JP2716601B2 - Manufacturing method of lithographic printing plate precursor - 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 an electrophotographic lithographic printing plate precursor made by an electrophotographic method, and more particularly to a direct-drawing lithographic printing plate suitable for an office printing plate. And a method for producing the same.

[0002]

2. Description of the Related Art At present, a direct drawing type lithographic printing plate precursor having an image receiving layer on a support is widely used as an office printing plate precursor. In order to form a plate, that is, to form an image on such a printing original plate, a method is generally adopted in which oil-based ink is drawn by hand on the image receiving layer, or printing is performed by a typewriter, an inkjet method, a transfer-type heat-sensitive method, or the like. In addition, a method of transferring and fixing a toner image formed on a photoreceptor through a charging, exposing and developing process using a plain paper electrophotographic copying machine (PPC) to an image receiving layer has recently started to be used. In any case, the printing original plate after plate making is subjected to surface treatment with a desensitizing solution (so-called etchant) to desensitize non-image portions, and then subjected to lithographic printing as a printing plate.

[0003] In the conventional direct-lithography lithographic printing plate precursor, a surface layer is provided on both sides of a support such as paper via a back layer and an intermediate layer. The back layer or the intermediate layer is formed of a water-soluble resin such as PVA starch, a water-dispersible resin such as a synthetic resin emulsion, and a pigment. The surface layer is formed of a pigment, a water-soluble resin, and a waterproofing agent.

As a typical example of such a direct drawing type lithographic printing plate precursor, as described in US Pat. No. 2,532,865, a water-soluble resin binder such as PVA, silica, It is composed mainly of an inorganic pigment such as calcium carbonate and a waterproofing agent such as a melamine-formaldehyde resin precondensate.

Further, as a binder used in the image receiving layer of the direct drawing type lithographic printing plate precursor, the binder contains a functional group which forms a carboxyl group, a hydroxyl group or a thiol group, an amino group, a sulfone group and a phosphono group by decomposition. ,heat/
It contains a light-curable functional group and is previously cross-linked. (Japanese Patent Application Nos. 63-54609, 63-117035, and JP-A-1-269593), and a heat / photocurable resin in combination (JP-A-1-266546 and JP-A-1-275191;
Japanese Patent Application No. 63-139344) and a crosslinking agent in combination (Japanese Patent Application Laid-Open Nos. 1-267093, 1-271292 and 1-3).
No. 09067) are being studied to improve the hydrophilicity of the non-image area and the film strength of the image receiving layer, and to further improve the printing durability.

[0006]

However, in the conventional printed matter obtained in this manner, in order to improve the printing durability, the amount of the water-proofing agent to be added is increased or the hydrophobic resin is used. When the hydrophobicity is increased, 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. . In particular, in a high-temperature use environment of 30 ° C. or more, the surface layer was dissolved in immersion water used for offset printing, and there were major drawbacks such as reduction in printing durability and printing stains.

[0007] Further, the lithographic printing plate precursor draws an oil-based ink or the like as an image portion on an image receiving layer, and if the adhesiveness between the receiving layer and the oil-based ink is not good, even if the non-image portion has sufficient hydrophilicity. However, even if the above-described printing stains do not occur, 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 is directed to improving the problems of the above-described 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 background stain as an offset master plate. An object of the present invention is to improve the adhesiveness between the oil-based ink and the image-receiving layer in the image area, and to maintain the hydrophilicity of the non-image area even when the number of printed sheets is increased in printing, without causing background smear. An object of the present invention is to provide a lithographic printing original plate having high printing durability.

[0009]

SUMMARY OF THE INVENTION The above-mentioned objects are attained in a direct-drawing lithographic printing plate precursor having an image receiving layer on a support, the same as the maximum particle size of the photoconductive zinc oxide particles during image reception. Exposing the electrophotographic photoreceptor containing at least one of the following non-aqueous solvent-based dispersed resin particles having a particle diameter of less than or equal to the size of a toner image to a toner image portion, The photoconductive layer in the non-image area is desensitized with a processing solution containing a hydrophilic compound having at least a person's nucleophilic constant n of 5.5 or more to obtain a printing original plate. This is achieved by a method for producing a lithographic printing plate precursor.

The non-aqueous solvent-based dispersed resin particles [L] include:
In a nonaqueous solvent system, a monofunctional monomer [A] having a formyl group and at least one functional group represented by the following general formula (1) and a substituent containing a silicon atom and / or a fluorine atom are included. And copolymer resin particles obtained by subjecting the monomer [A] to a dispersion polymerization reaction with a monofunctional monomer [B] to be copolymerized in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. It is something that is.

The above-mentioned dispersed resin particles are preferably resin particles characterized by forming a high-order network structure.

The dispersion stabilizing resin preferably contains at least one polymerizable double bond group represented by the following general formula (1) in the polymer chain. It is a polymer.

[0013]

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(However, in the above general formula (1), R
₁ and R ₂ may be the same or different and each represents a hydrocarbon group, or R ₁ and R ₂ each represent an organic residue linked to each other to form a ring). The particles are preferably particles forming a higher-order network structure. Further, it is preferable that the dispersion stabilizing resin contains at least one polymerizable double bond group represented by the following general formula (2) in the polymer chain.

[0015]

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[0016]

According to the present invention, there is provided an offset printing original plate which is provided with an image receiving layer and which is subjected to desensitization treatment on a non-image portion of the image receiving layer to be hydrophilic to be used as a printing original plate.

The image receiving layer of the present invention contains at least photoconductive zinc oxide particles, a binder resin, and non-aqueous solvent-based dispersed resin particles (hereinafter sometimes referred to as resin particles [L]). It is a feature.

The average particle diameter of the resin particles [L] used in the present invention is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the particle diameter distribution is narrow and the particle diameters are uniform. The resin particles [L] have at least two important properties. One of them is that when treated with a treatment liquid containing at least one hydrophilic compound having nucleophilic reactivity, the terminal of the formyl group of the resin particles and the functional group represented by the general formula (1) has a nucleophilic reactivity. Is capable of undergoing an addition reaction, whereby the particles can exhibit hydrophilicity, and at the same time, when the resin particles have a cross-linked structure, they have hydrophilicity at this time and also have an affinity for water. It is insoluble or hardly soluble and has water swellability.

Another one is that a polymer containing a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom is bonded to the surface of the photoconductive layer to transfer the polymer. -It is characterized by causing a concentration phenomenon. The polymer as a dispersion stabilizing resin containing a fluorine atom and / or a silicon atom is obtained by physically and chemically adsorbing an insoluble component or a polymerizable double bond group moiety represented by the above general formula (2). In the case of the contained dispersion stabilizing resin, both polymer components are chemically bonded.

The mechanism by which the resin particles [L] of the present invention are hydrophilized by a nucleophilic reactive hydrophilic compound is represented by the following reaction formula (1), typically using sulfite ions as the nucleophilic hydrophilic compound. ).

[0021]

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[0022]

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That is, the resin particles of the present invention have a nucleophilic reactivity such that the nucleophilic constant n of the person in the processing solution is 5.5 or more only when the non-image area is desensitized as a lithographic printing plate precursor. A hydrophilic group is added to the terminal by reacting with the hydrophilic compound as described above, thereby expressing hydrophilicity, and characterized in that it is made hydrophilic by the treatment liquid as described above. Does not react, so there is no problem with regard to storage stability.

On the other hand, when the nucleophilic constant n of the person in the processing solution is 5.5 or less, the hydrophilic reaction does not proceed at all or the hydrophilicity of the printing original plate is insufficient, and the background smear becomes remarkable. .

Since the formyl group according to the present invention is a functional group that reacts very quickly with a nucleophilic compound, rapid expression of hydrophilicity is possible.

Further, as shown in the reaction formula (1), the functional group represented by the general formula (1) can easily undergo a deacetalization reaction by acid treatment and can be converted into a formyl group. And a formyl group.

Further, the insoluble polymer component in the resin particles [L] has a substituent containing a fluorine atom and / or a silicon atom together with the functional group-containing component which exhibits hydrophilicity by the nucleophilic reaction. It is characterized in that it is formed by combining polymer components. Preferably, two or more fluorine atoms and silicon atoms are contained in the substituent.

For the lithographic printing plate precursor, it is important that the surface portion of the non-image area is sufficiently hydrophilized. On the other hand, a known resin of the type which generates a hydrophilic group by the above decomposition reaction is used. Alternatively, the resin particles are uniformly dispersed throughout the photoconductive layer. Therefore, in order to sufficiently hydrophilize the surface of the known resin or resin particle, the surface becomes a printable hydrophilic state only when a hydrophilic group-forming functional group is present in the entire surface layer and in a large proportion. .

On the other hand, the resin particles of the present invention [L]
In the surface layer, since it contains a fluorine atom and / or silicon atom-containing component having extremely high lipophilicity, it migrates and concentrates on the surface portion of the surface layer.

