JPH0534949A - Production of planographic printing original plate - Google Patents

Abstract

PURPOSE:To obtain a planographic printing original plate with the water hoding property improved by the appropriate interaction of the zinc oxide, spectral sensitizing pigment, resin A and dispersed resin grains, having excellent printed picture and high plate wearing resistance even in severe conditions and effective in the scanning exposure using a semiconductor laser beam. CONSTITUTION:The planographic printing original plate incorporates at least one kind among the polymer components of the repeating ingredient shown by the formula and at least one kind among the nonaqueous solvent-based dispersed resin grains obtained by polymerizing the resin A consisting of the polymer component contg. a specified polar group and having 1X10<3>-2X10<4> weight average mol.wt. and a monomer C having formyl and/or a functional group to be converted to formyl group by acid treatment in the presence of a dispersion stabilizing resin having a substituent contg. silicon atom and/or fluorine atom. In the formula, a1 and a2 are respectively hydrogen atom, hydrocarbonic groups, etc., and R03 is a hydrocarbonic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lithographic printing plate precursor prepared by electrophotography, and more particularly to a composition for forming a photoconductive layer and a desensitizing treatment for the lithographic printing plate precursor. Regarding the improvement of the method.

[0002]

2. Description of the Related Art At present, various types of offset master plates for direct plate making have been proposed and put into practical use. Among them, photoconductive particles such as zinc oxide and a binder resin are mainly used on a conductive support. The photoconductor provided with the photoconductive layer as a component is subjected to a usual electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is treated with a desensitizing solution called an etchant. A technique for obtaining an offset original plate by selectively making the non-image portion hydrophilic is widely used.

In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoreceptor is easily compatible with the desensitizing solution, and at the same time the non-image area is sufficiently hydrophilicized. It has water resistance, and in printing, the surface conductive layer having an image does not come off, and it is well compatible with fountain solution, so that it does not stain even when the number of printed sheets increases, It is necessary to have such properties as maintaining hydrophilicity. It has been clarified that these performances are greatly influenced by the type of binder resin in the photoconductive layer, and as an offset master plate, various zinc oxide binder resins that improve the desensitizing property have been investigated. Has been done. Especially, methacrylate (or acrylate)
Examples include multi-component copolymers containing at least a component,
For example, Japanese Patent Publication No. 50-31011 and Japanese Patent Laid-Open No. 53-402.
7, JP-A-57-202544, and JP-A-58-68.
No. 046 is known.

Further, as a binder resin, a resin using a resin containing a functional group capable of generating a hydrophilic group by decomposition has been investigated. Sho 62-195684
JP-A-62-210475, JP-A-62-210
No. 476) or containing a functional group capable of generating a carboxyl group upon decomposition (JP-A-62-21269), or containing a functional group capable of generating a hydroxyl group or a carboxyl group upon decomposition and bridging between polymers. To prevent water stain and improve printing durability by imparting water solubility and water swelling property (JP-A 1-19
1157, JP-A-1-197765, JP-A 1-1
91860, JP-A-1-185667, JP-A-1-
190552, JP-A-1-191158, etc.) are known.

However, even if the resin is said to be effective in improving the desensitizing property, when actually evaluated,
Background stains and printing durability were still unsatisfactory.

Further, JP-A-1-232356 and 1-26.
1657 describes that the addition of resin particles containing a hydrophilic group to the photoconductive layer is effective in improving water retention.

It was confirmed that the water retention property was remarkably improved by improving these photoconductive compositions.

[0008]

However, when evaluated in more detail as a lithographic printing plate precursor, environmental fluctuations (high temperature
At high humidity or low temperature / low humidity, electrophotographic characteristics (especially charge retention in the dark, photosensitivity, etc.) fluctuated, and stable and good copied images could not be obtained. As a result, as a result, the print image of the printed matter using this as a printing original plate is deteriorated or the background stain prevention effect is reduced.

Further, in the electrophotographic lithographic printing plate precursor as a digital direct lithographic printing plate, when a scanning exposure system using a semiconductor laser beam is adopted, it takes longer time than the whole surface simultaneous exposure system using visible light, In addition, since there are restrictions on the exposure intensity, electrostatic characteristics,
In particular, higher performance is required for dark charge retention characteristics and photosensitivity.

On the other hand, in the above-mentioned known original plate, the electrophotographic characteristics are deteriorated, and the actual copy image is apt to cause the background fog, and the fine lines are skipped or the characters are blurred.
As a result, when printing as a lithographic printing plate precursor, the image quality of the printed matter deteriorates, and the effect of preventing scumming due to the hydrophilicity improvement of the non-image portion of the binder resin is lost.

The present invention solves the above-mentioned problems of the conventional electrophotographic lithographic printing plate precursor.

That is, the first object of the present invention is to provide a copy image which is excellent in electrostatic characteristics (in particular, dark charge retention and photosensitivity), which is faithful to the original image, and which is a uniform surface as an offset original plate. This is a method for producing a lithographic printing plate precursor that is excellent in desensitization and does not generate stains or spot stains.

An object 2 of the present invention is a method for producing a lithographic printing plate precursor having a clear and high-quality image even when the environment at the time of forming a copied image changes such as low temperature and low humidity and high temperature and high humidity.

A third object of the present invention is a method for producing a lithographic printing plate precursor which is not easily affected by the types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even in a scanning exposure system using a semiconductor laser beam.

[0015]

The present invention has the above-mentioned object of providing at least a photoconductive layer containing at least photoconductive zinc oxide particles, a spectral sensitizing dye and a binder resin on a conductive support. In the electrophotographic lithographic printing plate precursor having one layer, at least one of the following resins [A] is contained as the binder resin, and the maximum particle of the photoconductive zinc oxide particles is contained in the photoconductive layer. The electrophotographic photosensitive member containing at least one kind of non-aqueous dispersion resin particles [L] having the average particle diameter equal to or smaller than the above diameter is subjected to image exposure to form a toner image. The photoconductive layer of the non-image area other than the toner image area is desensitized with a processing liquid containing a hydrophilic compound having a nucleophilic constant n of at least a value of 5.5 or more to obtain a printing original plate. A lithographic stamp characterized by It is achieved by the manufacturing method of use original.

As the resin [A], 1 × 10 ³ to 2 × 10
Having a weight average molecular weight of ⁴ and having a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more,
_{-PO 3 H 2, -SO 3 H} , -COOH, -P (= O)
(OH) R ₀₁ [R ₀₁ is a hydrocarbon group or a -OR ₀₂ group (R ₀₂
Represents a hydrocarbon group)

[0017]

[Chemical 5]

And 0.5 as a polymer component having at least one polar group selected from the group containing a cyclic acid anhydride.
Resin containing about 15% by weight,

[0019]

[Chemical 6]

[However, in the above formula (I), a ₁ , a
Each ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. The non-aqueous dispersion resin particles [L] contained in the photoconductive layer of the present invention have a formyl group and / or the following general formula, which are soluble in the non-aqueous solvent but insolubilized by polymerization in the non-aqueous solvent. (I
A dispersion soluble in the solvent, which comprises at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom, and a monofunctional monomer [C] having at least one functional group represented by I). The copolymer resin particles are obtained by carrying out a dispersion polymerization reaction in the presence of a stabilizing resin.

[0021]

[Chemical 7]

[However, in the above formula (II), A ₁ ,
A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A ₂ represent organic residues which are linked to each other to form a ring. That is, as a result of various studies, an electrophotographic photosensitive member containing the resin [A] and the dispersed resin particles [L] of the present invention contains a hydrophilic compound having a person nucleophilic constant n of 5.5 or more. The conventional drawbacks could be overcome by the method for producing a lithographic printing plate precursor that is desensitized with the treatment liquid.

Further, the resin [A] is preferably a resin represented by the following general formula (I) as a copolymer component represented by the general formula (I).
It is preferable to contain at least one of a) and the aryl group-containing methacrylate component represented by the following general formula (Ib) (hereinafter referred to as resin [A ′]).

[0024]

[Chemical 8]

[In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR ₀₄ or-
COOR ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ are each -COO-
Represents a single bond or a linking group having 1 to 4 linking atoms for connecting the benzene ring] In the present invention, the resin has a formyl group and / or a functional group represented by the general formula (II). The coalescence component may have a crosslinked structure, and in this case, the resin has water resistance when it exhibits hydrophilicity by reacting with the hydrophilic treatment liquid, which is preferable.

Further, as the dispersion stabilizing resin in the present invention, the following general formula (III) is contained in the polymer chain.
Those containing at least one polymerizable double bond group moiety represented by are particularly preferable.

[0027]

[Chemical 9]

[In the general formula (III), V ₀ is -O
-, - COO -, - OCO -, - (CH 2) p -OCO
_{-, - (CH 2) p} -COO -, - SO 2 -, - CON
_{R 1 -, - SO 2 R} 1 -, - C 6 H 4 -, - CONHC
Represents OO- or -CONHCONH- (provided that p is
Represents an integer of 1 to 4, R ₁ represents a hydrogen atom or a carbon number of 1
Represents a hydrocarbon group of 18), b ₁ and b ₂ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or a hydrocarbon group. -COO-R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)].

The lithographic printing plate precursor of the present invention is insensitive to the non-image area of the photoconductive layer containing at least the photoconductive zinc oxide particles, the spectral sensitizing dye and the binder resin in the uppermost photoconductive layer. This is a printing original plate of a system in which the surface is made hydrophilic by treatment with an emulsifying solution to obtain a lithographic printing plate.

The photoconductive layer of the present invention comprises a low molecular weight resin [A] containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a specific copolymer component, and non-aqueous solvent-based dispersed resin particles (hereinafter referred to as resin). Particles [L] may be abbreviated in some cases).

The resin particles [L] used in the present invention have an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and have a narrow particle diameter distribution and a uniform particle diameter. In addition, 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 nucleophilic reactive hydrophilic compound, the nucleophile is attached to the terminal of the formyl group of the resin particles and / or the functional group represented by the general formula (II). A reactive hydrophilic compound is capable of undergoing an addition reaction, whereby the particles can express hydrophilicity and at the same time,
When the resin particles have a crosslinked structure, at this time, they have hydrophilicity and are insoluble or slightly soluble in water and have water swellability.

As another one, the resin particles [L] of the present invention are prepared in the presence of a dispersion stabilizing resin containing at least a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom. The polymer as a dispersion stabilizing resin containing a fluorine atom and / or a silicon atom, which is obtained by a dispersion polymerization reaction, is formed by physicochemically adsorbing an insoluble component or a polymerizability represented by the above formula (III). In the case of a dispersion-stabilizing resin containing a double bond group portion, it is considered that both polymerizable components are chemically bonded, and therefore it is presumed that migration / concentration phenomena occur on the surface portion of the photoconductive layer. It

The mechanism of the resin particles [L] of the present invention being hydrophilized by the nucleophilic reactive hydrophilic compound is represented by the following reaction formula using the sulfite ion as the nucleophilic reactive hydrophilic compound as a representative example. It is shown in 1).

