one containing a silicon atom and / or a fluorine atom. As the substituent containing a fluorine atom, for example, -C _h F _{2h + 1} (h
Represents an integer of 1 to 12),-(CF ₂ ) _j CF ₂ H
(J represents an integer of 1 to 11),

Embedded image Is mentioned.

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

Embedded image And a polysiloxane structure. Where R ₁₅ ,
R ₁₆ and R ₁₇ may be the same or different and represent an optionally substituted hydrocarbon group or an —OR ₂₁ group (R ₂₁ represents the same content as the hydrocarbon group of R ₁₅ ). R ₁₅ is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, 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 and the like, and optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, , 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., and an optionally substituted aralkyl group having 7 to 12 carbon atoms (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 (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., 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, dodecylylamidophenyl group, etc.). . In the —OR ₂₁ group, R ₂₁ represents the same content as the above-mentioned hydrocarbon group of R ₁₅ . R ₁₈ , R ₁₉ and R ₂₀ may be the same or different and represent the same contents 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.

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

Embedded image And a bonding group selected from the following. 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 represent the same meaning as R ₁ in formula (I).

As the divalent aliphatic group, for example,

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

The divalent aromatic group includes, for example, a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (hetero atoms constituting a heterocyclic ring are selected from oxygen, sulfur and nitrogen atoms. Containing at least one heteroatom). These aromatic groups may have a substituent, for example, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group) , A butyl group, a hexyl group, an octyl group, etc.) and a C1-C6 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) are mentioned as examples of the substituent.
Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-
Oxazoline ring and the like.

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 an organic residue linked thereto include the following, but are not limited thereto.
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 1-4
Indicates an integer.

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In the total of the 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 units in total.
% By weight or more, more preferably 60 to 100% by weight. When the content of the above components of the present invention is less than 40% by weight, the effect of concentrating the resin particles dispersed in the image receiving layer, particularly on the surface portion, is reduced, and as a result, the effect of improving the water retention as a printing original plate is reduced. Would.

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example,
A) a method by ionic polymerization, in which a terminal of a living polymer obtained by anionic or cationic polymerization is reacted with various reagents 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, or an amino group in the molecule; A radical polymerization method of reacting various reagents to obtain a monofunctional polymer [M]; c) polymerizing the polymer obtained by polyaddition or polycondensation reaction in the same manner as in the above radical polymerization method. Examples include a method by a polyaddition condensation method for 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, High Polymer, 31 , 988 (1982), Shiro Kobayashi, High Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan, 18 , 536 (1982), Koichi Ito,
Polymer synthesis, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, and the like, and synthesis can be performed according to the methods described in the references and patents.

More specifically, as a method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radical polymerizable monomer is disclosed in
No. 67563, Japanese Patent Application No. 63-64970, Japanese Patent Application Nos. 1-206989 and 1-69011, each of which is described in the specification of the application, and contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] to be obtained is disclosed in Japanese Patent Application Nos. 1-56379 and 1-58989.
It is obtained in the same manner as the method described in the specification of the application as each of the above-mentioned 1-56380.

As described above, the dispersed resin particles of the present invention are obtained by decomposing the functional group-containing monofunctional monomer (A) which generates at least one hydroxyl group with 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 be at least partially crosslinked. Resin particles in which at least a part of the polymer has been cross-linked in advance (a resin having a cross-linked structure in the polymer), when the hydroxyl group-forming functional group contained in the resin generates 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 hydroxyl group-forming functional group-containing monofunctional monomer (A) as a main component [Polymer component (A ) Is bridged between the polymers to form a higher-order network structure.

That is, the dispersed resin particles of the present invention are composed of a non-aqueous solvent composed of a portion insoluble in a non-aqueous dispersion solvent composed of the polymer component (A) and a polymer soluble in the solvent. When it is a latex and has a network structure, the molecules of the polymer component (A) forming a part insoluble in the solvent are bridged. As a result, the network resin particles after the generation of the 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 as follows.

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) a method of containing at least a monomer corresponding to the polymer component (A). A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups when performing a polymerization reaction by It can be carried out by a method such as a method of cross-linking the united component (A) with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction.

As the crosslinking agent in the method (a), there can be mentioned compounds which are usually used as a crosslinking agent.
Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" Taiseisha (1981), edited by the Society of Polymer Science, "Basic Edition of Polymer Data Handbook", Baifukan (1986), etc. Can be used.