Thus, the resin particles [L] which generate a nucleophilic reaction in the desensitization treatment and exhibit hydrophilicity are present on the surface portion, so that the effective surface layer can exhibit hydrophilicity. Was. Further, the particles having a crosslinked structure have a water absorbing ability, so that the water retention can be further enhanced. Here, in the monomer (B) containing a substituent containing a fluorine atom and / or a silicon atom, the total number of fluorine atoms and silicon atoms is 2
If not, the effect of concentrating the surface of the resin particles will not be sufficiently achieved, and the effect of the present invention will not be effective. More preferably, when only fluorine atoms are contained, the total number is 4 or more, and when silicon atoms are present, the total number of silicon atoms is 2 or more.

In addition, the resin particles of the present invention are physicochemically or chemically bonded to the insoluble polymer portion of the polymer portion serving as the dispersion stabilizing resin. Interacts with resin. Further, when a component containing a light and thermosetting functional group is contained in the dispersion stabilizing resin, the resin particles are modified to be hydrophilic by a desensitizing treatment because they are chemically bonded to themselves and the binder resin. Is suppressed from the photoconductive layer, and the water retention effect of the non-image area is sufficiently maintained.

Further, the non-aqueous solvent-based dispersed resin particles of the present invention are characterized in that the average particle diameter is equal to or smaller than the maximum diameter of the photoconductive zinc oxide particles and the particle diameters are uniform. Things.

A printing original plate of a type in which a non-image portion of a surface layer containing non-aqueous solvent-based dispersed resin particles and a binder resin is treated with a desensitizing liquid to make the surface hydrophilic to form a lithographic printing original plate. In the above, since the resin particles of the present invention are concentrated and present on the surface as described above, it is possible to disperse only a small amount (50% to 10% of the amount of the known hydrophilic resin particle technology) by dispersing the resin particles. The water retention of the image area is dramatically improved. Furthermore, since the amount present in the surface layer is small, the electrophotographic characteristics are not impaired at all, and good performance can be stably maintained even under severe conditions of high temperature and high humidity or low temperature and low humidity. It became like.

The resin particles of the present invention have the above-mentioned average particle size, and a film of the resin formed by applying a solution obtained by dissolving the resin in an arbitrary soluble solvent has a contact angle (with respect to distilled water) of distilled water. It is a hydrophilic substance having a value of 50 degrees or less, preferably 30 degrees or less (measured by a goniometer).

On the other hand, when the resin particles of the present invention have a particle diameter larger than the zinc oxide particle diameter,
The electrophotographic characteristics are degraded, and in particular, uniform chargeability cannot be obtained. As a result, in the copied image, the density unevenness of the image portion,
Characters, fine lines are cut, jumped, or fogged in the non-image area.

Specifically, the resin particles of the present invention have a maximum particle size of 3 μm or less, preferably 1 μm or less. The average particle size of the particles is 0.8 μm or less, preferably 0.5 μm or less. The smaller the particle diameter, the larger the specific surface area of the resin particles. The resin particles have a good effect on the above electrophotographic properties, and the colloidal particles (0.01 μm or less) are sufficient. Because it is similar to the case of dispersion and the effect of being particles for improving water retention is diminished,
It is preferable to use it at 0.001 μm or more. As a result, the printing plate precursor for plate making according to the present invention reproduces a copied image that is faithful to the original image, has good hydrophilicity in the non-image area, does not cause background fouling, and has smoothness and electrostatic properties of the surface layer. And good printing durability.

Furthermore, the printing plate precursor for plate making of the present invention is not affected by the environment during the plate making process, is very excellent in the preservability before the process, and is rapidly hydrophilized and elutes the non-image area. It has the feature of being performed.

In the present invention, if the resin particles form a high-order network structure, the dissolution property in water can be further suppressed, and on the other hand, water swelling can be exhibited, and the water retention can be further improved.

In the present invention, resin particles that do not form a higher-order network structure as described above, or resin particles that form a higher-order network structure (hereinafter referred to as network resin particles).
Is an amount of 0.1 to 60 parts by weight, preferably 0.5 to 60 parts by weight, based on 100 parts by weight of the total composition used in the image receiving layer.
40 parts by weight. 0.1 or less resin particles or network resin particles
If the amount is less than the weight part, the hydrophilicity of the non-image part is not sufficient,
Conversely, if the amount is more than 60 parts by weight, the hydrophilicity of the non-image portion can be improved, but the film strength under severe printing conditions decreases, the image quality of the printed matter deteriorates, and the printed image deteriorates.

Hereinafter, 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 dispersion polymerization in a so-called non-aqueous solvent system. In the resin particles [L], the monofunctional monomer [A] used has at least a formyl group and / or
Or it contains a functional group represented by the general formula (1).

[0041]

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However, in the above general formula (1),
R ₁ and R ₂ may be the same or different and each represents a hydrocarbon group, or R ₁ and R ₂ represent an organic residue linked to each other to form a ring.

When R ₁ and R ₂ each represent a hydrocarbon group,
R ₁ and R ₂ are preferably an optionally substituted aliphatic group having 1 to 12 carbon atoms (for example, an optionally substituted alkyl group having 1 to 12 carbon atoms: a methyl group, an ethyl group, a propyl group; Butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, methoxymethyl, ethoxymethyl, 2-hydroxyethyl, 2-
Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxymethyl group, 2-ethoxymethyl group,
3-hydroxypropyl group, 3-methoxypropyl group and the like, and an optionally substituted alkenyl group having 2 to 12 carbon atoms: specific examples include a propenyl group, a butenyl group,
An aralkyl group having 7 to 12 carbon atoms which may be substituted, such as a hexenyl group, an octenyl group, a dodecenyl group or a dodecenyl group: specific examples include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, and −
A naphthylethyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a methoxybenzyl group, a dimethoxybenzyl group, a chlorobenzyl group, a bromobenzyl group, a fluorobenzyl group, and a dichlorobenzyl group; Alicyclic group which may be substituted:
Specific examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.

When R ₁ and R ₂ represent an organic residue forming a ring by being linked to each other, preferably, a functional group represented by the general formula (1a), that is, a cyclic acetal group is exemplified.

[0045]

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In the general formula (1a), R ₇ and R ₈ are
They may be the same or different from each other, and include a hydrogen atom and a carbon number of 1 to 1.
Represents an optionally substituted hydrocarbon group of 12 or an —OR ₉ group (R ₉ represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms), and n represents an integer of 1 to 4.

Preferred examples of the group in which R ₇ , R ₈ and R ₉ are a hydrocarbon group having 1 to 12 carbon atoms which may be substituted include an aliphatic group (specific examples include those exemplified for R ₁ and R ₂ ). The same content), aromatic group (for example, phenyl group, tolyl group, xylyl group, methoxyphenyl group, chlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, dimethoxyphenyl group, chloromethylphenyl group, naphthyl group, etc.) And the like.

More preferably, the general formulas (1) and (1)
In a), when R ₁ , R ₂ , R _{7 to} R ₉ are an aliphatic group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and an aralkyl group having 7 to 9 carbon atoms are preferable. .

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

The copolymer component containing a formyl group and a functional group represented by the general formula (1) used in the present invention includes those represented by the following general formula (3).

[0051]

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The general formula (3) will be described in more detail.

[0053]

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Wherein r ₁ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl,
Octyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-methoxyethyl, 2-
A hydroxyethyl group, a 3-bromopropyl group and the like, an optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, a benzyl group, a phenethyl group, a 3-phenylpropyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc., and optionally substituted aryl group (for example, phenyl group, tolyl group, xylyl group, mesityl group, methoxyphenyl group) Chlorophenyl group, bromophenyl group, chloro-methoxy-phenyl group, etc.).

[0055] Y is a direct bond or represents an organic residue connecting the -Z- and -W _O. When Y represents an organic residue to be linked,
This linking group represents a carbon-carbon bond which may be via a hetero atom (hetero atoms include an oxygen atom, a sulfur atom and a nitrogen atom),

[0056]

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A ₃ and a ₄ may be the same or different, and may be a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.),
A cyano group, a hydrocarbon group (for example, a substituted group such as a methyl group, an ethyl group, a propyl group, a butyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonylmethyl group, an ethoxycarbonylmethyl group, a butoxycarbonylmethyl group; And an aralkyl group such as an alkyl group having 1 to 12 carbon atoms, a benzyl group and a phenethyl group, and an aryl group such as a phenyl group, a tolyl group, a xylyl group and a chlorophenyl group.

[0058]

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Hereinafter, specific examples of the polymer component containing a formyl group and / or a functional group represented by the general formula (1) of the present invention will be described. In Examples (a-1) to (a-15), a
It represents -H or -CH _3. However, the present invention is not limited to this.

[0060]

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[0061]

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[0062]

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Specific examples of the functional group represented by the general formula (1a) of the present invention are also shown, but the examples (a'-1) to (a'-)
In 9), R _10, R ₁₁ represents an alkyl group or a -CH ₂ C ₆ H ₅ 1 to 4 carbon atoms, R ₁₂ is an alkyl group having 1 to 4 carbon atoms, -CH ₂ C ₆ H ₅ or phenyl Represents a group.