[0034]

[Chemical 10]

That is, the resin particles of the present invention have a nucleophilic reactivity such that the nucleophilic constant n of the person in the treatment liquid is 5.5 or more only when the non-image area is desensitized as a lithographic printing plate. By adding a hydrophilic group to the terminal by reacting with the hydrophilic compound as described above, the hydrophilicity is thereby expressed, that is, it is made hydrophilic, and it does not react with moisture in the atmosphere. There are no concerns about storability. Since the formyl group according to the present invention is a functional group that reacts very quickly with a nucleophilic compound, it is possible to rapidly develop hydrophilicity.

When a nucleophilic reactive hydrophilic compound having a person's nucleophilic constant n of less than 5.5 is used, the hydrophilicity of the non-image area becomes insufficient. Furthermore, since the functional group represented by the general formula (II) can be converted into a formyl group by the acid treatment, the deacetalization reaction easily proceeds by the acid treatment, as shown in the reaction formula (1). It can be used similarly to the formyl group.

The resin [A] of the present invention is a low molecular weight polymer containing the specific polymer component represented by the formula (I) and the specific polar group-containing polymer component. Characterize.

The photoconductive layer of the present invention is dispersed by the photoconductive zinc oxide particles, the spectral sensitizing dye, and the resin [A] containing at least the resin particles [L] as a binder resin, Furthermore, the resin particles [L] immediately migrate to the surface portion after the photoconductive layer is formed and are concentrated and exist in the surface vicinity portion.

That is, when the photoconductive zinc oxide particles, the spectral sensitizing dye, the resin particles [L] and the resin [A] are dispersed,
A low molecular weight resin [A] containing a specific polar group
Adsorbs on stoichiometric defects of photoconductive zinc oxide, and compensates for trapping of photoconductive zinc oxide by properly covering and interacting with zinc oxide and dye. At the same time, it is considered that while the humidity characteristics are dramatically improved, the photoconductive zinc oxide is sufficiently dispersed and the aggregation is suppressed.

Particularly in the case of the conventional binder resin, when the kind of the spectral sensitizing dye is changed, the interaction such as adsorption is disturbed and satisfactory electrophotographic characteristics cannot be obtained. However, when the resin [A] of the present invention is used, remarkably excellent electrophotographic characteristics can be satisfied even with a dye used for spectral sensitization especially for semiconductor laser light.

Further, as an original plate of the electrophotographic lithographic printing system, it is important to obtain good electrophotographic characteristics and at the same time,
That is, the non-image portion has a high water-holding property that is sufficiently hydrophilized by the desensitizing treatment and does not cause ink adhesion during printing. In the lithographic printing plate precursor of the present invention, the resin particles [L] concentrated and present on the surface portion of the photoconductive layer generate a hydrophilic group by the desensitizing treatment of the present invention to express hydrophilicity. , The non-image portion is sufficiently modified to be hydrophilic and exhibits sufficient water retention without causing scumming. Furthermore, resin [A]
It is also possible to use a method in which the zinc oxide particles uniformly dispersed are subjected to desensitization treatment by a known method to make the non-image area hydrophilic.

That is, the original plate of the present invention solves the difficult problem of excellent water retention in the non-image area after the formation of a good copy image due to the excellent electrophotographic characteristics and the desensitization treatment after the copy image formation. I was able to.

On the other hand, in the resin particles of the present invention, when the resin particles having a particle size larger than the zinc oxide particle size are present, electrophotographic characteristics are deteriorated (especially uniform charging property cannot be obtained). In the copied image, density unevenness in the image portion, breakage of characters / fine lines, jumping, or background fog in the non-image portion occurs.

Specifically, the resin particles of the present invention have a maximum particle diameter of 2 μm or less, preferably 0.5 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 size of the resin particles, the larger the specific surface area of the resin particles, which brings about a better effect on the electrophotographic characteristics. Colloid particles (0.01 μm or less) are sufficient, but they are too small. If it is too much, it will be similar to the case of molecular dispersion, and the effect of being particles for improving the water retention ability will be weakened. Therefore, it is preferably used at 0.001 μm or more.

Further, in the present invention, the resin particles are those in which a hydrophobic polymer component, that is, a polymer component corresponding to the dispersion stabilizing resin, is bound, and the hydrophobic portion serves as the binder resin of the photoconductive layer. Since they interact with each other, the anchor effect of this portion does not elute with dampening water during printing, and good printing characteristics can be maintained even when printing a large number of sheets.

Further, when a heat and / or photocurable group is contained as one of the polymer components as the dispersion stabilizing resin, further elution is further suppressed by further chemically bonding with a binder resin. can do.

Further, in the present invention, the resin particles having a crosslinked structure can further suppress the elution property with water, while exhibiting the water swelling property and further improving the water retention property. In the present invention, the resin particles that do not form the above-mentioned crosslinked structure or the resin particles that form the crosslinked structure (hereinafter simply referred to as “resin-resin particles”) are 0.1% by weight based on 100 parts by weight of photoconductive zinc oxide. It is preferably used in an amount of 05 to 30% by weight. If the amount of resin particles or tie-line resin particles is less than 0.05% by weight, the hydrophilicity of the non-image area will not be sufficient. The electrophotographic characteristics under the conditions deteriorate, and the copied image deteriorates.

Furthermore, the resin particles adsorb or chemically bond with a polymer component containing a fluorine atom and / or a silicon atom, so that the particles migrate to the surface portion of the photoconductive layer.
It is also possible to add a very small amount to cause a concentration phenomenon and to bring about an effect (water holding property) similar to that of the known technique.

As a result, the lithographic printing plate precursor produced according to the present invention reproduces a copied image faithful to the original image even when the environmental conditions are changed or a low output laser beam is used, and a non-image is produced. Since the part has good hydrophilicity, it does not cause scumming, and the photoconductive layer has good smoothness and electrostatic properties, and further has excellent printing durability.

Further, the electrophotographic photosensitive member according to the present invention is not affected by the environment during the plate-making process, and is very excellent in the preservability before the process.

The binder resin (A) used in the present invention is described below.
Will be described in detail. In the weight [A], the weight average molecular weight is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 1.
0 ³ a to 1 × 10 ^4, a glass transition point of the resin (A) is preferably -30 ° C. to 110 ° C., more preferably -20
C to 90C.

When the molecular weight of the resin [A] is less than 10 ³ , the film forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even the resin of the present invention, In particular, in the case of photoconductors using near-infrared to infrared spectral sensitizing dyes, the dark decay retention rate and the photosensitivity change slightly under severe conditions of high temperature / high humidity, low temperature / low humidity, and stable copying is possible. The effect of the present invention that an image is obtained diminishes.

The proportion of the polymer component corresponding to the repeating unit of the general formula (I) of the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the polymer component containing a specific polar group is The abundance ratio is 0.5 to 15% by weight, preferably 1
10 to 10% by weight.

The content of polar groups in the resin [A] is 0.5
If the amount is less than wt%, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group is more than 15% by weight, dispersibility is lowered no matter how low molecular weight the compound is, and scumming is increased when it is used as an offset master.

The low molecular weight resin [A] has a specific substituent at the 2-position and / or at the 2-position and 6-position represented by the above-mentioned general formulas (Ia) and (Ib). The resin [A] (hereinafter, this low molecular weight compound is referred to as resin [A ']) containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring is preferable.

The proportion of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (Ia) and / or the formula (Ib) in the resin [A '] is 30% by weight or more, preferably 50%.
The amount of the polymer component containing a specific polar group is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the resin [A '].

Next, the resin [A] is contained in an amount of 30% by weight or more. The repeating unit represented by formula (I) will be further described. In the general formula (I), a ₁ and a ₂ are preferably hydrogen atom, cyano group, alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.),
COO-R ₀₆ or -COO-R via a hydrocarbon group
₀₆ (R ₀₆ represents a hydrogen atom or an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 1 to 18 carbon atoms, which may be substituted. ₍ Represents the same content as that described for ₀₃ ).

Examples of the hydrocarbon in the —COO—R ₀₆ group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

R ₀₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, Tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group,
Octenyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (benzyl group having carbon number, phenethyl group,
Naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl group having 5 to 8 carbon atoms (for example, cyclopentyl group, cyclohexyl group,
Cycloheptyl group etc.), optionally substituted aryl group (eg phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl Group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.) and the like.

More preferably, the copolymer component corresponding to the repeating unit of the general formula (I) is a methacrylate component containing a specific aryl group represented by the general formula (Ia) and / or the general formula (Ib). The copolymer component (resin [A ']) represented is mentioned.

In the formula (Ia), preferred T ₁ and T ₂
Independently of each other, in addition to a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group), aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl group) -Benzyl group) and aryl groups (for example, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₀₄ and -C.
OOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms) can be mentioned.

In the formulas (Ia) and (Ib), L ₁ and L
₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) n1 - (} n 1 represents an integer of 1 to 3), -
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2
O) _m1 - (m ₁ represents an integer of 1 or _2), - CH 2 C
A connecting group having 1 to 4 connecting atoms such as H ₂ O-,
More preferably, a direct bond or a linking group having 1 to 2 bonding atoms can be mentioned.

Formula (Ia) used in the resin [A] of the present invention
Specific examples of the copolymerization component corresponding to the repeating unit represented by (Ib) are shown below. However, the scope of the present invention is not limited to this. The following (a-1) to (a
-20), n is an integer of 1 to 4 and m is 0 or 1
3 is an integer, p is an integer of 1 to 3, and R _{10 to} R ₁₃ are all-
C _n H _{2n + 1} or _{- (CH 2) m -C 6} H 5 ( where
n and m are the same as above), X ₁ and X ₂ may be the same or different and each represent a hydrogen atom, —Cl, —Br or —I.

[0065]

[Chemical 11]

[0066]

[Chemical 12]

[0067]

[Chemical 13]

[0068]

[Chemical 14]

[0069]

[Chemical 15]

Next, the polar group in the polar group-containing component of the characteristic of the low molecular weight resin [A] will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH, -P (=
It is preferable that at least one selected from O) (OH) R ₀₁ and a cyclic acid anhydride-containing group.

The --P (═O) (OH) R ₀₁ group means the above R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group), and specifically R ₀₁ represents an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group Group, fluorobenzyl group, methoxybenzyl group, etc.) or an aryl group which may be substituted (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro- A methyl-phenyl group,
Dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc., and R ₀₂ has the same content as R ₀₁ .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride to be contained include an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. Things can be mentioned.

Examples of the aliphatic dicarboxylic acid anhydride include:
Succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid ring Acid anhydride ring,
2,3-bicyclo [2,2,2] octadicarboxylic acid anhydride ring and the like, and these rings are, for example, chlorine atom,
A halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group may be substituted.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-dicarboxylic acid anhydride ring, and the like. These rings are
For example, chlorine atom, halogen atom such as bromine atom, methyl group, ethyl group, propyl group, alkyl group such as butyl group,
Hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as the alkoxy group, for example, methoxy group,
Ethoxy group etc.) may be substituted.