For example, organic silane compounds (for example, vinyltrimethoxysilane, vinyltributoxysilane,
silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.), polyisocyanate-based compounds (eg, toluylene diisocyanate, o-toluene) Range isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, γ-hydroxyp Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
"New epoxy resin" edited by Hiroshi Kakiuchi, Shokodo (1985), "Epoxy resin" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (1969), etc., melamine resin (for example, Ichiro Miwa, Hideo Matsunaga) Compounds described in “Uria Melamine Resin” edited by Nikkan Kogyo Shimbun (1969) and the like, and poly (meth) acrylate compounds (for example, “Oligomer” Kodansha (1976) edited by Shin Okawara, Takeo Saegusa, Toshinobu Higashimura Compounds described in Eizo Omori, “Functional Acrylic Resin” Techno System (published in 1985) and the like. 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 methacrylates thereof.

Polymerization of a polyfunctional monomer (also referred to as a polyfunctional monomer (D)) or a polyfunctional oligomer containing two or more polymerizable functional groups coexisting by the method (b). As the functional functional group, specifically,

Embedded image And the like. 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, monomers or oligomers having the same polymerizable functional group, such as styrene derivatives such as divinylbenzene and trivinylbenzene; 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, or the like, or polyhydroxyphenol (e.g., 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, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

Examples of the monomer or oligomer having a different polymerizable functional group include carboxylic acids having a vinyl group (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, allyloyl). Reactants of propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride, etc. with alcohols or amines (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) Ester derivative or amide derivative containing a vinyl group such as an acid or the like (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloy) Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene ester, N- allyl acrylamide, N-
Allyl methacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group And a condensate with a carboxylic acid containing the same.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is a monomer (A)
And 10% based on the total amount of other monomers coexisting with (A).
Polymerization is carried out using not more than 5 mol%, preferably not more than 5 mol% to form a resin.

Further, when a chemical bond is formed by the reaction of reactive groups between polymers in the above method (c) to form a bridge between the polymers, the reaction between the ordinary organic low molecular weight compound and The same can be done. Specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymers" Kodansha (1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (1976),
JP-A-61-43775, Japanese Patent Application No. 1-149030.
No. 5 is described in detail in the specification and the like.

For example, a polymer reaction using a combination of a functional group of Group A and a functional group of Group B shown in Table 1 below is a well-known method. Note that R ₂₃ and R _{24 in} Table 1 are used.
Is a hydrocarbon group, and has the same contents as g ₄ and g ₅ in —Si (g ₄ ) (g ₅ ) — described above.

[Table 1] In dispersion polymerization, monodisperse particles having a uniform particle diameter are obtained, and fine particles of 0.5 μm or less are easily obtained. (B) 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 molecular weight between the molecular chains. Polymer particles having a bridged structure.

The non-aqueous solvent used for 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, and may be used alone or as a mixture 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,
Ethers such as tetrahydrofuran and dioxane; carboxylic esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; and fats having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane. Group hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, the present invention is not limited to the compound examples described above.

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by a dispersion polymerization method, the average particle diameter of the resin particles can be easily reduced to 0.8 μm or less, and the distribution of the particle diameter is very narrow and monodispersed. Particles. Specifically, KEJ Barrett "Dispersion Polymerization
in Organic Media "John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto, Toyoyoshi Tange, Journal of the Adhesion Society of Japan 9 , 183 (197)
3), Tokichi Tange, Journal of the Adhesion Society of Japan 23 , 26 (198)
7), DJ Walbridge, NATO. Adv. Study. Inst. Se
r. E. No. 67, 40 (1983), UK Patent 893
429, 934038, U.S. Pat.
Nos. 2397, 3900412 and 460689, JP-A-60-179751, 60-18596
The method is disclosed in three publications.

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A) and the monofunctional polymer [M],
In the case of forming a network structure, a polyfunctional monomer (D) is co-present if necessary, and in any case, it is important that the resin synthesized from these monomers is added to 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,
The monofunctional polymer [M] is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight,
Particularly preferably, it is 5 to 25% by weight. When other copolymerizable monomers are used, the amount of other monomers is 20% by weight or less. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ to 10
⁶ , 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. In a non-aqueous solvent benzoyl peroxide, azobisisobutyronitrile,
Heat polymerization may be performed 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 of dropping or arbitrarily adding a mixture of the polymerizable compound and the polymerization initiator to an aqueous solvent, and the like. The method is not limited to these, and any method can be used to produce.