However, the scope of the present invention is not limited to these specific examples.

[0065]

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In the resin [L] of the present invention, the polymer component containing a formyl group and / or the functional group of the general formula (1) may be completely copolymerized when the resin [L] is a copolymer. It is preferably from 30 to 99% by weight, especially from 50 to 95% by weight in the combined.

The polymer of the resin has a molecular weight of 10 ³ to
It is preferably 10 ⁶ , particularly preferably 5 × 10 ^{3 to} 5 × 10 ⁵ . The monofunctional monomer [A] having a formyl group and / or a functional group represented by the general formula (1) of the present invention as described above can be synthesized by a conventionally known synthesis method.

For example, as a method of synthesizing a compound containing a formyl group, see the New Chemical Chemistry Course, Vol. 14, edited by The Chemical Society of Japan.
P. 636 (1978), published by Maruzen Co., Ltd .; Mulle
r, "Method der Organisch.
en Chemie, p. 13 (1954), Geor
g Methods published by Thiem Verlag, edited by The Chemical Society of Japan, New Experimental Chemistry Course, Vol. 19, p. 231, (1957) Maruzen Co., Ltd., and the like. As the polymerizable functional group in the above-described monomer synthesis, a normal polymerizable double bond group, specifically,

[0069]

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And the like.

The monofunctional group containing a substituent containing at least two fluorine and silicon atoms which can be copolymerized with the monofunctional group monomer (A) containing a formyl group and / or an acetal group as described above. Describing the monomer (B), the monofunctional monomer (B) of the present invention may be any compound as long as it satisfies the above requirements. The specific contents of the substituents will be described below, but the present invention is not limited to these chemical structures.

[0072]

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However, R ₃ , R ₄ and R ₅ may be the same or different, and may be an optionally substituted hydrocarbon group or —O.
Represents an R ₉ group (R ₉ represents the same content as the hydrocarbon group of R ₃ ).

R ₃ represents an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, -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 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), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chloro) Benzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, A cyclohexyl group, a 2-cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

In the —OR ₉ group, R ₉ has the same content as the above-mentioned hydrocarbon group of R ₃ .

R ₆ , R ₇ and R ₈ may be the same or different and represent the same symbols as R ₃ , R ₄ and R ₅ .

Next, specific examples of the monofunctional monomer (B) 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.

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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And the like.

Along with the specific functional group-containing monomer (A) and the fluorine atom and / or silicon atom-containing monomer (B) as described above, other copolymerizable monomers other than these are used. It may be contained as a polymer component.

The other monomer is represented by the following general formula (3)
Or a monomer corresponding to the repeating unit of the general formula (3)
And those copolymerized with a monomer corresponding to the component represented by.

As the polymerization component in the resin, the monomer (A)
Is 30% by weight or more, preferably 50% by weight or more, and the monomer (B) is present in an amount of 0.5% by weight to 3% by weight.
0% by weight, preferably 1% to 20% by weight. When containing other copolymerizable monomers, at most 20
% By weight or less.

What is important as the polymerization component that becomes insoluble in the non-aqueous solvent is that the hydrophilicity represented by the above-mentioned contact angle with distilled water satisfy 50 degrees or less.

Next, the dispersion stabilizing resin of the present invention will be described. It is important that the dispersion stabilizing resin is solvated with a non-aqueous solvent and is soluble, and plays a role of dispersion stabilization in so-called non-aqueous solvent-based dispersion polymerization, and specifically, 100 parts by weight of a non-aqueous solvent. However, at least 5 parts by weight at 25 ° C. may be used.

The weight average molecular weight of the dispersion stabilizing resin is 1 ×
10 ^{3 to} 5 × 10 ⁵ , preferably 2 × 10 ³ to 1
× 10 ⁵ , particularly preferably 3 × 10 ^{3 to} 5 × 10 ⁴ . If the weight average molecular weight of the resin is less than 1 × 10 ³ , the resulting dispersed resin particles will aggregate, making it impossible to obtain fine particles having a uniform average particle size. 5 × 10
^If it exceeds ⁵ , the effect of the present invention of improving water retention while satisfying electrophotographic properties when added to the photoconductive layer is diminished.

The dispersion stabilizing resin of the present invention may be any polymer as long as it is a polymer soluble in the nonaqueous solvent. E. FIG. J. Barrett "Dispersio
n Polymerization in Organic
ic Media "John Wiley and So
ns (1975); Dowpenco, D.C.
P. Hart, Ind. Eng. Chem. Prod.
Res. Developer. Volume 12, (No. 1) 14
(1973), Tokichi Tange, Journal of the Japan Adhesion Association, 23
(1), 26 (1987); J. Walbridge
ge, NATO. Adv. Study Inst. Se
r. E. FIG. No. 67, 40 (1983); Sasa
ki and M.S. Yabuta, Proc, 10t
h, Int. Conf. Org. Coat. Sci. T
Enol, 10, 263 (1984), etc., each of which is cited in the review.

For example, olefin polymers, modified olefin polymers, styrene-olefin copolymers, aliphatic carboxylic acid vinyl ester copolymers, modified maleic anhydride copolymers, polyester polymers, polyether polymers, methacrylate homopolymers Coalescent, acrylate homopolymer, methacrylate copolymer, acrylate copolymer, alkyd resin and the like.

More specifically, the polymer component used as a repeating unit of the dispersion stabilizing resin of the present invention includes a component represented by the following general formula (4).

[0094]

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In the general formula (4), X ₂ represents V in the general formula (2)
_It represents the same content as _0, and the details are described in the description of V _{0 in} the general formula (2).

R ₂₁ is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, dosaconyl group, 2- (N, N-dimethylamino) ethyl group,
-(N-morpholino) ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2- (α-thienyl) ethyl group, 2-carboxyethyl group, 2-methoxycarbonylethyl group,
A 2,3-epoxypropyl group, a 2,3-diacetoxypropyl group, a 3-chloropropyl group, a 4-ethoxycarbonylbutyl group and the like, an alkenyl group having 3 to 22 carbon atoms which may be substituted (for example, an allyl group, Hexenyl group, octenyl group, dodecenyl group, dodecenyl group, tridecenyl group,
An octadecenyl group, an oleyl group, a linoleyl group, etc.), an optionally substituted aralkyl group having 7 to 22 carbon atoms (for example, a benzyl group, a phenethyl group, a 3-phenylpropyl group,
2-naphthylmethyl group, 2- (2′-naphthyl) ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
A methoxybenzyl group, a dimethoxybenzyl group, a butylbenzyl group, a methoxycarbonylbenzyl group, etc., an alicyclic group having 4 to 12 carbon atoms which may be substituted (for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a chloro group) Cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.)
22 optionally substituted aromatic groups (for example, phenyl group,
Tolyl, xylyl, mesityl, naphthyl, anthranyl, chlorophenyl, bromophenyl, butylphenyl, hexylphenyl, octylphenyl, decylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, Octyloxyphenyl, ethoxycarbonylphenyl, acetylphenyl, butoxycarbonylphenyl, butylmethylphenyl, N, N-dibutylaminophenyl, N
-Methyl-N-dodecylphenyl group, thienyl group, hydranyl group and the like).

C ₁ and c ₂ are a ₁ and a _{2 in the} general formula (2)
Represents the same contents as the above, and details are described in a ₁ and a 2 in the general formula (2).
It is described in the description of ₂ .

As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the components described above.

The other polymer component may be any as long as it can be copolymerized with a monomer corresponding to the component represented by the general formula (4).
α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (for example, a pyran ring, a pyrodrine ring, an imidazole ring, a pyridine ring and the like), and vinyl group-containing carboxylic acids (for example, acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid, etc.), vinyl group-containing carboxamides (eg acrylamide, methacrylamide, crotonic amide,
Itaconamide, itaconic half-amide, itaconic diamide and the like).

In the dispersion stabilizing resin of the present invention, the polymer component represented by the general formula (4) is the total polymer 10 of the resin.
It is at least 30 parts by weight, preferably at least 50 parts by weight in 0 parts by weight.

In the dispersion stabilizing resin of the present invention, the light and / or thermosetting functional group may be contained in an amount of 30 parts by weight or less, preferably 20 parts by weight or less based on 100 parts by weight of the whole polymer of the resin. Good.

The light and / or thermosetting functional groups to be contained include those other than the polymerizable functional groups, and specific examples thereof include a functional group for forming a crosslinked structure of particles described later.

Further, the dispersion stabilizing resin of the present invention preferably contains at least one polymerizable double bond group represented by the above general formula (2) in the polymer chain.

The polymerizable double bond group will be described below.

[0105]

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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).

[0107]

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Examples of the substituent include 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.), an alkoxy group (For example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

A ₁ and a ₂ may be the same or different from each other and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, COOR ₂ (R ₂ via a butyl group) -COO-R ₂ or hydrocarbons, hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, fat Represents a cyclic group or an aryl group, which may be substituted, and specifically represents the same contents as those described for R ₁ above).