The copolymerizable component containing a polar group of the resin [A] is, for example, a monomer corresponding to the repeating unit represented by the general formula (I) [including general formulas (Ia) and (Ib)]. Any vinyl compound having a polymerizable polar group may be used, and it is described, for example, in "Polymer Data Handbook [Basic Edition]" edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α -Fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α
-Chloro-β-methoxy form, α, β-dichloro form, etc.),
Methacrylic acid, itaconic acid, itaconic acid half-esters,
Itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-
Hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid,
Maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivative of vinyl group or allyl group of dicarboxylic acids, and carvone or sulfonic acid thereof And the compound having the polar group in the substituent of the amide derivative.

The polar group-containing copolymerization component will be exemplified below. Here, e ₁ represents H or CH ₃ , e ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₅ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and c is 1 to
3 is an integer, d is an integer of 2 to 11, and e is 1 to
11 is an integer, f is an integer of 2 to 4, and g is 2 to
Indicates an integer of 10.

[0077]

[Chemical 16]

[0078]

[Chemical 17]

[0079]

[Chemical 18]

[0080]

[Chemical 19]

[0081]

[Chemical 20]

[0082]

[Chemical 21]

[0083]

[Chemical formula 22]

[0084]

[Chemical formula 23]

[0085]

[Chemical formula 24]

[0086]

[Chemical 25]

[0087]

[Chemical formula 26]

[0088]

[Chemical 27]

[0089]

[Chemical 28]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ']) means a monomer other than these together with the monomer of the general formula (I), (Ia) and / or (Ib) and the monomer containing the polar group. The body may be contained as a copolymerization component.

Examples of such other copolymerization component include, for example, methacrylic acid esters, acrylic acid esters, crotonic acid esters containing a substituent other than those described in the general formula (I), and α-olefins. , Vinyl carboxylates or acrylic esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (for example, Dimethyl ester, diethyl ester, etc., acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphtha). Phthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like. 30% by weight of these other monomers in the resin [A]
It is desirable not to exceed.

The resin [A] has a weight average molecular weight of 1 × 10.
These are low molecular weight random copolymers having a molecular weight of ^{3 to} 2 × 10 ⁴ , and these polymerization methods can be easily synthesized by radical polymerization, ionic polymerization, etc. by selecting polymerization conditions in the conventionally known method. be able to. Monomers that polymerize,
The radical polymerization reaction is advantageous from the setting temperature of the polymerization solvent reaction and the like, which is advantageous in terms of purification, apparatus reaction method and the like.

Specific examples of the polymerization initiator include commonly known azobis type initiators and peroxides.
In particular, as a characteristic of synthesizing a low molecular weight substance, a known method such as increasing the amount of the initiator used or increasing the polymerization set temperature may be applied. Specifically, the amount of the initiator used is within the range of 0.1 to 20 parts by weight, and the polymerization temperature is within the range of 30 to 200 ° C., based on the total amount of the monomers.

Further, a method of using a chain transfer agent in combination is also known. For example, a desired weight average molecular weight can be adjusted by using a mercapto compound, a halogenated compound or the like in the range of 0.01 to 10 parts by weight with respect to the total amount of monomers.

Low molecular weight resin [A] as described above
(Including [A ′]) is preferably used in combination with the above-mentioned known resin for photoconductive zinc oxide. The use ratio of the low molecular weight resin and the other resin is preferably 5 to 50/50 to 90 (weight ratio).

In the present invention, the use ratio of photoconductive zinc oxide, resin (total binder resin) and resin particles [L] is preferably 100/10 to 100 / 0.5 to 10 (weight ratio). Further, the resin [A] is preferably 5 to 50% by weight in all the binder resins 10 to 100.

Other resins to be used in combination include a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ , preferably 5 × 10 ^{4 to} 5.
× 10 ^{5 is} a medium to high molecular weight substance. The glass transition point of the resin used in combination is -10 ° C to 120 ° C, preferably 0 ° C.
~ 90 ° C.

For example, 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 and the like.

Specifically, Ryuji Shibata and Jiro Ishiwatari, "Polymer," Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8), page 9, Koichi Nakamura, "Practical technology of binders for insulating materials"
Chapter 10, C.I. H. C. Published (1985), D.M.
D. Tatt, S.M. C. Heidecker, Tapp
i, 49 (No. 10), 439 (1966), E.I.
S. Baltazzi, R .; G. Blanklotte
et al, Photo. Sci. Eng. 16 (N
o. 5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography 18 (No.
2), 28 (1980), JP-B-50-31011, JP-A-53-54027, 54-20735, 57-.
The materials disclosed in JP-A-202544 and JP-A-58-68046 are cited.

As a medium to high molecular weight resin, which is a preferable resin to be used in combination, the above-mentioned physical properties are satisfied, and preferably 30% by weight or more of the polymer component of the repeating unit represented by the following general formula (IV) is contained. Polymers may be mentioned.

[0101]

[Chemical 29]

[In the formula (IV), V is —COO—, —O
_{CO -, - (CH 2)} q -OCO -, - (CH 2) q -
COO -, - O-or -SO ₂ - represents a. However, q is 1
In the general formula (IV), d ₁ and d ₂ are a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, methyl). Group, ethyl group, propyl group, butyl group, etc.)
Represents

R ₀₇ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, Tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a 2-naphthylethyl group). , Methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.),
Optionally substituted cycloalkyl group having 5 to 8 carbon atoms (for example, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl group (for example, phenyl group, tolyl group, xyl group, mesityl group, Naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, nitrophenyl Groups and the like).

The medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (IV) is, for example, a resin of a random copolymer containing the polymer component represented by the formula (IV). (Japanese Patent Laid-Open Nos. 63-49817 and 63-2201)
49, 63-220148, etc.), a resin in which the random copolymer and a crosslinkable resin are used in combination (JP-A 1-211
766, JP-A 1-102573), a copolymer containing a polymer component represented by the formula (IV) and partially cross-linked in advance (JP-A-2-34860 and JP-A-2-40660), The graft-type block copolymer obtained by polymerizing a monofunctional macromonomer consisting of the polymer component of the repeating unit of (1) and a monomer corresponding to the component represented by the formula (IV) (JP-A-2-53064 and JP-A-2-56558). , 3-2
9957, 3-77954, 3-92861, 3
-53257, etc.) and the like.

Next, the resin particles [L] of the present invention will be described. The monofunctional monomer [C] used in the resin particles [L] contains at least a formyl group and / or a functional group represented by the general formula [II].

[0106]

[Chemical 30]

In the above formula (II), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ , A ₂
A ₂ represents an organic residue which is linked to each other to form a ring.
When A ₁ and A ₂ each represent a hydrocarbon group, A ₁ and A ₂ are preferably an aliphatic group having 1 to 12 carbon atoms which may be substituted (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted). Group: Specific examples are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, methoxymethyl group, ethoxymethyl group, 2-hydroxyethyl group, 2 -Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
An alkenyl group having 2 to 12 carbon atoms which may be substituted, such as a methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group, and a 3-methoxypropyl group:
Specific examples thereof include a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a docenyl group, a dodecenyl group, and the like, which may have a carbon number of 7 to 12 and which may be substituted; benzyl group, phenethyl group, 3 -Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, dimethoxybenzyl group, chlorobenzyl group, bromobenzyl group, fluorobenzyl group, dichlorobenzyl group And the like, and C 3-12 optionally substituted alicyclic groups: specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and the like.

When A ₁ and A ₂ represent an organic residue which is linked to each other to form a ring, a functional group represented by formula (IIa), that is, a cyclic acetal group is preferable.

[0109]

[Chemical 31]

In the formula (IIa), A ₃ and A ₄ may be the same or different from each other, and are each a hydrogen atom or a carbon number of 1 to 1.
2 optionally substituted hydrocarbon groups, or an -OA ₅ group (A
₅ represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.

Preferred examples in which A ₃ , A ₄ and A ₅ are hydrocarbon groups of hydrocarbons 1 to 12 which may be substituted include:
Aliphatic group (specific examples represent the same contents as those exemplified for A ₁ and A ₂ ), 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 formulas (II) and (II
In a), when A _{1 to} A ₅ are aliphatic groups, the number of carbon atoms is 1
Are preferably an alkyl group having 6 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and an aralkyl group having 7 to 9 carbon atoms.

Further, n is more preferably an integer of 1 to 3. Examples of the copolymerization component containing a formyl group and / or a functional group represented by (II) used in the present invention include those represented by the repeating unit of the following general formula (V).

[0114]

[Chemical 32]

[However, in the formula [V], Z is -COO-,
-OCO -, - O -, - CO -, - CONr 1 -, - S
O ₂ Nr ₁ - (r ₁ represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCONH- , C
H ₂ COO-, CH ₂ OCO- or -C ₆ H ₄ - represents a.

Y represents an organic residue which directly bonds or connects -Z- and -W _0- . Furthermore,-[Z-Y]-

[0117]

[Chemical 33]

The part and -W ₀ may be directly connected. W ₀ represents a formyl group or a functional group represented by (II).
f ₁ and f ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (V) will be described in more detail.

Preferably, Z is --COO--, --OCO.
-, - O -, - CO -, - CONr 1 -, - SO 2 Nr
₁ - or -C ₆ H ₄ - represents a. However, r ₁ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group, octyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc., and optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3
-Phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (e.g., phenyl group, tolyl group, xylyl group,
Mesityl group, methoxyphenyl group, chlorophenyl group,
Bromophenyl group, chloro-methoxy-phenyl group, etc.)
Etc.

Y represents a direct bond or an organic residue connecting -Z- and -W ₀ . When Y represents an organic residue to be linked,
The linking group represents a carbon-carbon bond which may be passed through a hetero atom (the hetero atom includes an oxygen atom, a sulfur atom and a nitrogen atom), for example,-[C (r ₂ )
(R _{3)] -, - C 6 H 10 -} , - C 6 H 4 -, - (CH
= CH) -, - O - , - S -, - Nr 4 -, - COO
-, - CONH -, - SO 2 -, - SO 2 NH -, - N
HCOO -, - NHCONH -, - Si (r 5)
(R ₆ )-or the like, or a combination of bonding units. (However, r ₂ , r ₃ , r ₄ , r ₅ , r
₆ represents the same content as r ₁ above).

F ₁ and f ₂ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group). , Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonylmethyl group, ethoxycarbonylmethyl group,
Represents an optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group, aryl group such as chlorophenyl group) .

Furthermore, the-[ZY] -bonding residue in formula (V) is

[0123]

[Chemical 34]

The part and the -W ₀ part may be directly linked. Specific examples of the polymer component containing the formyl group and / or the functional group represented by the general formula (II) of the present invention are shown below.
In Examples (c-1) to (c-15), a is -H or-.
Represents CH ₃ . However, the present invention is not limited to this.

[0125]

[Chemical 35]

[0126]

[Chemical 36]

[0127]

[Chemical 37]

[0128]

[Chemical 38]

Specific examples of the functional group represented by the general formula (IIa) of the present invention are also shown below. Examples (c'-1) to (c'-)
In 9), R ₁₀ and R ₁₁ represent an alkyl group having 1 to 4 carbon atoms or —CH ₂ C ₆ H ₅ , and 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.