The total amount of the polymerizable compound is about 5 to 80 parts by weight per 100 parts by weight of the non-aqueous solvent, and preferably 10 to 80 parts by weight.
５０50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound. The polymerization temperature is 30
To 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) provided for the image receiving layer of the present invention, all resins conventionally known as various binder resins can be used. Typical 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., as well as water-soluble polymer compounds, polyvinyl alcohol, modified polyvinyl alcohol, Examples include starch, oxidized starch, carboxymethylcellulose, hydroxyethylcellulose, gelatin, casein, polyacrylic acid, polyvinylpyrrolidone, polyvinylether-maleic anhydride copolymer, polyamide, and polyacrylamide.

The molecular weight of the resin of the matrix provided 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 from -10 ° C to 120 ° C.
° C, more preferably 0 ° C to 85 ° C. The content ratio of the resin particles in the image receiving layer is about 1 to 80 parts by weight of the resin particles with respect to 100 parts by weight of the matrix resin. If the amount is less than 1% by weight, background smearing occurs, and if it is more than 80% by weight, the image strength is undesirably reduced.

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

In addition, a crosslinking agent may be added to the image receiving layer in order to further improve the film strength. As the cross-linking agent, ammonium chloride, an organic peroxide, ordinarily used,
Metallic soaps, organic silanes, polyurethane crosslinking agents, epoxy resin curing agents, and the like can be used. Specifically, it is described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents", Taiseisha Publishing (1981) and the like.

Examples of the support used in the present invention include high-quality paper, wet-strengthened paper, plastic films such as polyester films, and metal plates such as aluminum plates.

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. (A back layer) can be provided. Here, the intermediate layer is an emulsion resin such as an acrylic resin, an ethylene-butadiene copolymer, a methacrylate-butadiene copolymer, an acrylonitrile-butadiene copolymer, an ethylene-vinyl acetate copolymer, an epoxy resin, a polyvinyl butyral. It is composed mainly of at least one kind of solvent-type resin such as polyvinyl chloride and polyvinyl acetate, and the above-mentioned water-soluble resin, and can add an inorganic pigment or a water-proofing agent as needed. . The configuration of the back coat layer is almost the same as that of the intermediate layer.

When used as a PPC plate, in order to further reduce background contamination of the printing original plate of the present invention, the image receiving layer and the image receiving layer are further adjusted 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 inorganic or organic. Inorganic ones include salts of monovalent or polyvalent metals such as Na, K, Li, Mg, Zn, Co, and Ni. Examples thereof include a cationic polymer conductive agent such as polyvinylbenzyltrimethylammonium chloride and a quaternary ammonium salt modified with an acrylic resin, and a polymeric anionic dielectric agent such as a polymer sulfonate. The amount of these conductive agents to be added is 3 to 40% by weight, preferably 5 to 20% by weight of the binder used in each layer.
% By weight.

In order to prepare the direct-lithographic lithographic printing plate precursor according to the present invention, an aqueous solution containing an intermediate layer component, if necessary, is applied to one surface of the support and dried to form an intermediate 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 lithographic printing plate precursor of the present invention is prepared by forming and fixing an image on the direct-drawing lithographic printing plate precursor having the above-described structure by a known technique,
After desensitizing non-image areas by surface treatment with desensitizing solution,
Used as a printing plate for lithographic printing.

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 as one of the methods depending on the decomposition reactivity of the protected hydroxyl group. acidic conditions of pH 1-6,
A method of hydrolyzing with an aqueous solution under an alkaline condition of pH 8 to 12 is exemplified. Adjustment of these pH can be easily performed by a known compound. Alternatively, a method by a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and as these compounds, known compounds can be used, for example, hydrous hydrazine, sulfite, lipoic acid, hydroquinones, formic acid, Thiosulfate, hydrogen peroxide, persulfate, quinones and the like.

The treatment liquid may contain another compound for accelerating the reaction or improving the storage stability of the treatment liquid. For example, 1 to 50 parts by weight of an organic solvent soluble in water may be contained in 100 parts by weight of water. 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.), 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.