Examples of the hydrocarbon in the —COO—R ₂ group via the above hydrocarbon include a methylene group, an ethylene group and a propylene group.

[0111]

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These polymerizable double bond group-containing moieties are directly bonded to the main chain of the polymer chain or bonded with an arbitrary linking group. Specifically, the linking group is a divalent organic residue,

[0113]

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As the divalent aliphatic group, for example,

[0115]

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｛E ₁ and e ₂ may be the same or different and each is 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, For example, methyl group, ethyl group,
Propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.)
Represents Q is -O -, - S- or -NR ₂₀ - represents,
R ₂₀ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —
Represents 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.

The above-mentioned polymerizable double bond group-containing portion is, specifically, randomly bonded in a polymer chain.
Alternatively, it is bonded only to one end of the main chain of the polymer chain. Preferably, a polymer in which a polymerizable double bond group-containing portion is bonded to only one end of a polymer chain main chain (hereinafter, referred to as a monofunctional polymer [M]) is used.

The monofunctional polymer [M] represented by the general formula (2)
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 is -Cl or -
Represents Br, n represents an integer of 2 to 12, and m represents an integer of 1 to 4.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group in a side chain of a polymer, and the synthesis of this polymer can be carried out by a conventionally known method.

For example, a method of copolymerizing a monomer containing two polymerizable double bond groups having different polymerization reactivities in a molecule, a method in which a carboxyl group, a hydroxyl group, an amino group, an epoxy group, etc. After polymerizing a monofunctional monomer containing a reactive group to obtain a polymer, a polymerizable duplex containing another reactive group capable of chemically bonding to the reactive group in the polymer side chain Perform a reaction with a low-molecular organic compound containing a bonding group,
A method of introducing by a so-called polymer reaction, etc., are usually well-known methods.

As the above-mentioned method, for example,
185962.

As the above method, specifically, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (1)
976), JP-A-61-43775, and Japanese Patent Application No. 1-149305.

For example, a polymer reaction based on a combination of a functional group of Group A and a functional group of Group B in Table 1 below is a well-known method. Note that R ₂₂ and R _{23 in} Table 1 are hydrocarbon groups,

[0131]

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[0132]

[Table 1]

The monofunctional polymer [M] containing a polymerizable double bond group at one end of the main chain, which is more preferable as the dispersion stabilizing resin of the present invention, can be produced by a conventionally known synthesis method. it can. For example, a) a method using an ionic polymerization method, in which various reagents are reacted with the terminal of a living polymer obtained by anionic or cationic polymerization to obtain a monofunctional polymer [M], b) a carboxyl group or a hydroxyl group in the molecule. Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as an amino group or an amino group to react a polymer having a terminal reactive group bond obtained by radical polymerization with various reagents to obtain a monofunctional compound A method by a radical polymerization method for obtaining a polymer [M]; c) a polyaddition condensation method for introducing a polymerizable double bond group into a polymer obtained by a polyaddition or polycondensation reaction in the same manner as in the radical polymerization method described above. And the like.

More specifically, P.S. Dreyfuss &
R. P. Quirk, Encycl. Polym. Sc
i. Eng. , Vol. 7, 551 (1987);
F. Rempp, E.A. Franta, Adv. Po
lym. Sci. , Vol. 58, 1 (1984),
V. Persec, Appl. Poly. Sci. ,
Vol. 285, 95 (1984); Asami,
M. Takari, Macromol. Chem. Su
ppl. , Vol. 12, 163 (1985); R
empp. , Et al, Macromol. Che
m. Suppl. , Vol. 8, 3 (1984), Yusuke Kawakami, Chemical Industry, Vol. 38, 56 (1987), Yuya Yamashita, Polymer, Vol. 31, 988 (1982), Shiro Kobayashi, Polymer, Vol. 30, 625 (1981), Toshinobu Higashimura, Journal of the Adhesion Society of Japan, Vol. 18, 536 (1982),
Koichi Ito, Polymer Processing, 35, 262 (198
6), Takashiro Higashi, Takashi Tsuda, Functional Materials, No. 10,5
(1987) and the methods described in the literature and patents cited therein.

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

As described above, the dispersed resin particles of the present invention have a specific functional group-containing monofunctional monomer [A] and a silicon atom and / or fluorine atom-containing monofunctional monomer [B ] Is a copolymer resin particle obtained by dispersion polymerization in the presence of the dispersion stabilizing resin. Further, when the dispersed resin particles of the present invention have a network structure, the above-mentioned monofunctional monomer [A] and the monofunctional monomer [B] containing a fluorine atom and / or a silicon atom overlap. The polymers constituting the coalesced component (referred to as polymer component [A]) are bridged between the polymers to form a higher-order network structure. That is,
The dispersed resin particles of the present invention are a non-aqueous latex composed of a portion insoluble in a non-aqueous dispersion solvent composed of a polymer component [A] and a polymer soluble in the solvent. In the case where the polymer component [A] has a structure, the molecules of the polymer component [A] forming a portion insoluble in the solvent are crosslinked.

Thus, the network resin particles become hardly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.
% By weight or less. The crosslinking of the present invention can be performed 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 having two or more polymerizable functional groups when performing a polymerization reaction by (c).
The polymer component [A] can be crosslinked with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction.

As the cross-linking agent in the above method (a), there can be mentioned compounds usually used as a cross-linking agent.
Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents" Taiseisha (1981), edited by The Society of Polymer Science, "Basic 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" Urea Melamine Resin ", Nikkan Kogyo Shimbun (1969), etc.), 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.

Further, 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 above method (b) As the functional functional group, specifically,

[0141]

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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, as monomers or oligomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene; Alcohols (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 polyhydroxyphenol (eg, hydroquinone, resorcinol, catechol) Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid; and dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid) , Itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or allylamides; polyamines (e.g., ethylenediamine, 1,3-propylenediamine, 1,4-
Condensates of butylene diamine and the like and carboxylic acids having a vinyl group (for example, 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, allylloyl propion). A reactant of an acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic anhydride, etc. with an alcohol or an amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid) Ester derivatives or amide derivatives containing a vinyl group such as vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, Vinyl loyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide , Methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol,
1-aminopropanol, 1-aminobutanol, 1-
Condensates of aminohexanol, 2-aminobutanol, etc.) with a carboxylic acid containing a vinyl group.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention may be a monomer [A]
And 1 to the total amount of other monomers coexisting with [A].
Polymerized using 0 mol% or less, preferably 5 mol% or less,
Form a resin.

Further, in the case of forming a chemical bond by the reaction between the reactive groups between the polymers in the above method (c) and bridging between the polymers, the usual reaction of a low molecular organic compound is carried out. Can be performed in the same manner. Specifically, it can be synthesized according to the same method as described in the synthesis method of the dispersion stabilizing resin.

In dispersion polymerization, monodisperse particles having a uniform particle size are obtained, and fine particles having a particle size of 0.5 μm or less are easily obtained. The method (b) using a monomer is preferred.

As described above, the network-dispersed resin particles of the present invention comprise a polymer component containing a repeating unit having a polar group, a repeating unit having a fluorine atom and / or a silicon atom-containing substituent, and the non-aqueous solvent. And a polymer component having a structure in which the molecular chains are bridged to a higher degree.

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, 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, ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone, diethyl ether, tetrahydrofuran and dioxane. Ethers, carboxylic esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; aliphatic hydrocarbons having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane; , Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene,
Examples include 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 the dispersion polymerization method, the average particle diameter of the resin particles can be easily reduced to 1 μm or less, and the particle diameter distribution is very narrow and the monodispersed particles are dispersed. It can be.

Specifically, K.I. E. FIG. J. Barrett
"Dispersion Polymerizati
on in Organic Media "John
Wiley (1975), Koichiro Murata, Polymer Processing,
Vol. 23, 20 (1974), Tsunetaka Matsumoto, Toyoyoshi Tange, Journal of the Adhesive Society of Japan, Vol. 9, 183 (1973), Toyokichi Tange, Journal of the Adhesive Society of Japan, Vol. 23, 26 (1987),
D. J. Walbridge, NATO. Adv. s
study. Inst. Ser. B. No. 67, 40
(1983), British Patent No. 893,429, British Patent No. 934,038, U.S. Pat.
No. 2,397, U.S. Pat. No. 3,900,412, U.S. Pat. No. 4,606,989, JP-A-60-179751, JP-A-60-18596.
No. 3 discloses such a method.

The dispersion resin of the present invention comprises at least one of each of the monomers [A] and [B] and a dispersion stabilizing resin. In any case, it is important to obtain a desired dispersion resin if the resin synthesized from these monomers is insoluble in the non-aqueous solvent. it can. More specifically, the dispersion stabilizing resin is added in an amount of 1 to 50% by weight based on the insoluble monomer [A] and the monomer [B].
It is preferably used, more preferably 2 to 30% by weight. Further, the polymerization conditions of the dispersion resin of the present invention are such that the temperature is about 30 ° C. to 180 ° C., preferably 40 to 1 ° C.
20 ° 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 provided in the image receiving layer of the present invention, all resins conventionally known as various binder resins can be used. Typical ones 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 water-soluble polymer compound polyvinyl alcohol, modified polyvinyl alcohol, starch, oxidized starch, carboxymethyl cellulose, hydroxyethyl cellulose,
Examples include casein, gelatin, polyacrylate, 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 . Further, the glass transition point of this resin is preferably −10 ° C. to 120 ° C.,
More preferably, it is 0 ° C to 90 ° C.