[0131]

[Chemical Formula 39]

[0132]

[Chemical 40]

The polymer component containing a formyl group and / or the functional group represented by the general formula (II) in the resin particle [L] of the present invention can be used when the resin particle [L] is a copolymer.
It is preferably from 30 to 99% by weight, particularly from 50 to 95% by weight, based on the total copolymer.

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

For example, as a method for synthesizing a compound containing a formyl group, the Chemical Society of Japan, New Experimental Chemistry, Volume 14,
636 (1978) Maruzen Co., Ltd., E.I. Mulle
r, "Methoden der Organisehe
n Chemie ”, p. 13 (1954), Georg.
The methods described in Theme Verlag, edited by The Chemical Society of Japan, New Experimental Chemistry Lecture, vol. 19, page 231 (1957) published by Maruzen Co., Ltd. may be mentioned.

As the polymerizable functional group in the above-mentioned monomer synthesis, an ordinary polymerizable double bond group, specifically CH
_{2 = CH-CH 2 -,} CH 2 = CH-CO-O-, CH
_{2 = CH (CH 3) -CO} -O-, CH (CH 3) = C
_{H-CO-O-, CH 2} = CH-CONH-, CH 2 =
_{C (CH 3) -CONH-, CH} 2 = C (CH 3) -C
_{ONHCOO-, CH 2 = C (CH} 3) -CONHCO
_{NH-, CH (CH 3) =} CH-CONH-, CH 2 =
_{CH-O-CO-, CH 2} = CH-C 6 H 4 -, CH 2
_{= C (CH 3) -O-} CO-, CH 2 = CH-CH 2 -
_{O-CO-, CH 2 = CH} -NHCO-, CH 2 = CH
_{-CH 2 -NHCO-, CH 2 = CH} -SO 2 -, CH
_{2 = CH-CO-, CH 2} = CH-O-, CH 2 = CH
-S- and the like can be mentioned.

The resin particles [L] of the present invention are composed of the monomer [C]
It may be polymerized together with other monomers. Any other monomer may be used as long as it can be copolymerized with the monomer [C] and the copolymer becomes an insoluble polymer in the non-aqueous solvent.

Other monomers copolymerizable with these monomers include, for example, aliphatic vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate or allyl esters. Esters or amides of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid, styrene derivatives such as styrene, vinyltoluene and α-methylstyrene, α-olefins , Vinyl group-substituted heterocyclic compounds such as acrylonitrile, methacrylonitrile, and N-vinylpyrrolidone.

The amount of these other monomers is 60 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total insoluble polymer component. If the amount of the other monomer exceeds 60 parts by weight, the effect of improving the water retention property as the offset printing original plate decreases.

Next, in the non-aqueous solvent-based dispersed resin particles of the present invention, a soluble dispersion-stabilizing resin for stabilizing the dispersion of the resin particles in the non-aqueous solvent system will be described. The dispersion stabilizing resin for use in the present invention is characterized in that the polymer contains a substituent containing a fluorine atom and / or a silicon atom.

The repeating unit having a substituent containing a fluorine atom and / or a silicon atom will be described. Examples of the chemical structure of the repeating unit include those obtained from radical addition-polymerizable monomers, those consisting of a polyester structure or those consisting of a polyether structure, and the like, in the side chains in the repeating units of these polymer structures, Any one may be used as long as it contains a fluorine atom and / or a silicon atom.

Examples of the fluorine atom-containing substituent include --C _h F _{2h + 1} (h represents an integer of 1 to 12) and-(CF
₂ ) _j CF ₂ H (j represents an integer of 1 to 11), -C ₆
H _l F _{l '} [(l and l'are each an integer of 1 to 5, where l + l' =
5) or (l = 5-l ', l'is an integer of 1 to 5)] and the like.

Examples of the substituent containing a silicon atom include:
−Si (R ₃ ) (R ₄ ) (R ₅ ), − (Si (R ₆ ) (R ₇ ) O) _k −R ₈
(K represents an integer of 1 to 20), a polysiloxane structure, and the like.

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

R ₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2 -Chloroethyl group, 2-
Bromoethyl group, 2,2,2-trifluoroethyl group, 2
-Cyanoethyl group, 3,3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2
-Methoxycarbonylethyl group, 2,2,2,2 ',
2 ′, 2′-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg,
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4
-Methyl-2-hexenyl group, etc.), an aralkyl group having 7 to 12 carbon atoms and which may be substituted (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro) Benzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.) and an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, 2- A cyclohexyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg,
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propylamidophenyl group, dodecyloylamidophenyl group, etc.).

In the —OR ₉ group, R ₉ has the same meaning as the hydrocarbon group for R ₃ above. R ₆ , R ₇ and R ₈ may be the same or different and represent the same symbol content as R ₃ , R ₄ and R ₅ .

Next, the above-mentioned fluorine atom and / or
Specific examples of repeating units having a substituent containing an iodine atom
An example is shown below. Where a is H or CH₃And Rf is
-CH ₂C_hC_{2h + 1} -(CH₂)₂-(CF₂)_jCF₂Show H
Then R₁′, R₂′, R₃′ Is C₁~₁₂The alkyl group of
R ″ is --Si (CH₃)₃And h is an integer from 1 to 12
Number, j is an integer from 1 to 11, and p is an integer from 1 to 3.
Is a number, l is an integer of 1 to 5, and q is an integer of 1 to 20.
A number, r is an integer from 30 to 150, and t is
An integer of 2 to 12 is shown. However, the scope of the invention is
It is not limited to.

[0148]

[Chemical 41]

[0149]

[Chemical 42]

[0150]

[Chemical 43]

[0151]

[Chemical 44]

[0152]

[Chemical formula 45]

[0153]

[Chemical formula 46]

[0154]

[Chemical 47]

[0155]

[Chemical 48]

[0156]

[Chemical 49]

In addition, the dispersion stabilizing resin may contain other components in addition to the component containing a fluorine atom and / or a silicon atom. The other component to be copolymerized may be any as long as it can be copolymerized with the corresponding polymer, and as the corresponding monomer, for example, α-olefins, styrenes, acrylonitrile, methacrylonitrile, Vinyl-containing heterocycles (as the heterocycle, for example, a pyran ring, a pyradrine ring, an imidazole ring, a pyridine ring, etc.),
Vinyl group-containing carboxylic acids and esters thereof (eg acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and esters thereof), vinyl group-containing carboxamides (eg acrylamide, methacrylamide, crotonic acid amide, Itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.) and the like.

In the dispersion stabilizing resin of the present invention, the amount of the polymer component containing a fluorine atom and / or a silicon atom is 30 parts by weight or more, preferably 50 parts by weight or more based on 100 parts by weight of the total polymer of the resin.

In the dispersion stabilizing resin of the present invention, the polymer component containing a fluorine atom and / or a silicon atom is arbitrarily adjusted.

In the dispersion stabilizing resin of the present invention, the light and / or thermosetting functional group is 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 total polymer of the resin. You may. Examples of the photo- and / or thermosetting functional group to be contained include those other than the polymerizable functional group, and specific examples thereof include functional groups for forming a crosslinked structure of the particles described later.

Furthermore, the dispersion stabilizing resin of the present invention preferably contains at least one polymerizable double bond group moiety represented by the above general formula (III) in the polymer chain. The polymerizable double bond group component will be described below.

[0162]

[Chemical 50]

In the general formula (III), V ₀ is -O
−, −COO −, −OCO −, −CH ₂ OCO−, −CH ₂ COO
−, −SO ₂ −, −CONR ₁ −, −SO ₂ NR ₁ − or −C ₆ H
₄ - I represent a.

In addition to hydrogen atom, R ₁ is preferably a hydrocarbon group which may be substituted and has 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) Or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl Group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group Group, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

[0165] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group) Group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

B ₁ and b ₂ may be the same as or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg Methyl group, ethyl group, propyl group, butyl group, etc.)-COO-R ₂ or hydrocarbon-mediated COOR
₂ (R ₂ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically, the above R _It represents the same contents as those described for _1. ).

Examples of the hydrocarbon in the —COO—R ₂ group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, the general formula (II
In I), V ₀ is, -COO -, - OCO -, - CH 2 OC
_{O -, - CH 2 COO -} , - O -, - CONH -, - SO 2 NH- or -C ₆ H ₄ - represents, b _1, b _2, which may be the same or different, a hydrogen atom, methyl Group, -COOR ₂ or -CH ₂ COOR ₂ , (R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) Represents
Even more preferably, one of b ₁ and b ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group component represented by the general formula (III), specifically, CH ₂ ═CH—CO—O—
, CH ₂ = C (CH ₃ ) -CO-O-, C (CH ₃ ) H = CH-CO-O-, CH ₂ =
C (CH ₂ COOCH ₃ ) -CO-O-, CH ₂ = C (CH ₂ COOH) -CO-O-
, CH ₂ = CH-CONH-, CH ₂ = C (CH ₃ ) -CONH-, C (CH ₃ ) H = C
H-CONH-, CH ₂ = CH-O-CO-, CH ₂ = CH-CH ₂ -O-CO-, CH ₂
= CH-O-, CH ₂ = C (COOH) -CH ₂ -CO-O-, CH ₂ = C (COOCH ₃ )-
CH ₂ -CO-O-, CH ₂ = CH-C ₆ H _4- and the like can be mentioned.

The polymerizable double bond group moiety represented by the general formula (III) is one end of the main chain of a polymer containing at least a repeating unit having a substituent containing a fluorine atom and / or a silicon atom. And are directly bonded or bonded by any linking group. Specifically as a group to be linked, it is a divalent organic residue, and is -O- or -S.
−, −Nq ₁ −, −SO−, −SO ₂ −, −COO −, −OCO
−, −CONHCO−, −NHCONH−, −CONq ₂ −, −SO ₂ Nq ₃
- and _{-Si (q 4) (q 5} ) - from selected linking groups may be the interposed, a divalent aliphatic group or a divalent aromatic group,
Or, it represents an organic residue constituted by a combination of these divalent residues. Here, q _{1 to} q ₅ have the same contents as R ₁ in formula (III).

As the divalent aliphatic group, for example, -C (q ₆ )
_{(q 7) -, - C} (q 6) = C (q 7) -, - (C≡C) -, - C
₆ H ₁₀ −,

[0171]

[Chemical 51]

{Q ₆ and q ₇ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or an alkyl group having 1 to 12 carbon atoms ( For example, methyl group, ethyl group,
(Propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.)
Represents Q is -O -, - S- or -NR ₁₀ - represents,
R ₁₀ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂
Represents Br}.

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

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like.

The above-mentioned polymerizable double bond group-containing moiety is specifically bonded only in the polymer chain, or a polymerizable dipolymerizable bond group is formed only at one end of the main chain of the polymer chain. A polymer in which the containing portion is bound (hereinafter, a monofunctional polymer [M]
Abbreviated). The above monofunctional polymer [M]
Specific examples of the polymerizable double bond group component represented by the general formula (III) and the moiety composed of the organic residue linked thereto include the following, but are not limited to these. Absent. 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 represents an -Cl or -Br, n is 2 to 12 Is shown, m shows the integer of 1-4.