Further, 0.1 to 20 parts by weight of a surfactant may be contained in 100 parts by weight of water. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi “New Surfactant” Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura “Synthesis of Surfactant and Its Application” Maki Shoten (1980) Can be used.

The scope of the present invention is not limited to the specific compound examples described above. The condition of the treatment is a temperature of 15 ° C.
The immersion time at ６０60 ° 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, production examples of the monofunctional polymer [M] for resin particles and resin particles will be described. Production Example 1 of Monofunctional Polymer [M]: [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 a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of azobisisobutyronitrile (abbreviated as AIBN) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and t
0.5 g of butylhydroquinone was added, and the temperature was 100 ° C.
For 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of a white powder. The weight average molecular weight of the polymer [M-1] was 4000. Monofunctional polymer [M-1]

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Production Example 2 of Monofunctional Polymer [M]: [M-
2] A mixed solution of 96 g of a monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to a temperature of 70 ° C under a nitrogen stream. A. I. B. N.
1.0 g was added and reacted for 8 hours. Next, 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. 15 g of dicyclohexylcarbonamide (abbreviated as DCC), 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 the mixture was stirred for 1 hour. The precipitated insoluble material was separated by filtration, and the filtrate was reprecipitated in 1 liter of n-hexane. The precipitated viscous material was collected by decantation, dissolved in 100 ml of tetrahydrofuran, filtered again to remove insoluble material, and then reprecipitated in 1 liter of n-hexane. The polymer [M-2] obtained by drying the precipitated viscous material had a weight average molecular weight of 5.2 × 10 5 in a yield of 60 g.
^{Was 3} . Monomer (MA-1)

Embedded image Monofunctional polymer [M-2]

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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. while stirring under a nitrogen stream. 2,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) 2 g
Was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 1 liter of methanol, and the obtained polymer was dried. Next, 50 g of this polymer and 2-hydroxyethyl methacrylate 11
g, dissolved in 150 g of benzotrifluoride, at a temperature of 25 ° C.
And The mixture was stirred with 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 further stirred for 4 hours. Thereafter, 3 g of formic acid was added and the mixture was stirred for 1 hour. Next, the precipitated insoluble matter was separated by filtration, 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)

Embedded image Monofunctional polymer [M-3]

Embedded image

Production Examples 4 to 22 of Monofunctional Polymer [M]:
[M-4] to [M-22] In Production Example 2, other monomers (monomers corresponding to the polymer components described in Table 2) instead of the monomer (MA-1)
The 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 of Monofunctional Polymer [M] 23 to 3
0: [M-23] to [M-30] In Production Example 2 of the monofunctional polymer [M], the monomer (M
A-1) and 2-hydroxyethyl methacrylate are
Instead of the compound corresponding to each of the polymers in Table 3 below,
Otherwise, each monofunctional polymer [M] was produced in the same manner. 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) having the following structure 70 g, glycidyl methacrylate 3
g and a mixed solution of 200 g of benzotrifluoride were 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 the reaction mixture, and the mixture was stirred at 110 ° C. for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, and a slightly brownish oily substance was collected and dried. The yield was 73 g and the weight average molecular weight was 3.6 × 10 ⁴ . Monomer (MA-3)

Embedded image Monofunctional polymer [M-31]

Embedded image

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 a temperature of 60 ° C. while stirring under a nitrogen stream. To this, 2,2'-azobis (isovaleronitrile) (abbreviation: AIV.
N. ) 0.8 g was added 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 D.C. C. C. 6 g, 4- (N, N-dimethylamino) pyridine 0.1 g and methylene chloride 15 g
Was added dropwise over 1 hour, and the mixture was further stirred for 3 hours. Next, 10 g of water was added, and the mixture was stirred for 1 hour. The precipitated insoluble matter was separated by filtration, and the filtrate was reprecipitated in 1 liter of methanol to collect an oily substance. Furthermore, this oily substance is
After dissolving in 50 g, insolubles were separated by filtration and reprecipitated again in 1 liter of methanol to collect and dry the oil. Yield 5
The weight average molecular weight of 6 g was 8 × 10 ³ .