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 sulfide, and alumina.

The ratio of the binder resin / pigment in the image receiving layer differs depending on the kind of the material and, in the case of the pigment, further depending on the particle size.
Generally, the weight ratio is 1 / 0.5 to 1/5, preferably 1
About /0.8 to 1 / 2.5 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 “Handbook of Crosslinking Agents” edited by Shinzo Yamashita and Tosuke Kaneko, Taiseisha (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 for the purpose of improving water resistance and interlayer adhesion between the support and the image receiving layer, and a back coat layer (for preventing curling) is provided on the surface of the support opposite to the image receiving layer. Back layer).

Here, the intermediate layer is made of acrylic resin, ethylene-
Emulsion resins such as butadiene copolymer, methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-vinyl acetate copolymer; epoxy resins, polyvinyl butyral, polyvinyl chloride, polyvinyl acetate, etc. Solvent-type resin; composed of at least one of the above-described water-soluble resins as a main component, and an inorganic pigment or a water-proofing agent can be added as necessary. 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 the background contamination of the printing plate precursor of the present invention, the image receiving layer and the image receiving layer must have a volume resistivity of 10 ¹⁰ to 10 ¹³ Ωcm as the printing plate precursor. A dielectric agent can be added to the intermediate layer and / or the back coat layer. The dielectric agent may be an inorganic one or an organic one. In the case of an inorganic one, Na, K, Li, Mg, Zn, Co, Ni, etc.
Salts of polyvalent or polyvalent metals, and, in the case of organic compounds, a polymeric cationic conductive agent such as polyvinylbenzyltrimethylammonium chloride and quaternary ammonium salt modified with an acrylic resin, or a polymeric anionic conductive agent such as a polymeric sulfonate. No. The amount of these conductive agents to be added is 3 to 40% by weight, preferably 5 to 2% by weight of the binder used for each layer.
0% by weight.

To prepare the direct-drawing lithographic printing plate precursor of 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.

In the desensitization treatment used in the present invention, it is important to express a protected carboxyl group in the resin particles of the present invention. The decomposition reaction includes a decomposition reaction of the protected functional group. It is arbitrarily selected depending on sex. One of them is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 or alkaline conditions of pH 8 to 12.

The pH can be easily adjusted with a known compound. Alternatively, a method based on 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, hydrazine hydrate, sulfite,
Examples include lipoic acid, hydroquinones, formic acid, thiosulfate, hydrogen peroxide, persulfate, quinones and the like. The treatment liquid may contain other compounds 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 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), etc. are used. be able to. 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 10C is preferably 10 seconds to 5 minutes.

Further, in the case of containing a protective group that generates a hydroxyl group by photolysis, light irradiation is performed after forming an image on the image receiving layer.

The "chemically active light" used in the present invention includes visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray,
Any of γ-rays and α-rays may be used, but ultraviolet rays are preferred. More preferably, a wavelength of 310 nm to a wavelength of 5
Those capable of emitting light in the range of 00 nm are preferable, and a high-pressure or ultra-high-pressure mercury lamp or the like is generally used. Light irradiation treatment is usually performed from a distance of 5 cm to 50 cm.
Irradiation for 0 seconds to 10 minutes can be sufficiently performed.

When zinc oxide is present in the image-receiving layer of the present invention as an inorganic pigment together with the receiving particles of the present invention, a hydrophilic treatment by desensitizing zinc oxide is used in combination with a conventionally known method. You may.

Desensitization of zinc oxide has been conventionally performed by using a desensitizing treatment liquid of this type, a treatment liquid containing a cyanide compound containing ferrocyanate and ferricyanate as main components, an ammine cobalt complex, phytic acid and derivatives thereof. There are known a cyan-free treatment liquid containing a guanidine derivative as a main component, a treatment liquid containing an inorganic acid or an organic acid that forms a chelate with zinc ions as a main component, and a treatment liquid containing a water-soluble polymer.

For example, as a cyanide-containing treatment solution,
JP-B-44-9045, JP-B-46-39403, JP-A-5
2-76101, 57-107889, 54-11
No. 7201, each of which is described.

Examples of the treatment solution containing a phytic acid compound include:
JP-A-53-83807, JP-A-53-83805 and JP-A-53-83805
-102102, 53-109701, 53-12
Nos. 7003, 54-2803, and 54-44901.

Examples of the processing solution containing a metal complex compound such as a cobalt complex include JP-A-53-104301 and JP-A-53-1.
40103, 54-18304, JP-B-43-284
No. 04 publications.

Examples of the treating solution containing an inorganic or organic acid include JP-B-39-13702, JP-B-40-10308, and JP-B-43-2.
8408, 40-26124, JP-A-51-1185.
01 publications and the like.

Examples of the guanidine compound-containing treatment solution include those described in JP-A-56-11695.

Examples of the processing solution containing a water-soluble polymer include those described in JP-A-52-126302, JP-A-52-134501, and JP-A-52-134501.
3-49506, 53-59502, 53-104
302, Japanese Patent Publication Nos. 38-9665 and 39-22263,
40-763, 40-2202 and JP-A-49-36
No. 402 publications.

In any of the above desensitizing treatments,
Zinc oxide in the surface layer ionizes into zinc ions,
It is believed that these ions cause a chelation reaction with a compound forming a chelate in the desensitizing solution to form a zinc chelate, which is deposited in the surface layer and hydrophilized.

Therefore, the printing original plate produced according to the present invention is prepared by the above desensitizing treatment.

[0181]

According to the present invention, there is provided an offset printing original plate which is provided with an image receiving layer and which is subjected to desensitization treatment on a non-image portion of the image receiving layer to be hydrophilic to be used as a printing original plate.

In the present invention, at least one
The resin particles containing at least one functional group that produces two hydroxyl groups and having at least a part thereof crosslinked are dispersed in the surface layer separately and as particles from the binder resin which is a matrix of the surface layer. It is important that the resin particles contain a copolymer component containing at least a fluorine atom and / or a silicon atom.

As a result, the lithographic printing plate precursor according to the present invention reproduces a copied image that is faithful to the original image, has good hydrophilicity in the non-image area, does not cause background stains, and further has a non-image area hydrophilic property. Has the advantage that the printing durability is excellent due to the improvement of the durability.

For the lithographic printing plate precursor, it is important that the surface portion of the non-image portion is sufficiently hydrophilized, while a known resin of a type that generates a hydrophilic group by the above decomposition reaction is used. Are uniformly dispersed throughout the surface layer.
Therefore, in order to sufficiently hydrophilize the surface of the known resin, a printable hydrophilic state is reached only when a hydrophilic group-forming functional group is present in the entire surface layer and in a large proportion.

However, in the image receiving layer of the present invention, since the resin particles to be provided contain a copolymer component containing at least one fluorine atom and / or silicon atom, the resin particles are concentrated on the surface portion of the surface layer. Can exist. As a result, the particles of the present invention, in which a hydrophilic group is expressed by a desensitizing treatment such as a hydrolysis reaction, a redox reaction, or a photolysis reaction, effectively expresses the hydrophilicity of the surface layer by being present on the surface portion. At the same time, the effect is improved by the water retention of the particles themselves. Further, the particles having a crosslinked structure have a water absorbing ability, so that the water retention is further enhanced.

On the other hand, the particles of the present invention are bonded to the lipophilic dispersion stabilizing resin and interact with the binder resin layer on the surface layer. It has the effect of suppressing the elution of the particles converted into.

In order to produce the dispersed resin particles used in the present invention as described above, generally, a monomer [A], a monomer [B], a dispersion stabilizing resin, and a polyfunctional monomer [ D]
May be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solvent of a monomer [A], a monomer [B], a dispersion stabilizing resin and a polyfunctional monomer [D], ii) A method in which a mixture of the polymerizable compound and the polymerization initiator is added dropwise or arbitrarily to a non-aqueous solvent, and the like, and the method is not limited thereto, and any method can be used for the production.

The total amount of the polymerizable compound is about 5 to 80 parts by weight based on 100 parts by weight of the non-aqueous solvent, 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.

As described above, the non-aqueous solvent-based dispersed resin produced according to the present invention becomes fine particles having a uniform particle size distribution. Examples of the binder resin of the photoconductive layer of the present invention include alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, and the like, as cited in the description of conventionally known resins. Ryuji Kurita and Jiro Ishiwatari, Polymer, Vol. 17, pp. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging,
A review material on page 9 of 1973 (No. 8) includes known materials cited.