[0176]

[Chemical 52]

[0177]

[Chemical 53]

[0178]

[Chemical 54]

[0179]

[Chemical 55]

[0180]

[Chemical 56]

[0181]

[Chemical 57]

Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group moiety in the side chain of the polymer, and the polymer can be synthesized 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 carboxyl group, a hydroxyl group, an amino group, an epoxy group and the like in a molecule. After polymerizing a monofunctional monomer containing a reactive group to obtain a polymer, a polymerizable double-chain containing another reactive group that can chemically bond with the reactive group in the side chain of the polymer. Reacting with an organic low-molecular compound containing a bonding group,
Examples of well-known methods include a method of introducing by a so-called polymer reaction.

As the above method, for example, JP-A-60-
The method described in Japanese Patent No. 185962 may be used. As the above method, specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (Published in 1977), Ryohei Oda "Polymer Fine Chemical" Kodansha (Published in 1976), JP-A-6
It is described in detail in the specification filed as Japanese Patent Application Laid-Open No. 1-43757 and Japanese Patent Application No. 1-149305.

For example, a polymer reaction by a combination of the functional group of group A and the functional group of group B in Table 1 below is a well known method. Note that R ₂₁ and R _{22 in} Table-1
Is a hydrocarbon group and has the same content as the hydrocarbon group for R ₁ in the above formula (III).

[0186]

[Table 1]

Further preferred as the dispersion stabilizing resin of the present invention is to contain a polymerizable double bond group moiety at one end of the main chain--
The functional polymer [M] can be produced by a conventionally known synthesis method. For example, a) an ionic polymerization method in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to obtain a monofunctional polymer [M], and b) a carboxyl group and a hydroxyl group in the molecule. Monofunctional by reacting a polymer having a terminal reactive group bond obtained by radical polymerization with various reagents using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a group or an amino group. Method by radical polymerization method for obtaining polymer [M], c) Polyaddition condensation method in which a polymerizable double bond group is introduced into the polymer obtained by polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. And the like.

Specifically, P.I. Dreyfuss &
R. P. Quirk, Bncycl. Polym. Sc
i. Eng. , 7 , 551 (1987), p. F. Re
mpp, E.I. Franta, Adv. Polym. Sc
i. , 58 , 1 (1984), V.I. Percec, Ap
pl. Poly. Sci. , 285 , 95 (198
4), R.A. Asami, M .; Takari, Macro
mol. Chem. Suppl. , 12 , 163 (19
85), P.I. Rempp. , Et al, Macrom
ol. Chem. Suppl. , 8 , 3 (1984),
Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982), Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Association, 18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Azuma, Takashi Tsuda,
Functional Materials, 1987 , No. It can be synthesized according to the methods described in the review articles such as 10, 5 and the references and patents cited therein.

More specifically, as the method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radical-polymerizable monomer is described in JP-A No. 1993/1999.
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application Nos. 1-206989 and 1-69011, and the like, and also contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] is prepared according to Japanese Patent Application Nos. 1-56379 and 1-58989.
It can be obtained in the same manner as the methods described in the specification of the application, etc., as Nos. 1-56380.

As described above, the dispersed resin particles of the present invention contain the polar group-containing monofunctional monomer (C) containing at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. It is a copolymer resin particle obtained by dispersion polymerization in the presence of a dispersion stabilizing resin.

Further, when the dispersed resin particles of the present invention have a crosslinked structure (including a higher-order network structure), a polymerizable component containing the above polar group-containing monofunctional monomer (C) as a main component. The polymers of [Abbreviated as polymer component (C)] are bridged between polymers to form a high-order network structure.

That is, the dispersed resin particles of the present invention are a non-aqueous latex composed of a portion insoluble in the non-aqueous dispersion solvent composed of the polymer component (C) and a polymer soluble in the solvent. In the case of having a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged.

As a result, the network resin particles are sparingly soluble or insoluble in water. In particular,
The solubility of the resin in water is 80% by weight or less, preferably 5
It is 0% by weight or less.

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

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

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

Polymerization of a polyfunctional monomer (also referred to as a polyfunctional monomer (D)) or a polyfunctional oligomer containing two or more polymerizable functional groups to be coexisted in the above method (b). the sexual functional group, in particular _{CH 2 = CH-CH 2 -} , CH 2 = CH-CO-O-,
_{CH 2 = CH-, CH 2 =} C (CH 3) -CO-O-,
_{CH (CH 3) = CH-} CO-O-, CH 2 = CH-C
_{ONH-, CH 2 = C (CH} 3) -CONH-, CH
_{(CH 3) = CH-CONH-} , CH 2 = CH-O-C
_{O-, CH 2 = C (CH} 3) -O-CO-, CH 2 = C
_{H-CH 2 -O-CO-,} CH 2 = CH-NHCO-,
_{CH 2 = CH-CH 2 -NHCO-} , CH 2 = CH-S
_{O 2 -, CH 2 = CH} -CO-, CH 2 = CH-O-,
CH ₂ = CH-S-, and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

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

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

Further, in the case of the above method (c), in the case of forming a chemical bond by the reaction of the reactive groups between the polymers to form a bridge between the polymers, the reaction with the usual organic low molecular compound is performed. You can do the same. Specifically, it can be synthesized according to the same method as described in the method of synthesizing the dispersion stabilizing resin.

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

As described above, the network-dispersed resin particles of the present invention include a repeating unit containing a formyl group and / or a functional group represented by the general formula (II), and the molecular chains are cross-linked at a high degree. And a polymer component soluble in the non-aqueous solvent, which contains at least a repeating unit having a fluorine atom and / or silicon atom-containing substituent, .

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, which may be used alone or in combination of two or more. Good.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, diethyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane, decane, dodecane, tridecane , Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples include halogenated hydrocarbons such as trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle diameter of the resin particles easily becomes 0.8 μm or less, and the distribution of the particle diameter is very narrow and monodispersed. Can be particles.

Specifically, K. B. J. Barrett
"Dispersion Polymerization
in Organic Media "John Wil
ey (1975), Koichiro Murata, Polymer processing, 23 ,
20 (1974), Tsunetaka-Toyokichi Tange Matsumoto, Japan Journal of the Adhesion Society of 9, 183 (1973), Toyokichi Tange, Journal of the Adhesion Society of Japan
23 , 26 (1987), D.I. J. Walbridge
e, NATO. Adv. study. Inst. Se
r. B. No. 67, 40 (1983), British Patent No. 8
93429, 934038, US Pat. No. 1
122397, 394012, and 4606989, JP-A-60-179751, and 60-185.
The method is disclosed in each of the 963 publications and the like.

The dispersed resin particles of the present invention contain the monomer (C).
And at least one kind of dispersion stabilizing resin, and in the case of forming a network structure, a polyfunctional monomer (D) is allowed to coexist as necessary. In any case, the important thing is If the resin particles synthesized from these monomers are insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, the dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, and more preferably 2 to 30% by weight, based on the insoluble monomer (C). The molecular weight of the dispersed resin particles of the present invention is 10 ³ to 10 ⁶ ,
It is preferably 5 × 10 ^{3 to} 5 × 10 ⁵ .

In order to produce the dispersed resin particles used in the present invention as described above, the monomer (C), the dispersion stabilizing resin and the polyfunctional monomer (D) are generally used as a non-aqueous solvent. Among them, the heat polymerization may be carried out in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of a monomer (C), a dispersion stabilizing resin and a polyfunctional monomer (D), and (ii) a non-aqueous solvent. , A method of adding the mixture of the polymerizable compound and the polymerization initiator dropwise or arbitrarily, and the like, and the method is not limited to these, and any method can be used for production.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, relative to 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight.

The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 30 to 180.
The temperature is about C, preferably 40 to 120C. The reaction time is preferably 1 to 15 hours.

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

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Further, as another inorganic photoconductor, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide or the like may be used in combination.

However, the content of these other photoconductive materials is 40% by weight or less, preferably 20% by weight or less of the photoconductive zinc oxide.

If the content of other photoconductive material exceeds 40% by weight,
The effect of improving the hydrophilicity of the non-image area as a lithographic printing original plate is diminished. As the photoconductive zinc oxide according to the present invention, those conventionally known in this technical field may be used. Not only so-called zinc oxide, but zinc oxide is acid-treated, dye and pretreated, It may be kneaded and then ground again (so-called press treatment) or the like, and there is no particular limitation.

In the lithographic printing plate precursor of the present invention, the total amount of the binder resin used with respect to the photoconductive zinc oxide is 10 to 100 parts by weight based on 100 parts by weight of the photoconductive zinc oxide. It is particularly preferably used in a proportion of 15 to 50 parts by weight.

In the binder resin used for the photoconductive layer,
The resin [A] and the other binder resin are used in a ratio of 5 to 90/95 to 5 parts by weight with respect to 100 parts by weight of all the binder resins.
The weight ratio is preferably 10 to 60/90 to 40.

When the proportion of the resin [A] used is 5 parts by weight or less, the electrophotographic characteristics are deteriorated, and particularly when combined with a spectral sensitizing dye for semiconductor laser light, the effect is remarkably reduced.

If it is more than 90 parts by weight, the film strength of the photoconductive layer is deteriorated, and if it is used as an original plate for offset printing, printing durability is deteriorated. The amount of the resin particles [L] used in the present invention is 0.
1 to 30 parts by weight is preferable.

If the proportion of the resin particles [L] used is 0.1 parts by weight or less, the effect of improving water retention will be diminished. If it is more than 30 parts by weight, electrophotographic characteristics may be deteriorated.
This is a concern especially for semiconductor laser light.

The spectral sensitizing dye used in the photoconductive layer of the present invention may be any conventionally known dye, and these may be used alone or in combination. For example,
Harumiya Miyamoto, Hidehiko Takei: Imaging 1973 (No.
8) Page 12, C.I. J. Young et al .: RCA Rev
iew 15 , p. 469 (1954), Kouhei Kiyota et al .: The Institute of Electrical Communication, J63-C (No. 2), p. 97 (1)
980), Yuji Harasaki et al., Industrial Chemistry Magazine 66 , 78 and 1.
88 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35 , 2
Carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, which are cited in the review articles such as page 08 (1972),
Examples thereof include xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, cytylyl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes, and phthalein type dyes are described in JP-B-51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyani
neDyes and Related Compou
The dyes described in "nds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11059.
1, 3121008, 3125447, 3128
No. 179, No. 3132942, No. 3622317, British Patent Nos. 12268892, No. 1309274, No. 1405898, and Japanese Patent Publication Nos. 48-7814 and 55-18892.

[0224] Further, in the near-infrared region with a long wavelength of 700 nm or more,
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, JP-A-49-5034, JP-A-49-45122,
57-46245, 56-351141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Pat. Nos. 3,361,954 and 4,175,956.
Each issue, "Research Disclosure
e ", those described in 1982, 216, pages 117 to 118 and the like. The photoconductor of the present invention is excellent in that the performance thereof does not easily vary depending on the sensitizing dye even when various sensitizing dyes are used in combination.