Monomer (MA-4)

Embedded image Monofunctional polymer [M-32]

Embedded image

Production Examples of Monofunctional Polymer [M] 33 to 3
9: [M-33] to [M-39] Monofunctional polymers [M] in Table 4 below were synthesized by performing the reaction as 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]

Preparation Example 1 of Resin Particles: [L-1] 10 g of monofunctional polymer [M-32] and n-octane 2
While stirring 00 g of the mixed solution under a nitrogen stream, the temperature was 60 ° C.
Was heated. 50 g of the following monomer (A # 1), 5 g of ethylene glycol dimethacrylate, I. V.
N. A mixed solution of 0.5 g and 240 g of n-octane was added dropwise over 2 hours, and the mixture was reacted for 2 hours. Further, A.I.
I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. It was a latex having an average particle size of 0.20 μm.
Measure particle size with APA-500 (manufactured by Horiba, Ltd.). Monomer (A-1)

Embedded image

Production Examples 2-11 of Resin Particles: [L-2]-
[L-11] Resin particles were prepared in the same manner as in Production Example 1 of resin particles except that the monomers (A-1) and the monofunctional polymer [M-32] were replaced with the compounds shown in Table 5 below. 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 [macromonomer manufactured by Toagosei Co., Ltd .: macromonomer having dimethylsiloxane structure as a repeating unit: weight Average molecular weight 1.
5 × 10 ⁴ ] 7.5 g and methyl ethyl ketone 133 g
Was heated to 60 ° C. while stirring under a nitrogen stream. 50 g of the following monomer (A-12), 5 g of diethylene glycol dimethacrylate, I. V. N.
A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour. I. V. N. 0.25g
Was added and reacted for 2 hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.18.
μm. Monomer (A-12)

Embedded image

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

Embedded image

Production Example 14 of Resin Particles: [L-14] 50 g of monomer (A-14), 2 g of ethylene glycol diacrylate, 8 g of monofunctional polymer [M-33] and 230 g of dipropyl ketone were introduced in a nitrogen stream. The mixture was dropped into a solution of 200 g of dipropyl ketone heated to a lower temperature of 60 ° C. with stirring for 2 hours. After the reaction as it was for 1 hour, A.I.
I. V. N. 0.3 g was added and reacted for 2 hours. After cooling, the dispersion obtained through a 200-mesh nylon cloth had an average particle size of 0.28 μm. Monomer (A-14)

Embedded image

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

[Table 13]

Production Examples 26 to 31 of Resin Particles: [L-2
6] to [L-31] In the resin particle production example 12, the dispersion stabilizing resin AK-
Resin particles [L] were produced in the same manner as in Production Example 12 except that each monofunctional polymer [M] shown in Table 7 below was used instead of 5 . 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, monomer (A-13),
Resin particles [L] were 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 the 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 (as solid content) of resin particles [L-1] and resin [B-1]: methyl methacrylate / acrylic acid (99%)
/ 1, weight ratio) (weight average molecular weight 4500)
0): 20 g, zinc oxide 100 g and toluene 300 g
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 is coated with a wire bar on a middle layer of a support having a back layer on one side and a middle layer on the other side of a high-quality paper so that the dry adhesion amount is 18 g / m ^2. And 1
After drying at 00 ° C. for 1 minute, a lithographic printing original plate was prepared. Next, the plate was made using a commercially available PPC, and the resulting plate was etched once using an aqueous solution obtained by diluting a desensitizing solution ELP-EX manufactured by Fuji Photo Film Co., Ltd. 5 times with distilled water. I passed. Further, a solution obtained by diluting 0.5 mol monoethanolamine in 1 liter of distilled water [treatment solution (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, manufactured by Sakurai Seisakusho Co., Ltd.) and printed on high quality paper. Even if the number of sheets exceeds 3,000, no problem was caused in the background stain on the non-image portion and the image quality of the image portion of the printed matter.

Examples 2 to 15 The same procedures as in Example 1 were carried out except that the copolymer shown in Table 9 was used instead of the resin particles [L-1] of the present invention. Thus, each lithographic printing original plate was prepared.

[Table 16] By operating this in the same manner as in Example 1, the density of the obtained master plate for offset printing in which an original plate was prepared was 1.
At two or more, the image quality was clear. Further, when the sheet was etched and printed by a printing machine, the printed matter after printing 3000 sheets had no fog in the non-image portion and the image was clear.