The molecular weight of the resin to be provided is preferably 10
^{It is 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, more preferably 0 ° C to 85 ° C.

Preferably, a random copolymer group containing, as a polymer component, methacrylate known as a binder resin of an electrophotographic photosensitive member using photoconductive zinc oxide as an inorganic photoconductor is mentioned as one of them. For example, Japanese Patent Publication No. 50-2242, Japanese Patent Publication No. 50-31011, Japanese Patent Application Laid-Open No. 50-98324, Japanese Patent Application Laid-Open No. 50-98325, Japanese Patent Publication No. 54-13977, Japanese Patent Publication No. 59-35013,
JP-A-54-20735, JP-A-57-202544
And the like.

As the photoconductive zinc oxide according to the present invention, any of those conventionally known in the technical field of this type may be used, and not only so-called zinc oxide, but also one obtained by treating zinc oxide with an acid, a dye and a pre-treatment. Any of those obtained by kneading and kneading and pulverizing again (so-called pressing) may be used, and there is no particular limitation.

The lithographic printing plate precursor of the present invention has a ratio of 10 parts by weight to 100 parts by weight, particularly preferably 15 parts by weight, of the binder resin to 100 parts by weight of photoconductive zinc oxide.
Used in a proportion of 50 parts by weight.

In the present invention, various dyes can be used in combination as a spectral sensitizer, if necessary. For example, Harumiya Miyamoto, Hidehiko Takei “Imaging”, 1973 (No. 8)
Page 12, C.I. J. RCA Review, Young et al.
w VOL. 15, 469 (1954), Kohei Kiyota, IEICE Transactions J63-C (No. 2), 9
7 (1980), Yuji Harasaki et al., Industrial Chemistry Magazine, No. 66
Volume, pages 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, Volume 35, page 208 (1
972) and the like. Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.) Metal may be contained).

More specifically, the following are mainly used: carbonium dyes, triphenyl methane dyes, xanthene dyes, and phthalein dyes.
JP-A-50-90334, 50-114227, and 5
3-39130, JP-A-53-82353, U.S. Pat. Nos. 3,052,540, 4,054,450 and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include those described in F.I. M. Harmmer "The Cyanin
eDyes and Related Component
dyes described in US Pat. Nos. 3,047,384 and 3,11.
0,591, 3,121,008, 3,12
5,447, 3,128,179, 3,13
2,942, 36,22,317, British Patents 1,226,892, 1,309,274,
1,405,898, JP-B-48-781
And the dyes described in JP-A Nos. 55-18892, and the like.

Further, as polymethine dyes for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, JP-A-47-44180, and JP-B-51-4 are available.
1061, JP-A-49-5034 and JP-A-49-4512
2, 57-45245, 56-35141, 57
-157254, 61-26044, 61-275
51, U.S. Pat. Nos. 3,619,154 and 4,175,956, "Research D
isclosure ", 1982, 216, 117-
And those described on page 118 and the like.

The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye.

Further, if necessary, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination. For example, electron accepting compounds (eg, halogen, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Development and practical application of recent photoconductive materials and photoconductors", Chapters 4 to 6, published by Japan Science Information Co., Ltd. (1986) Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like cited in the reviews are mentioned. The amounts of these various additives are not particularly limited, but are usually 0.0001 to 2.10 parts by weight based on 100 parts by weight of the photoconductor.
0 parts by weight.

The thickness of the photoconductive layer is preferably 1 μm to 100 μm, particularly preferably 10 μm to 50 μm. When a photoconductive layer is used as the charge generation layer of the stacked photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 μm.
m to 1 μm, particularly preferably 0.05 μm to 0.5 μm.

Examples of the charge transporting material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, virazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is 5 μm to 40 μm, particularly 10 μm
３０30 μm is preferred.

Typical resins used for forming the charge transport layer include polystyrene resins, polyester resins, cellulose resins, polyether resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, and polyacrylic resins. Resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, thermoplastic resins such as silicone resins, and curable resins are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably electrically conductive. As the electrically conductive support, for example, a base material such as metal, paper, or a plastic sheet is impregnated with a low-resistance substance, just as in the related art. A substrate that has been subjected to a conductive treatment, for example, by applying a conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further has at least one layer coated for the purpose of preventing curling,
A support provided with a water-resistant adhesive layer on the surface of the support, a support provided with at least one or more pre-coat layers as necessary on the surface layer of the support, and a plastic made conductive by vapor deposition of aluminum or the like. Those laminated on paper can be used.

More specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, "Electrophotography", Vol.
1, page 2 to page 11 (1975), Hiroyuki Moriga, "Chemistry of Introductory Special Paper," Polymer Publishing Association (1975), M.
F. Hoover, J. et al. Macromol. Sci. C
hem. A-4 (6), pp. 1327-1417 (19
70) etc. are used. The scope of the present invention is not limited to the specific compound examples described above.

The printed matter using the electrophotographic lithographic printing plate precursor of the present invention is prepared by forming a copy image on the electrophotographic lithographic printing plate precursor having the above-described structure by a conventional method, and then making the non-image area insensitive to oil. It is created by processing.

In the desensitizing treatment used in the present invention, both the desensitizing reaction of zinc oxide (hereinafter referred to as A reaction) and the desensitizing reaction of resin particles (hereinafter referred to as B reaction) proceed.
As a method of desensitization, for example, a method of performing a B reaction treatment after performing an A reaction treatment, and a method of performing a B reaction treatment,
There are a method of performing a reaction treatment and a method of simultaneously treating the A reaction and the B reaction, and any of these methods may be used.

As a method for desensitizing zinc oxide, any of conventionally known treatment solutions can be used. For example,
Using a ferrocyanide compound as the main agent of desensitization,
JP-A-62-239158, JP-A-62-292492, JP-A-63-99993, JP-A-63-9994, JP-B-40-7
334, 45, 33683, JP-A-57-19788
9. JP-B 46-21244, 44-9045, 4
7-32681, 55-9315, JP-A-52-10
No. 1102, and the like.

Also, JP-B-43-28408, JP-B-45-24609, and JP-B-43-28408 using a phytic acid compound as a main ingredient.
JP-A-51-103501, JP-A-54-10003, JP-A-5
3-83805, 53-83806, 53-127
002, 54-49001, 56-2189, 5
7-2796, 57-20394, 59-2072
Japanese Patent Publication No. 38-966, which uses a water-soluble polymer capable of forming a metal chelate as a main ingredient.
5, 39-22263, 40-763, 43-2
8404, 47-29642, JP-A-52-1263.
JP-A-53-104301, JP-B-55-104301, JP-B-53-104301 and JP-B-55-104302, each of which is described in JP-A-53-104301, JP-A-53-49506, JP-A-53-59502, and JP-A-53-104302. JP-B-39313, JP-B-54-41924, or JP-B-39-139 using an inorganic or organic acid compound as a main agent.
-13702, 40-10308, 46-2612
4, JP-A-51-118501, JP-A-51-111695
Examples described in each of the publications are listed.

The desensitizing treatment of the resin particles [L] used in the present invention is carried out by a solution containing a hydrophilic group-containing compound that easily undergoes a nucleophilic reaction with a formyl group (aqueous solution or mixed solution containing a water-soluble organic solvent). Solution).

Examples of the hydrophilic compound that causes a nucleophilic substitution reaction on a formyl group include a nucleophilic constant n [R.
G. FIG. Person, H .; Sobel, J. et al. Songst
ad, J. et al. Amer. Chem. Soc. , VOL. 9
0,319 (1968)] contains a substituent having a value of 5.5 or more and is soluble in 1 part by weight or more in 100 parts by weight of distilled water.

The desensitizing treatment of the resin particles [L] used in the present invention is carried out by a solution containing a hydrophilic group-containing compound that easily undergoes a nucleophilic reaction with a formyl group (aqueous solution or mixed solution containing a water-soluble organic solvent). Solution).

Examples of the hydrophilic compound which causes a nucleophilic substitution reaction on a formyl group include a nucleophilic constant n [R.
G. FIG. Person, H .; Sobel, J. et al. Songst
ad, J. et al. Amer. Chem. Soc. , VOL. 9
0,319 (1968)] contains a substituent having a value of 5.5 or more and is soluble in 1 part by weight or more in 100 parts by weight of distilled water.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and further contains at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Examples include hydrazide compounds, sulfinic acid compounds, primary amine compounds and secondary amine compounds.

For example, as mercapto compounds, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mecaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, Mercaptobenzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl- 2-mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid Dicarboxybenzenesulfinic acid and the like, as hydrazide compounds, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid, etc. As a primary or secondary amine compound, for example, N- (2-hydroxyethyl) amine, N,
N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, tri (2
-Hydroxyethyl) ethylenediamine, N- (2,3
-Dihydroxypropyl) amine, N, N-di (2,3
-Dihydroxypropyl) amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2
-Carboxyethylmorpholine, 3-carboxypiperazine and the like.

These nucleophilic compounds are used by being contained in the desensitizing solution of the photoconductor described above, or
The resin particles are used by being contained in a treatment liquid for separate treatment. The amount of the nucleophilic compound present in these treatment solutions is 0.1
Mol / l to 10 mol / l, preferably 0.5 mol / l
５5 mol / l. Further, the pH of the treatment liquid is preferably 4 or more. The processing conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. 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, 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 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), etc. Can be used. The scope of the present invention is not limited to the specific compound examples described above.

The method of desensitizing the functional group-containing resin of the present invention represented by the general formula (1) is performed by performing a dehydrohalogenation reaction as shown in the reaction formula (1). It is characterized in that the nucleophile undergoes a nucleophilic reaction on the double bond to be hydrophilized. Since the dehydrohalogenation reaction easily proceeds in a processing solution having a pH of 6 or more,
By setting the pH of the desensitizing solution containing at least the nucleophilic compound to 6 or more, hydrophilization by dehydrohalogenation and nucleophilic reaction is achieved. More preferably, the pH of the treatment liquid is preferably 8 or more. Further, after the dehydrohalogenation reaction is allowed to proceed with a solution having a pH of 6 or more, desensitization treatment with a treatment solution containing a nucleophilic compound may be used. Furthermore, the same effect can be obtained in the hydrophilization treatment containing the nucleophilic compound by using the nucleophilic compound in a fountain solution during printing.

[0218]

EXAMPLES Examples of the present invention will be described below, but the content of the present invention is not limited to these examples. Production Example 1 of Dispersion Stabilizing Resin: [P-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and stirred for 4 hours, and 0.5 g of AIBN was further added and stirred for 4 hours. Next, methacrylic acid 5 was added to the reaction mixture.
g, N, N-dimethyldodecylamine (1.0 g) and t-butylhydroquinone (0.5 g) were added, and the mixture was stirred at 110 ° C. for 8 hours. After cooling, 2000 ml of methanol
After re-precipitation, a slightly brownish oily substance was collected and dried. Weight average molecular weight (Mw) 3.6 × 10 with a yield of 73 g
^{Was 4} .

[0219]

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Production Example 2 of Dispersion Stabilizing Resin: [P-2] A mixed solution of 100 g of 2-ethylhexyl methacrylate, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2 '
2 g of -azobis (4-cyanovaleric acid) (abbreviation: ACV) was added and reacted for 4 hours, and 0.8 g of ACV was further added and reacted for 4 hours. After cooling, the precipitate was reprecipitated in 2000 ml of methanol, and the oil was collected and dried.

50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate, 150 g of tetrahydrofuran
And a mixed solution of 8 g of dicyclohexylcarbodiimide (abbreviated as DCC), 0.2 g of 4- (N, N-dimethylamino) pyridine and 20 g of methylene chloride is added dropwise at a temperature of 25 to 30 ° C. Stirred for hours. Next, 5 g of formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. After filtering off the precipitated insoluble matter, the filtrate was reprecipitated in 1000 ml of methanol to collect an oily substance. Further, this oily substance was dissolved in 200 g of tetrahydrofuran, and the insoluble substance was separated by filtration and then reprecipitated again in 1000 ml of methanol. The oily substance was collected and dried. The yield was 32 g and the weight average molecular weight (Mw) was 4.2 × 10 ⁴ .

[0222]

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Production Example 3 of Dispersion Stabilizing Resin: [P-3] A mixed solution of 96 g of butyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN
The reaction was performed for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2000 ml of methanol to obtain 82 g of an oily substance. The weight average molecular weight of the polymer was 5,600.

[0224]

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Production Example 4 of dispersion stabilizing resin: [P-4] A mixed solution of 100 g of n-butyl methacrylate, 4 g of β-mercaptopropionic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. did. 1.0 g of AIBN was added thereto and reacted for 6 hours. After cooling the reaction mixture and setting the temperature at 25 ° C., 10 g of 2-hydroxyethyl methacrylate and 1 g of DCC were added, and 8 g of DCC and 4- (N, N-dimethylamino) were added with stirring.
A mixed solution of 0.2 g of pyridine and 20 g of methylene chloride was added dropwise at a temperature of 25 to 30 ° C, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. After the precipitated insoluble matter was separated by filtration, the filtrate was reprecipitated in 1,000 ml of methanol, and the oily substance was collected by filtration. Further, this oily substance was dissolved in 200 g of tetrahydrofuran, and the insoluble substance was separated by filtration and then reprecipitated again in 2000 ml of methanol. The oily substance was collected and dried. Weight average molecular weight 8 with a yield of 68 g
× 10 ³ .

[0226]

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Production Examples of Dispersion Stabilizing Resins 5 to 12: [P-
5-P-12] In Production Example 4, n-butyl methacrylate 100 g
Was replaced by a group of monomers corresponding to Table 2 below,
Each resin was produced in the same manner as in Production Example 4. Mw of each resin
Was in the range of 5.5 × 10 ^{3 to} 7 × 10 ³ .

[0228]

[Table 2]

Production Examples of Dispersion Stabilizing Resins 13 to 16: [P
-13 to P-16] In Production Example 4, each resin was produced in the same manner as in Production Example 4, except that the compounds corresponding to Table 3 were used instead of 2-hydroxymethacrylate. Mw of each resin is 6 ×
It was in the range of 10 ^{3 to} 7 × 10 ³ .

[0230]

[Table 3]

Production Example 17 of Dispersion Stabilizing Resin: [P-1
7] A mixed solution of 80 g of hexyl methacrylate, 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. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN)
Was added and reacted for 4 hours.
Reacted for hours. After cooling the reaction to a temperature of 25 ° C., 4 g of methacrylic acid was added and 6 g of DCC,
A mixed solution of 0.1 g of (N, N-dimethylaminopyridine) and 15 g of methylene chloride 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, and the precipitated insoluble material was separated by filtration.
Re-precipitated in ml and collected the oil. Further, this oily substance was dissolved in 150 g of benzene, the insoluble matter was separated by filtration, and then reprecipitated again in 1000 ml of methanol. The oily substance was collected and dried. The yield was 56 g and Mw was 8 × 10 ³ .

[0232]

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Production Examples 18 to 22 of Dispersion Stabilizing Resins: [P
-18 to P-22] By carrying out the reaction as shown in Production Example 17, the Mw of each resin obtained by synthesizing the dispersion stabilizing resins shown in Table 4 below was 6 × 10
It was in the range of ^{3 to} 9 × 10 ³ .

[0234]

[Table 4]

Production Example 1 of Resin Particles: [L-1] A mixed solution of 10 g of dispersion stabilizing resin [P-17] and 200 g of dipropyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this, Akarolein [A-1]
A mixed solution of 47 g, 3 g of the following monomer [B-1], 2 g of ethylene glycol dimethacrylate, 0.5 g of AIVN and 235 g of bipropyl propyl ketone was added dropwise over 2 hours, and the mixture was reacted for 2 hours. Further, A.I. I. V. N.
0.3 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 0.18 μm. (CAPA-500 (Horiba, Ltd.)
And particle size measurement).

[0237]

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Production Examples 2-11 of Resin Particles: [L-2]-
[L-11] Production Example 1 was the same as Production Example 1 of the resin particles except that the monomers [A-1] and [B-1] were replaced by the monomers shown in Tables 5 and 6 below. Resin particles were produced in the same manner as described above. The average particle size of each particle was in the range of 0.15 to 0.30.

[0239]

[Table 5]

[0240]

[Table 6]

Production Example A12 of Resin Particles: [L-12] Resin AA-6 for dispersion stabilization [macromonomer manufactured by Toagosei Chemical Industry Co., Ltd .: macromonomer having methyl methacrylate as a repeating unit: weight average molecular weight Mw 1.5 × 10
⁴ ] A mixed solution of 7.5 g and 133 g of methyl ethyl ketone was heated to 60 ° C. while stirring under a nitrogen stream. 45 g of the following monomer [A-12] and the following monomer [B-
12] 4 g, diethylene glycol dimethacrylate 5
g, 0.5 g of AIVN and 15 of methyl ethyl ketone.
0 g of the mixed solution was added dropwise over 1 hour.
25 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 0.25 μm.

[0242]

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Production Example 13 of Resin Particles: [L-13] A mixed solution of 7.5 g of dispersion stabilizing resin P-5 and 235 g of methyl ethyl ketone was stirred for 60 hours under a nitrogen stream.
Warmed to ° C. To this, a mixed solution of 22 g of the monomer [A-5], 3 g of the monomer [B-7], 15 g of acrylamide, 0.5 g of AIVN and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and further reacted for 1 hour. .

Furthermore, after adding 0.25 g of AIVN and reacting for 2 hours, the dispersion was cooled, and the average particle size of the dispersion obtained through 200 mesh nylon was 0.28 μm.

Production Example 14 of Resin Particles: [L-14] 40 g of a monomer [A-13] having the following structure, and a monomer [B-
2] 4 g, 2 g of ethylene glycol diacrylate, 10 g of dispersion stabilizing resin P-7 and 235 g of methyl ethyl ketone were heated to a temperature of 60 ° C. under a nitrogen stream. This was dropped into a solution of 200 g of methyl ethyl ketone over 2 hours while stirring. After reacting for 1 hour, 0.3 g of AIVN was further added and reacted for 2 hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.2.
It was 0 μm.

[0246]

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Production Examples of Resin Particles 15 to 25: [L-15
~ L-25] Resin particles [L-1] in the same manner as in Production Example 14 except that in Preparation Example 1 of resin particles, a polyfunctional compound shown in Table 7 below was used in place of 2 g of ethylene glycol dimethacrylate.
5] to [L-25] were produced. The polymerization rate of each particle is 9
The average particle size was 0.15 to 0.25 μm at 5 to 98%.

[0248]

[Table 7]

Production Examples 26 to 31 of Resin Particles: [L-26
~ L-31] In Production Example 12 of the resin particles, the dispersion stabilizing resin [P-
17] was used in the same manner as in Production Example 12, except that each dispersion stabilizing resin shown in Table 8 below was used.

The average particle size of each particle was in the range of 0.20 to 0.25.

[0251]

[Table 8]

Production Examples of Resin Particles 32-35: [L-32
~ L-35] In Production Example 13 of resin particles, Production Example 13 was repeated except that the compounds of Table 9 below were used instead of the monomer [A-5], acrylamide, and the reaction solvent: methyl ethyl ketone.
Each particle was produced in the same manner as described above. The average particle size of each particle was in the range of 0.15 to 0.30.

[0253]

[Table 9]

Example 1 1.8 g of resin particles [L-12], 18 g of a binder resin [C-1] having the following structure, 100 g of zinc oxide and 15 g of toluene
0 g of the mixture is homogenized (manufactured by Nippon Seiki Co., Ltd.).
In the dispersion at a rotation speed of 6 × 10 ³ rpm for 10 minutes.
0.2 g of phthalic anhydride and 0.01 g of phenol
And further dispersed at 1 × 10 ³ rpm for 1 minute.

This dispersion was applied to 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 was 18 g / m ^2. And dried at 100 ° C for 30 seconds.
Heated for hours.

[0256]

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This lithographic plate obtained by making a plate using a commercially available PPC was used as a desensitizing solution ELP-EX (Fuji Photo Film Co., Ltd.)
After passing through the etching machine once using
5 mol / L diethanolamine aqueous solution: E
-1 for 3 minutes and then washed with water.

Next, this printing original plate was used as a fountain solution.
Using a liquid obtained by diluting the desensitizing solution E-1 with water 20-fold, an offset printing machine (Oliver 52, manufactured by Sakurai Seisakusho Co., Ltd.) was used to print on fine 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.

Example 2 3 g of resin particles [L-10], resin [C-2] having the following structure
30 g, zinc oxide 80 g, colloidal silica 10 g, 6 × 10 6 in a homogenizer (manufactured by Nippon Seiki Co., Ltd.)
³ r. p. m. At 10 rpm for 10 minutes.

To this dispersion was added 0.01 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and o
-0.005 g of chlorophenol was added, and the number of rotations was 1 x 1
0 ³ was dispersed for 1 minute at rpm. This dispersion is coated with a wire bar on an intermediate layer of a support having a back layer on one side of a high-quality paper and an intermediate layer on the other side so that the dry adhesion amount is 18 g / m ^2. After drying at 100 ° C. for 1 minute and further heating at 120 ° C. for 1 hour, a lithographic printing original plate was prepared.

[0261]

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This original plate was made in the same manner as in Example 1, and subjected to desensitization treatment before printing. 3,000 prints of clear image quality without fog were printed.

Example 3 1 g of resin particles [L-27], resin [C-3] having the following structure
2 g, 18 g of resin [C-4] having the following structure, zinc oxide 80
g, 10 g of titanium oxide and 200 g of toluene were dispersed in a homogenizer at a rotation speed of 6 × 10 ³ rpm for 10 minutes, and 0.05 g of maleic anhydride was further added to the dispersion.
It was dispersed at × 10 ³ rpm for 1 minute.

The dispersion thus obtained was used in Example 1
After coating on a support under the same conditions as described above, the resultant was dried at 100 ° C. for 30 seconds, and further heated at 120 ° C. for 1 hour to prepare a lithographic printing original plate.

[0265]

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After plate-making in the same manner as in Example 1, EL
It was passed once with an etching machine using P-EX, and further immersed in a treatment solution having the following formulation for 3 minutes.

Treatment liquid: E-2 • 80 g of thiomalic acid • 6 g of Newmar B4SN (manufactured by Nippon Emulsifier Co., Ltd.) • 100 g of methyl ethyl ketone dissolved in 1 liter of distilled water, and pH was adjusted with potassium hydroxide.
Adjusted to 10.5.

Using this master, printing was performed using a solution obtained by diluting E-2 20 times with water as a fountain solution.
Up to 1,000 prints were obtained with clear image quality without background contamination.

Examples 4 to 19 The operations of Example 3 were repeated, except that the copolymer shown in the following table was used in place of the resin particles [L-26]. A printing plate precursor was prepared.

[0270]

[Table 10]

After making these plates in the same manner as in Example 1, each of them was etched with an etching machine using ELP-FX.
After passing through, the sample was further immersed in a treatment solution having the following formulation: E-3 for 3 minutes.

Treatment liquid: E-3 • 75 g of 2-mercaptoethanesulfonic acid • 8 g of Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) • 80 g of benzyl alcohol in 1 liter of distilled water and pH with potassium hydroxide
It was adjusted to 11.0.

Using this master, printing was performed using a solution obtained by diluting E-3 20 times with water as a fountain solution.
The image quality of the printed matter after printing 1,000 sheets was a clear image without background fog.

Examples 20 to 24 In the same manner as in Example 1, except that the following particles were used in place of the resin particles [L-27] and maleic anhydride, a lithographic printing plate precursor was used. Was prepared.

[0275]

[Table 11]

Each lithographic printing plate was insulated and made insensitive in the same manner as in Example 3, and printing was performed. After printing 3000 sheets, the printed matter had no fog in the non-image area and the image was clear.

Examples 25 to 36 Using the photosensitive materials prepared in Examples 1 to 24, an etching process was performed as described below to prepare a master plate for offset printing.

After the original plate was passed through an etching machine once using ELP-EX, 0.5 mol of a nucleophilic compound shown in Tables 13 and 14 below, 100 g of an organic solvent, and Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) ) Distilled water was added to 10 g to make 1000 ml, and then the pH of each mixture was adjusted to 10.0. Each master was immersed in the above processing solution at 30 ° C. for 2 minutes.

The obtained plate was printed under the same printing conditions as in Example 1.

[0280]

[Table 12]

[0281]

[Table 13]

In each of the masters, the contact angle of the non-image portion with water was 1
It was sufficiently hydrophilized at 0 degrees or less. In addition, even when the number of prints was 5,000, the print quality of the printed matter was clear, with no background fogging, and was excellent.

Examples 37 to 40 Each original plate was prepared in the same manner as in Example 1 except that the resin particles [L] shown in Table 15 below were used instead of the resin particles [L-1]. .

[0284]

[Table 14]

After making each master plate in the same manner as in Example 1, the obtained master plate was immersed in ELP-FX for 3 minutes, and further immersed in a desensitizing solution E-2 for 1 minute. After the chemical conversion treatment, printing was performed in the same manner as in Example 1. As a result, 10,000 prints of clear image quality free of background stain were obtained.

[0286]

According to the present invention, it is possible to obtain a direct-drawing type lithographic printing plate precursor in which generation of background stains is suppressed well and good printing durability is obtained.

Claims (3)

(57) [Claims] 1. A direct-printing lithographic printing plate precursor having an image receiving layer on a support, wherein the image receiving layer has a particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles. A toner image is formed by imagewise exposing an electrophotographic body comprising at least one of the following nonaqueous solvent-based dispersed resin particles having a photoconductive layer in a non-image portion other than the toner image portion Is subjected to desensitization treatment with a treatment solution containing a hydrophilic compound having at least a person's nucleophilic constant n of 5.5 or more, to produce a printing plate precursor, characterized in that: . Non-aqueous solvent-based dispersed resin particles (L): Monofunctional monomer (A) having formyl group and / or at least one functional group represented by the following general formula (1) and silicon in a non-aqueous solvent system Monomer (A) containing a substituent containing an atom and / or a fluorine atom
Copolymer resin particles obtained by subjecting a monofunctional monomer (B) to be copolymerized with a monofunctional monomer (B) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. Embedded image (However, in the above general formula (1), R ₁ and R ₂ may be the same or different and each represents a hydrocarbon group, or
₁ and R ₂ represent an organic residue linked to each other to form a ring) 2. The method for producing a lithographic printing plate precursor according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 3. The dispersion stabilizing resin according to claim 1, wherein the polymer chain contains at least one polymerizable double bond group represented by the following general formula (2). Method for producing an electrophotographic lithographic printing plate precursor. Embedded image