Further, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers may be used in combination. For example, the review mentioned above: Imaging 19
73 (No. 8) page 12 and the like, electron-accepting compounds (eg, halogen, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon, et al., "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors", Chapters 4 to 6: Japanese Science Information Publishing Co., Ltd. (1986) The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc.

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
It is from 01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0 μ, particularly 10 to 50 μ is suitable.

When a photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 μm, and particularly 0.05 to
0.5μ is preferable.

Examples of the charge transport material for the laminated type photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μ, particularly 10 to 30 μ.

As the resin used for forming the charge transport layer,
Typical examples are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin. A resin, a melamine resin, a thermoplastic resin such as a silicone resin, and a curable resin 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 conductive, and as the conductive support, for example, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance as in the conventional case. Those which have been subjected to a conductive treatment by, for example, those which are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and for preventing curling, A body having a water-resistant adhesive layer provided on the surface thereof, a substrate having at least one precoat layer provided on the surface layer of the support, and a conductive electroconductive plastic substrate on which Al or the like is vapor-deposited on paper. Things etc. can be used.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), p2-11 (1975), Hiroyuki Moriga, "Science of Introductory Special Paper", Polymer Publishing (1975), M.S. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), pages 1327 to 1417 (1970) and the like are used.

A publicly known method can be applied to prepare a lithographic printing plate precursor using the electrophotographic photosensitive member of the present invention.
That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include scanning exposure with a semiconductor laser, He-Ne laser, or the like, reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and the like. Next, the electrostatic latent image is developed with toner. As a developing method, a conventionally known method, for example, cascade development, magnetic brush development, powder cloud development,
Various methods such as liquid development can be used. Among them, the liquid development is capable of forming a fine image and is suitable for producing a printed matter. The formed toner image can be fixed by a known fixing method such as heat fixing, pressure fixing, solvent fixing and the like.

The printing original plate of the present invention is produced by desensitizing the non-image area of the lithographic printing original plate thus formed. The desensitizing treatment used in the present invention is, as described above, desensitizing the resin particles of the present invention containing a formyl group and / or a functional group represented by the general formula (II), that is, imparting hydrophilicity, And desensitizing the zinc oxide particles.

The method for desensitizing (conferring hydrophilicity) the formyl group-containing resin particles of the present invention includes a solution (aqueous solution or water solution) containing a hydrophilic group-containing compound that easily nucleophilically reacts with the formyl group. It is achieved by treating with a mixed solution containing an organic solvent.

As a hydrophilic compound which causes a nucleophilic substitution reaction on a formyl group, a nucleophilic constant n [R. G. Person, H .; Sobel,
J. Songstad, J.M. Amer. Chem. So
c. , 90 , 319 (1968)] contains a substituent having a value of 5.5 or more, and 1 is contained in 100 parts by weight of distilled water.
A hydrophilic compound that dissolves by weight or more can be used.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate salt, etc., and 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 thereof include hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic 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, carboxybenzenesulfinate , Dicarboxybenzenesulfinic acid or the like as a hydrazide compound, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid As a primary or secondary amine compound such as 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
-Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

These nucleophilic compounds are used by being contained in a desensitizing solution for zinc oxide photoconductor, or
The binder resin is used by being contained in a treatment liquid for separate treatment. The amount of the nucleophilic compound present in these treatment solutions was 0.1.
The amount is mol / liter to 10 mol / liter, preferably 0.5 mol / liter to 5 mol / liter.

Further, the pH of the treatment liquid is preferably 4 or more.
The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid may contain other compounds in addition to the above-mentioned nucleophilic compound and pH adjusting agent. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.),
Ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.) ), Esters (methyl acetate, ethyl acetate, ethyl formate, etc.) and the like, and these may be used alone or in combination of two or more kinds.

The surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (published in 1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (published in 1980), etc. Can be used.

The scope of the present invention is not limited to the above specific compound examples. The method of desensitizing the functional group-containing resin of the present invention represented by the general formula (II) is as follows: as shown in the above reaction formula (1), a formyl group produced after a dealcoholization reaction by acid decomposition is carried out. The nucleophile is hydrophilized by nucleophilic reaction.

Since the dealcoholization reaction easily proceeds in a treatment solution having a pH of 5 or less, it is treated with the above-mentioned treatment solution for desensitizing zinc oxide (usually adjusted to pH 5 or less) or nucleophilic. PH before treatment to carry out reaction
A formyl group can be easily produced by treating in a treatment liquid of 5 or less, and then hydrophilized by a nucleophilic reaction.

Desensitization of zinc oxide has hitherto been carried out as a desensitizing treatment liquid of this kind by using a ferrocyan salt, a cyan compound-containing treatment liquid containing a ferricyanate as a main component, an amminecobalt complex, phytic acid and Known are cyanide-free treatment liquids containing their derivatives, guanidine derivatives as main components, treatment liquids containing inorganic or organic acids that form chelates with zinc ions as main components, or treatment liquids containing water-soluble polymers. .

For example, as a cyanide-containing treatment liquid,
JP-B-44-9045, JP-B-46-39403, JP-A-5-39
2-76101, ibid 57-107889, ibid 54-11.
Examples thereof include those described in each of the 7201 publications.

As the phytic acid compound-containing treatment liquid,
JP-A-53-83807, 53-83805, 53
-102102, 53-109701, 53-12
7003, 54-2803, and 54-44901 each are mentioned.

Treatment solutions containing a metal complex compound such as a cobalt complex are disclosed in JP-A-53-104301 and JP-A-53-1.
40103, 54-18304, JP-B-43-284
04 The thing described in each gazette is mentioned.

As the treatment liquid containing an inorganic or organic acid, JP-B-39-13702, 40-10308 and 43-2 are available.
8408, 40-26124, JP-A-51-1185.
No. 01, etc. are mentioned.

Examples of the guanidine compound-containing treatment liquid include those described in JP-A-56-111695. A treatment liquid containing a water-soluble polymer is disclosed in Japanese Patent Laid-Open No.
2-126302, 52-134501, 53-4
9506, 53-59502, 53-10430
2, JP-B-38-9665, 39-22263, 4
0-763, 40-2202, JP-A-49-3640.
2 The thing described in each gazette etc. is mentioned.

In any of the above desensitizing treatments,
Zinc oxide in the surface layer, which is the photoconductive layer, is ionized to become zinc ions, and this ion causes a chelation reaction with a compound forming a chelate in the desensitizing solution to form a zinc chelate, which is the surface. It is believed to be deposited in the layer and made hydrophilic.

Therefore, the printing original plate produced by the present invention is prepared by the desensitizing treatment as described above. Further, the hydrophilic treatment with the treatment liquid containing the nucleophilic compound can obtain the same effect even when the fountain solution at the time of printing contains the nucleophilic compound.

[0251]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. Synthesis Example of Binder Resin [A] 1: [A-1] A mixed solution of 95 g of benzyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to a temperature of 90 ° C. under a nitrogen stream, and then 2,2′-azobis. 6.0 g of isobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 2 g was added and reacted for 2 hours. The weight average molecular weight of the obtained copolymer [A-1] was 8,500. Synthesis Example 2/28 of Binder Resin [A]: [A-2] to [A-
28] Resins [A-2] to [A-28] shown in Table 2 below were synthesized in the same manner as in the polymerization conditions of Synthesis Example 1 of Resin [A].

[0252]

[Table 2]

[0253]

[Table 3]

[0254]

[Table 4]

[0255]

[Table 5]

[0256]

[Table 6]

[0257]

[Table 7]

[0258]

[Table 8]

Synthesis Example 29 of Binder Resin [A]: [A-2
9] A mixed solution of 95 g of 2,6-dichlorophenyl methacrylate, 5 g of acrylic acid, 2 g of n-dodecyl mercaptan and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream, and then A. I. B. N. Add 2g and react for 4 hours,
Then A. I. B. N. 0.5 g was added for 2 hours, and A. I. B. N. 0.5 g was added and reacted for 3 hours. After cooling, it was reprecipitated in 2 liters of a mixed solution of methanol / water (9/1), the precipitate was collected by decantation, and dried under reduced pressure. The yield of the obtained waxy copolymer is 78.
The weight average molecular weight in g was 6.3 × 10 ³ .

Next, specific examples of production of the dispersion stabilizing resin (monofunctional polymer) for resin particles and resin particles will be described.

Production Example of Dispersion Stabilizing Resin (Monofunctional Polymer) 1: [M-1] 95 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid and A mixed solution of 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.0 g of azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and t were added to the reaction solution.
-Butyl hydroquinone 0.5g was added and the temperature was 100 ° C.
The mixture was stirred for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight of the polymer [M-1] was 4000.

[0262]

[Chemical 58]

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

[0264]

[Chemical 59]

Production Example 3 of Dispersion Stabilizing Resin (Monofunctional Polymer): [M-3] A mixed solution of 95 g of a monomer [MA-2] having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was added with nitrogen. The mixture was heated to a temperature of 75 ° C while stirring under a stream of air. 2 g of 4,4′-azobis (4-cyanovaleric acid) (abbreviation ACV)
Was added and reacted for 8 hours. After cooling, it was reprecipitated in 1 liter of methanol and the obtained polymer was dried. Next, this polymer 5
0 g and 2-hydroxyethyl methacrylate 11 g,
It was dissolved in 150 g of benzotrifluoride and the temperature was adjusted to 25 ° C. This mixture was stirred under a D.I. C. C. 15g, 4-
A mixed solution of 0.1 g of (N, N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was stirred as it was for 4 hours. After that, 3 g of formic acid was added and stirred for 1 hour, then the precipitated insoluble matter was filtered off, and the filtrate was added with methanol 8
It was reprecipitated in 00 ml. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to obtain 30 g of a viscous material. The weight average molecular weight of the polymer [M-3] was 3.3 × 10 ⁴ .

[0266]

[Chemical 60]

Production Examples 4 to 22 of Dispersion Stabilizing Resin (Monofunctional Polymer): [M-4] to [M-22] Instead of the monomer (MA-1) in Production Example 2, another monomer is used. Polymer (monomer corresponding to the polymer component shown in Table 3)
Each dispersion stabilizing resin [M] was produced in the same manner as in Production Example 2 except that Each weight average molecular weight is 4 × 10 ³ ~
It was 6 × 10 ⁸ .

[0268]

[Table 9]

[0269]

[Table 10]

[0270]

[Table 11]

[0271]

[Table 12]

Production Examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [M-23] to [M-30] In Production Example 2 of the dispersion stabilizing resin, the monomer (MA-
1) and 2-hydroxyethyl methacrylate,
Instead of the compounds corresponding to each of the polymers in Table 4 below,
Other than that, each dispersion stabilizing resin [M] was manufactured by the same method. Each weight average molecular weight was 5 × 10 ^{3 to} 6 × 10 ³ .

[0273]

[Table 13]

[0274]

[Table 14]

[0275]

[Table 15]

Production Example 31 of dispersion stabilizing resin: [M-3
1] Octyl methacrylate 27 g, monomer (M
A-3) A mixed solution of 60 g glycidyl methacrylate 3 g and benzotrifluoride 200 g was heated to a temperature of 75 ° C while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (AIBN) was added and reacted for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110 ° C. for 8 hours. After cooling, reprecipitation was carried out in 2 liters of methanol, and a slightly brownish oily substance was collected and then dried. The yield was 73 g and the weight average molecular weight was 3.6 × 10 ⁴ .

[0277]

[Chemical formula 61]

Production Example 32 of dispersion stabilizing resin: M-32 A mixed solution of 80 g of the following monomer MA-4, 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was stirred at a temperature of 60 under a nitrogen stream. Warmed to ° C. To this, 2,2'-mazobis (isovaleronitrile) (abbreviation: AIV.
N. ) 0.8 g and reacted for 4 hours. I. V.
N. 0.4 g was added and reacted for 4 hours. After cooling the reaction product to a temperature of 25 ° C., 4 g of methacrylic acid was added, and the mixture was added with D. C. C. A mixed solution of 6 g, 0.1 g of 4- (N, N-dimethylamino) pyridine and 15 g of methylene chloride was added dropwise over 1 hour, and the mixture was stirred as it was for 3 hours. Next, 10 g of water was added, the mixture was stirred for 1 hour, the precipitated insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol to collect an oily substance. Further, this oily substance was mixed with benzene 150
After dissolving in g and filtering off the insoluble matter, it was reprecipitated again in 1 liter of methanol to collect an oily matter and dried. The yield was 56 g and the weight average molecular weight was 8 × 10 ³ .

[0279]

[Chemical formula 62]

Dispersion Stabilizing Resin Production Examples 33 to 39: M-
33 to M39 The reaction shown in Production Example 32 was carried out to give the following Table-5.
The respective dispersion stabilizing resins were synthesized. The weight average molecular weight of each resin was in the range of 6 × 10 ^{3 to} 9 × 10 ³ .

[0281]

[Table 16]

[0282]

[Table 17]

[0283]

[Table 18]

Production Example 1 of Resin Particles [L-1] A mixed solution of 10 g of the dispersion stabilizing resin [M-32] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. In addition, the following monomer [C-1] 40
g, 10 g of ethylene glycol dimethacrylate, A.I.
I. V. N. 0.5 g and 240 g of methyl ethyl ketone
The mixed solution of was added dropwise over 2 hours, and the reaction was continued for 2 hours. Furthermore, A. I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a 200 mesh nylon cloth was passed through to obtain a white dispersion. The latex had an average particle size of 0.20 μm. {: CAPA-500 [(manufactured by HORIBA, Ltd.)]
Particle size measurement}

[0285]

[Chemical formula 63]

Production Examples 2-12 of Resin Particles: [L-2]
[L-12] In Production Example 1 of resin particles, except that the resin [M-32] and the monomer [C-1] were replaced with the respective monomers shown in Table 6 below, Resin particles were manufactured in the same manner. The average particle size of each particle was within the range of 0.15 to 0.30 μm.

[0287]

[Table 19]

[0288]

[Table 20]

Production Examples 13 to 23 of Resin Particles: [L-1
3] to [L-23] Resin particles [L-23] were prepared in the same manner as in Production Example 1 except that polyfunctional compounds shown in Table 7 below were used instead of 10 g of ethylene glycol dimethacrylate in Production Example 1 of resin particles. −
13] to [L-23] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0290]

[Table 21]

Production Example 24 of resin particles: [L-24] A mixed solution of 7.5 g of the dispersion stabilizing resin [M-30] and 230 g of methyl ethyl ketone was stirred under a nitrogen gas stream while stirring.
Warmed to 0 ° C. To this, 22 g of monomer [C-1], 15 g of acrylamide, A. I. V. N. A mixed solution of 0.5 g and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. Furthermore, A. I. V.
N. 0.25g was added and reacted for 2 hours, then cooled to 200
The average particle size of the dispersion obtained through the mesh nylon cloth was 0.25 μm. Resin Particle Production Examples 25 to 3
4: Production Example 3 of [L-25] to [L-34] resin particles, except that each of the dispersion stabilizing resins shown in Table 8 below was used in place of the dispersion stabilizing resin [M-35]. Each particle was manufactured in the same manner as 12. The average particle size of each particle is 0.20
Was in the range of ˜0.25.

[0292]

[Table 22]

Production Examples 35-40 of Resin Particles: [L-3
5] to [L-40] Monomer [C-1] 22 in Production Example 24 of resin particles
g, 15 g of acrylamide and a reaction solvent: each particle was produced in the same manner as in Production Example 13 except that each compound shown in Table 9 below was used instead of methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 to 0.30.

[0294]

[Table 23]

Example 1 and Comparative Example A Example 1 6 g of resin [A-7] (as solid content), 32 g of resin [B-1] having the following structure (as solid content), 200 g of photoconductive zinc oxide and the following structure Methine dye [I] 0.018
g, 0.15 g of salicylic acid and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
10 ³ r. p. m. Was dispersed for 10 minutes at the rotation speed of. Dispersed resin particles [L-3] 2 g (as solid content) phthalic anhydride 0.05 g, o-chlorophenol 0.005
g was added and the number of revolutions was 1 × 10 ³ r. p. m. Dispersed for 1 minute. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 100 ° C. for 30 seconds, and further dried at 120 ° C. for 1 second.
Heated for hours. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

[0296]

[Chemical 64]

Comparative Example A An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 2 g of the resin particles [L-3] was used in Example 1. Comparative Example B In Example 1, 6 g of resin [A-7] and resin [B-
1] An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 38 g of only the resin [B-1] was used instead of 32 g.

Film formation (smoothness of the surface), electrostatic characteristics, desensitizing property of the photoconductive layer (expressed by the contact angle of the photoconductive layer after desensitizing treatment with water) and printing of these light-sensitive materials. I investigated the sex. As for printability, a lithographic printing plate obtained by exposing and developing an image on a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) with a developer ELP-T to form an image and desensitizing the plate. It examined using the printing plate. (Note that the printing machine used was a Hamada Star 800SX model manufactured by Hamada Star Co., Ltd.) The above results are summarized in Table-10.

[0299]

[Table 24]

Embodiments of the evaluation items shown in Table 10 are as follows. Note 1) Smoothness of photoconductive layer: Using the Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.), the smoothness (sec / cc) of the obtained photosensitive material was measured under the condition of an air capacity of 1 cc. It was measured. Note 2) Electrostatic characteristics: Corona discharge at −6 kV for 20 seconds using a paper analyzer (Paper Analyzer SP-428 manufactured by Kawaguchi Electric Co., Ltd.) for each light-sensitive material in a dark room at a temperature of 20 ° C. and 65% RH. After that, it was left for 10 seconds, and the surface potential V ₁₀ at this time was measured. Then, the potential V ₁₃₀ after standing still in the dark for 120 seconds is measured, and the potential retention after dark decay for 120 seconds, that is,
Dark decay retention [D. R. R. (%)] To [(V ₁₃₀ / V
₁₀ ) × 100 (%)].

Further, the surface of the photoconductive layer was-
After charging to 500 V, irradiation with monochromatic light having a wavelength of 780 nm is performed, and the time until the surface potential (V ₁₀ ) decays to 1/10 is obtained, and the exposure amount E _1/10 (erg / cm ² ) is calculated from this. To do. Environmental conditions at the time of imaging are I (20 ° C, 65% R
H) and II (30 ° C., 80% RH). Note 3) Imaging: 1 for each photosensitive material under environmental conditions I or II
I left it all day and night. Next, it is charged at −5 kV and used as a light source.
Using a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) with an output of 8 mW, a speed exposure of 50 μg / cm ³ and a pitch of 25 μm and a scanning speed of 330 m / sec was performed on the surface of the photosensitive material.
Fog and image quality of the copied image obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer were visually evaluated. Note 4) Raw plate water retention: The degree of hydrophilicity due to desensitizing treatment when the photosensitive material was used as a printing original plate was examined under the following forced conditions.

Each light-sensitive material itself (original plate not made into a plate:
That is, the etching machine was abbreviated as a raw plate. An etching machine was passed once using an aqueous solution prepared by diluting the desensitizing treatment liquid ELP-EX manufactured by Fuji Photo Film Co., Ltd. 5 times with distilled water. Furthermore, it was immersed for 3 minutes at a temperature of 35 ° C. in a desensitizing treatment solution of the following formulation: E-1. Desensitizing treatment liquid: E-1 Serine 80 g Neosoap (manufactured by Takemoto Resin Co., Ltd.) 15 g Benzyl alcohol 100 g This was dissolved in distilled water to a total volume of 1.0 liter, and then the pH was adjusted to 11.5 with potassium hydroxide. It was adjusted.

This desensitized plate was placed on an offset printing machine (Oliver 52 type, Sakurai Seisakusho Co., Ltd.), and the degree of background stain of the printed matter was visually evaluated. Note 5) Printing durability: Each light-sensitive material is made into a toner image under the same conditions as in Note 3) above to form a toner image, and desensitized under the same conditions as Note 4) above, and this is used as an offset master in Note 4 above. The number of sheets that can be printed under the same conditions as described in (1) above, without causing a background stain on the non-image area of the printed matter and on the image quality of the image area (the larger the number of printed sheets, the better the printing durability).

As shown in Table 10, the light-sensitive materials of the present invention and Comparative Example A have good photoconductive layer smoothness and electrostatic characteristics, and the actual copied image has no background fog and the copied image quality is clear. It was

Next, when it was used as an offset master original plate, the photosensitive material which was not made into a plate was diluted with a desensitizing solution, desensitized under severe conditions, and actually printed to examine the water retention. The product of the present invention showed good water retention without scumming after printing, and 10,000 sheets of clear printed matter without scumming were obtained even when the original plate actually made was used. On the other hand, Comparative Example A, in which the resin particles for promoting the hydrophilization were not added, had an insufficient water retention property, and the background stain of the printed matter was generated from the imprinting and was not eliminated even when imprinting.

In Comparative Example B, the electrostatic characteristics were remarkably deteriorated, and a satisfactory copy image was not obtained in the actual image pickup property. On the other hand, with respect to the water retention property as the offset original plate, the ink adhesion was remarkable and the stain was remarkable. This is due to the fact that the hydrophilic treatment is not sufficiently performed, and in fact, even if printing is performed with the original plate that has been subjected to the hydrophilic treatment under the normal desensitizing condition, the background stain of the printed matter is remarkable and the copied image is not printed on the original plate after plate making. Deteriorated and no prints of satisfactory print quality were obtained from the print.

From the above, it can be seen that an electrophotographic photosensitive member satisfying electrostatic characteristics and printing characteristics can be obtained only when both the resin [A] and the resin particles [L] of the present invention are used. Example 2 5.5 g of resin [A-18] (as solid content), 33 g of resin [B-2] having the following structure, resin particles [L-12] 2.
8 g (as solid content), a methine dye of the following structure [I
I] The electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 0.02 g was used.

[0308]

[Chemical 65]

The electrophotographic characteristics and printability of the obtained light-sensitive material were measured in the same manner as in Example 1 and the following results were obtained.

Electrostatic characteristics (30 ° C., 80% RH) V ₁₀ : −650 V D.I. R. R. : 81% E _1/10 : 35 erg / cm ² Imaging property I (20 ° C., 65% RH): Good II (30 ° C., 80% RH): Good water retention: ◎ Good printing durability: 10,000 sheets or more As described above, the electrostatic properties and printability were good. Examples 3 to 18: Resin [A] shown in Table 12 below, 6 g each (as solid content),
Resin particles [L] 2.5 g (as solid content), resin [B-3] 31.5 g having the following structure and methine dye [III]
Each light-sensitive material was prepared in the same manner as in Example 1 except that 0.018 g was used.

[0311]

[Chemical formula 66]

The electrostatic characteristics and printability of each photosensitive material were examined in the same manner as in Example 1. The results are shown in Table-11.

[0313]

[Table 25]

The electrostatic characteristics are 30 as shown in Table-11.
Very good results were shown even under severe conditions of ℃ and 80% RH. The actual image pick-up was good, the water retention as the master plate for these offset masters was good, and the printing durability was able to print up to 10,000 sheets. Examples 19 to 22 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 12 below were used instead of the spectral sensitizing dye [I].

[0315]

[Table 26]

[0316]

[Table 27]

With respect to each of the light-sensitive materials, the electrostatic characteristics and the printing characteristics were measured in the same manner as in Example 1. As a result, the chargeability, the dark charge retention rate and the photosensitivity were all excellent, and the actual copy image was high at high temperature. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image free of background fog and fine line skipping was provided.

Further, when the performance of the offset lithographic original plate was evaluated by desensitizing treatment in the same manner as in the examples, the water retention of the original plate was good, and 10,000 sheets could be printed even in the actual printing result after plate making. .

However, in the desensitizing treatment, instead of E-1 used in Example 1, a desensitizing treatment solution E- having the following formulation was used.
2 was used. Desensitizing treatment liquid: E-2 β-mercaptopropionic acid 85 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8 g Methyl ethyl ketone 100 g was dissolved in distilled water to a total volume of 1.0 liter, and the pH was adjusted to 11.0 with potassium hydroxide. It was adjusted. Example 23 and Comparative Example C (Example 23) 6 g of resin [A-10], 32 g of resin [B-5] having the following structure, 2 g of resin particles [L-33], 200 g of zinc oxide, 0.02 g of uranine, rose Bengal 0.
04 g, bromphenol blue 0.03 g, phthalic anhydride 0.20 g and toluene 300 g in a homogenizer at a rotation speed of 1 × 10 ⁴ r. p. m. Dispersion for 5 minutes, then, to this dispersion, 0.03 g of 1,2,4,5-benzenetetracarboxylic dianhydride and 0.001 g of phenol are added, and the rotation speed is further adjusted to 1 × 10 ³ r. p.
m. Dispersed for 1 minute. This was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 110 ° C. for 1 minute. Then in the dark at 20 ℃,
The electrophotographic photosensitive material shown in Table 14 below was prepared by leaving it under the condition of 65% RH for 24 hours.

[0320]

[Chemical formula 67]

(Comparative Example C) Example 3 was repeated except that in place of 4 g of the resin [A-10] and 32.0 g of the resin [B-5] in Example 23, only 36.0 g of the resin [B-5] was used. An electrophotographic photosensitive member was produced in the same manner as in No. 23. The characteristics of each photoconductor were examined in the same manner as in Example 1, and the results are shown in Table-1.
Noted in 3.

[0322]

[Table 28]

In the above measurement, the same operations as in Example 1 were carried out except that the electrostatic properties and the image pickup properties were in accordance with the following operations. Note 6) Method for measuring E _1/10 of electrostatic characteristics: The surface of the photoconductive layer was charged to −400 V by corona discharge, and then the surface of the photoconductive layer was irradiated with visible light having an illuminance of 2.0 lux to obtain the surface. The time until the potential (V ₁₀ ) decays to 1/10 is obtained, and the exposure dose E _1/10 (lux · sec) is calculated from this. Note 7) Imaging property: Each light-sensitive material was allowed to stand for one day under the following environmental conditions and then obtained by plate-making using ELP-T as a toner with a fully automatic plate-making machine ELP-404V (manufactured by Fuji Photo Film Co., Ltd.). The resulting copied image was visually evaluated for fogging and image quality. Environmental conditions at the time of imaging are 20 ° C and 65% R
It was carried out at 30 ° C. and 80% RH (II) with H (I). Note 8) Water retention and printing durability Instead of the desensitizing treatment liquid E-1 used in Example 1, the following desensitizing treatment liquid E-
The procedure was performed in the same manner as in Note 4) and Note 5) except that the number was changed to 3.

Desensitizing treatment liquid: E-3 Thioglycolic acid 80 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 6 g Benzyl alcohol 100 g was dissolved in distilled water to a total volume of 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide. It was adjusted.

In both of the present invention and Comparative Example C, the electrostatic characteristics were good and a clear copy image could be obtained. Further, when used as an offset master original plate, the present invention had good water retention property and printing durability of up to 10,000 sheets.
However, Comparative Example C excluding the resin particles did not have sufficient water retention after being hydrophilized as a forced condition, and when actually printed with desensitization under normal conditions, the background stains in the non-image area were Up to 5,000 prints could not be seen.

From the above, only the photosensitive material of the present invention was able to maintain excellent electrostatic characteristics and printing characteristics. Examples 24 to 31 In Example 23, 6 g of resin [A] shown in Table 14 below.
Each photosensitive material was prepared in the same manner as in Example 23 except that (as solid content), 2 g of resin particles [L] (as solid content) and 32 g of resin [B-5].

[0327]

[Table 29]

All of the light-sensitive materials of the present invention are excellent in chargeability, dark charge retention rate and photosensitivity, and actual copy images also cause fog in the harsh conditions of high temperature and high humidity (30 ° C., 80% RH). It gave a clear image without the occurrence of fine line skipping.

Further, when printing was carried out as an offset master original plate, a printed matter of clear image quality with no background stain was obtained even after printing 10,000 sheets. Examples 32 to 39 Photosensitive materials were produced in the same manner as in Example 1 except that the resin particles [L-3] shown in Table 15 below were used in place of the resin particles [L-3].

[0330]

[Table 30]

After plate-making each light-sensitive material in the same manner as in Example 1, the obtained original plate was dipped in ELP-FX for 3 minutes and further dipped in the desensitizing solution E-2 for 1 minute. After the desensitization treatment, printing was carried out in the same manner as in Example 1 to obtain 10,000 prints of clear image quality with no background stain. Examples 40 to 43 In the same manner as in Example 23 except that 31.5 g of the binder resin shown in Table 16 below was used in place of 32 g of the resin [B-5] in Example 23, each electrophotographic photosensitive member was prepared. Created.

[0332]

[Table 31]

When a plate was prepared using the same apparatus as in Example 1, the density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear. Further, when desensitizing treatment was performed and printing was performed by a printing machine, the printed matter after printing 10,000 sheets had no fog in the non-image area and the image quality was clear.

Further, this light-sensitive material was allowed to stand under the environmental conditions of 45 ° C. and 75% RH for 3 weeks, and then the same processing as the above was carried out, but there was no change from the time before. Examples 44 to 55 Using each of the photosensitive materials produced in Examples 1 to 43, an etching process was performed as described below to produce a master plate for offset printing. The original plate was passed through an etching machine once using ELP-FX, and then distilled to 0.5 g of a nucleophilic compound shown in Table 17 below, 100 g of an organic solvent and 10 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.). After adding water to 1 liter, adjust the pH of each mixture to 10.0.
Adjusted to. Each light-sensitive material was dipped 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.

[0336]

[Table 32]

The contact angle of each material with water in the non-image area is 1
It was sufficiently hydrophilized at 0 ° or less. Further, even when the number of printed sheets was 10,000, the print quality of the printed matter was good, with clear images without background fog.

[0338]

EFFECT OF THE INVENTION According to the method for producing a lithographic printing plate precursor of the present invention, a clear and high-quality image having excellent electrostatic characteristics (especially, electrostatic characteristics under severe conditions) is obtained, and an electrophotographic system is used. As a master plate for offset masters having good image quality, it is possible to obtain a printing master plate having good water retention and excellent printing durability. Further, the lithographic printing plate precursor obtained by the production method of the present invention is effective for a scanning exposure system using a semiconductor laser beam.

Claims (4)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive support and at least one photoconductive layer containing at least photoconductive zinc oxide particles, a spectral sensitizing dye, and a binder resin. The photoconductive layer contains at least one resin [A] having the following content as the binder resin, and the photoconductive layer has a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. An electrophotographic photoreceptor containing at least one kind of non-aqueous dispersion resin particles [L] having the following content having an average particle diameter is image-exposed to form a toner image, and then a non-image other than the toner image area is formed. Part of the photoconductive layer is desensitized with a treatment liquid containing a hydrophilic compound having a nucleophilic constant n of at least a value of 5.5 or more to obtain a lithographic printing plate. Original plate manufacturing method. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and having a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more, —PO ₃ H ₂ , -S
_{O 3 H, -COOH, -P (} = O) (OH) -R 01 [R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group)] and a cyclic acid anhydride-containing group as a polymer component having at least one polar group.
Resin containing 5 to 15% by weight. [Chemical 1] [However, in the above formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ₀₃ represents a hydrocarbon group. Non-aqueous dispersion resin particles [L]: at least a formyl group and / or a functional group represented by the following general formula (II), which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the non-aqueous solvent A monofunctional monomer [C] having one kind is dispersed in the presence of a dispersion stabilizing resin soluble in the solvent, which contains at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. Copolymer resin particles obtained by a polymerization reaction. [Chemical 2] [However, in the above formula (II), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or
₁ , A ₂ represents an organic residue which is linked to each other to form a ring] 2. The above-mentioned resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and general formula (Ib) as a copolymer component represented by the general formula (I). The method for producing a lithographic printing plate precursor according to claim 1, further comprising at least one. [Chemical 3] [In the formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ₀₄ or —COOR.
₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ each represent a single bond or a connecting atom number of 1 to 4 which connects —COO— and the benzene ring. Represents a linking group of. ] 3. In the above non-aqueous solvent-based dispersed resin particles,
The method for producing a lithographic printing plate precursor according to claim 1 or 2, wherein the polymer component having a formyl group and / or the functional group represented by the general formula (II) forms a crosslinked structure. 4. The dispersion stabilizing resin comprises a polymer chain in the polymer chain.
The method for producing a lithographic printing plate precursor according to any one of claims 1 to 3, which contains at least one polymerizable double bond group moiety represented by the following general formula (III). [Chemical 4] [In the general formula (III), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CONR 1 -, - S
_{O 2 NR 1 -, - C} 6 H 4 -, - CONHCOO- or -CONHCONH- a represents (wherein, p represents an integer of 1 to 4, R ₁ is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms , B ₁ and b ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or —CO via a hydrocarbon group.
Represents O—R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)