Example 16 A mixture of 4 g (as solid content) of resin particles [L-12], 29 g of a binder resin [B-2] having the following structure, 50 g of zinc oxide and 200 g of toluene was placed in a homogenizer at 6 × 1.
Disperse at 0 ³ rpm for 10 minutes.
g and 0.02 g of o-chlorophenol, and 1 ×
Dispersed 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
It dried at 00 degreeC for 30 second, and also heated at 110 degreeC for 1 hour, and produced the lithographic printing original plate. Binder resin [B-2]

Embedded image This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using 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. The image quality of the printed matter after printing 5,000 sheets was a clear image without background fog.

Example 17 A mixture of 15 g (as solid content) of resin particles [L-3], 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, and the mixture was dispersed in a ball mill for another 10 minutes to form a back layer on one side of the high-quality paper and an intermediate layer on the other side provided with an intermediate layer on the other side. 25 g / m ² of dry adhesion on top
Was applied with a wire bar and dried at 100 ° C. for 90 minutes to prepare a lithographic printing original plate. Resin [B-3]

Embedded image This original plate is treated with a desensitizing solution [Fuji Photo Film Co., Ltd.
ELP-EX] and passed once through an etching processor, and further added to the following desensitizing solution (E-2).
It was immersed at 5 ° C. for 3 minutes. Desensitization treatment liquid (E-2): Diethanolamine 75 g Neosoap (Matsumoto Yushi Co., Ltd.) 6 g Benzyl alcohol 100 g was dissolved in distilled water to make a total volume of 1 liter. A droplet of 2 μl of distilled water was placed on the printing plate thus obtained, and the contact angle with the formed water was measured with a goniometer and found to be 10 ° or less. In addition, it was 98 degrees before the desensitization treatment. This indicates that the non-image portion of the image receiving layer of the original plate of the present invention has changed from lipophilic to hydrophilic (normally, the non-image portion does not generate printing background stains and dot stains during printing. The degree of contact with water is 20 °
Must be :) Next, after the plate was made in the same manner as in Example 1, the desensitizing treatment was performed and printing was performed.
Even when the number of prints exceeded 000, no problem was caused in the background stain on the non-image portion and the image quality of the image portion of the printed matter.

Resins 18 to 22 Resins 18 to 22 were replaced by the compounds shown in Table 10 below in place of hexamethylene diisocyanate.
A lithographic printing original plate was produced in the same manner as in Example 1.

[Table 17] This was made into a plate using the same apparatus as in Example 1, then subjected to an etching treatment, and printed using 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. The image quality of the printed matter after printing 5,000 sheets was a clear image without background fog.

Examples 23 to 36 The same procedures as in Example 17 were carried out except that 15 g of the resin particles [L] shown in Table 11 below were used instead of 15 g of the resin particles [L-3]. A master was made.

[Table 18] Each master was made into a plate as in Example 17, and the master was passed through an etching machine once using ELP-EX, and then placed in a resin particle desensitizing solution (E-3) having the following formulation. The sample was immersed for 2 minutes to make it insensitive. Resin particle desensitized liquid (E-3): 65 g of boric acid 6 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 6 g of benzyl alcohol 80 g dissolved in distilled water to make a total volume of 1 liter, and then pH 10 with potassium hydroxide. Aqueous solutions adjusted to 5 were printed in the same manner as in Example 1. As a result, each of the original plates was printed with a clear image quality with no background smearing.
Zero or more sheets were obtained.

[0106]

According to the present invention, it is possible to obtain an original plate for direct drawing type lithographic printing which is excellent in suppressing occurrence of background fogging and has good printing durability.

Claims (2)

(57) [Claims] 1. A direct drawing lithographic printing plate precursor having an image receiving layer on a support, characterized in that the image receiving layer contains at least one kind of the following nonaqueous solvent-based dispersed resin particles. A lithographic printing original plate. Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, at least one functional group which is soluble in the non-aqueous solvent but insolubilized by polymerization, and which forms at least one hydroxyl group by decomposition is provided.
A monofunctional monomer (A) containing a species and a repeating unit containing at least a substituent containing a silicon atom and / or a fluorine atom, and at least one terminal of a main chain of a polymer having the following general formula ( Polymer resin particles obtained by subjecting a monofunctional polymer [M] obtained by bonding a polymerizable double bond group represented by I) to a dispersion polymerization reaction. Embedded image [However, in the above 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 a hydrocarbon group of over a -COO-R ₂ (R
₂ represents a hydrogen atom or a hydrocarbon group which may be substituted)
Represents 2. The direct drawing type lithographic printing plate precursor according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure.