JP2980714B2 - Electrophotographic lithographic printing original plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic lithographic printing plate precursor made by electrophotography, and more particularly to an improvement in a composition for forming a photoconductive layer of the lithographic printing plate precursor.

[0002]

2. Description of the Related Art At present, various types of offset original 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 photoreceptor provided with the photoconductive layer as a component undergoes a normal electrophotographic process to form a highly lipophilic toner image on the surface of the photoreceptor, and then the surface is treated with a desensitizing solution called an etch solution. A technique for obtaining an offset original plate by selectively hydrophilizing a non-image portion is widely used.

In order to obtain a good printed matter, first, the original image is faithfully copied onto an offset original plate, the surface of the photoreceptor is easily compatible with the desensitizing solution, and the non-image portion is sufficiently hydrophilized. It has water resistance, and furthermore, in printing, the surface conductive layer having an image does not separate, and the fountain solution and bleeding are good, and the non-image portion is sufficiently formed so that even if the number of printed sheets is increased, stains do not occur. That hydrophilicity is maintained,
And the like.

[0004] It has been found that these properties are greatly affected by the type of binder resin in the photoconductive layer. In particular, as an offset master, a zinc oxide binder resin having improved desensitization properties is used. Are variously studied. In particular, multi-component copolymers containing at least a methacrylate (or acrylate) component have been proposed, for example, Japanese Patent Publication Nos. 50-31011, 53-4027, 57-202544 and 58-58. No. 68046.

[0005]

However, even if the above-mentioned resin is said to be effective for improving the desensitization property, it is still satisfactory in terms of background stain and printing durability when actually evaluated. Was not. Further, JP-A-1-232356,
JP-A 1-261657 describes that addition of resin particles containing a hydrophilic group to a photoconductive layer is effective in improving water retention.

[0006] It has been confirmed that the water retention is remarkably improved by improving the photoconductive composition.
However, a more detailed evaluation of the lithographic printing plate precursor reveals that when environmental changes (high temperature / high humidity or low temperature / low humidity) occur,
Electrophotographic characteristics (especially charge retention in the dark, light sensitivity, etc.) fluctuated, and a stable and good copied image could not be obtained. As a result, as a result, the printed image of a printed material using the same as a printing original plate is deteriorated, or the effect of preventing background contamination is reduced.

In addition, when a scanning exposure method using a semiconductor laser beam is employed in an electrophotographic lithographic printing original plate as a digital direct lithographic printing original plate, the time becomes longer as compared with the whole-surface simultaneous exposure method using visible light. In addition, since the exposure intensity is limited, electrostatic characteristics,
In particular, higher performance is required for dark charge retention characteristics and light sensitivity.

On the other hand, in the above-mentioned known original plate, the electrophotographic characteristics are deteriorated, the ground fog is liable to occur in the actual copied image, and the thin lines are skipped and the characters are blurred.
As a result, when printed as a lithographic printing original plate, the image quality of the printed matter deteriorates, and the effect of preventing background contamination by improving the hydrophilicity of the non-image portion of the binder resin is lost.

The present invention is to improve the problems of the conventional electrophotographic lithographic printing plate precursor as described above.
That is, the first object of the present invention is to provide a copy image which is excellent in electrostatic characteristics (especially dark charge retention and light sensitivity), faithfully reproduces an original image, and is uniform as an offset original. Another object of the present invention is to provide a lithographic printing plate precursor which does not generate dot-like background stains and has excellent desensitization properties. A second object of the present invention is to provide a lithographic printing original plate having a clear and high-quality image even when the environment at the time of forming a copied image fluctuates, such as low temperature and low humidity or high temperature and high humidity. A third object of the present invention is to provide a lithographic printing plate precursor that is hardly affected by the type of sensitizing dye that can be used in combination and has excellent electrostatic characteristics even in a scanning exposure method using a semiconductor laser beam.

[0010]

According to the present invention, at least one photoconductive layer containing a photoconductive zinc oxide, a spectral sensitizing dye and a binder resin is provided on a conductive support. In the electrophotographic lithographic printing plate precursor provided, the binder resin contains at least one of the following resins [A], and further contains, in the photoconductive layer, a maximum particle size of the photoconductive zinc oxide particles. It can be achieved by an electrophotographic lithographic printing plate precursor characterized by containing at least one of the following nonaqueous solvent-based dispersed resin particles having the same or smaller particle size than that of the above.

Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component, and -PO ₃ H ₂ , -SO ₃ H, -C
OOH,

Embedded image [R ₁ represents a hydrocarbon group or —OR ₂ (R ₂ represents a hydrocarbon group)] and a repeating unit containing, as a substituent, at least one polar group selected from cyclic acid anhydride-containing groups. Copolymer containing 0.5 to 20% by weight as a polymer component: General formula (I)

Embedded image [However, in the above general formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₃ represents a hydrocarbon group]

Non-aqueous solvent-based dispersed resin particles (L): thiol group, phosphono group, amino group, sulfo group

Embedded image Copolymer resin particles obtained by subjecting a monofunctional monomer (A) containing at least one functional group that forms a group to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the solvent. It has the feature of Further, the resin particles preferably form a high-order network structure.

Further, the resin [A] is preferably of the general formula (I)
Contains at least one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib). General formula (Ia)

Embedded image General formula (Ib)

Embedded image [However, in the above formula (Ia) or (Ib), T ₁
And T ₂ each independently represent a hydrogen atom, a carbon number of 1 to 10
Hydrocarbon group, halogen atom, -COR ₄ or -COO
R ₅ (R ₄ and R ₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent a single bond or a connecting atom number of 1 to 4 connecting —COO— and a benzene ring. Represents two linking groups)

The lithographic printing plate precursor according to the present invention is a liquid for desensitizing the non-image area of the photoconductive layer, which contains at least the photoconductive zinc oxide, the spectral sensitizing dye and the binder resin in the photoconductive layer as the uppermost layer. This is a printing original plate of a type in which the surface is made hydrophilic by treating with a method described above to form a lithographic printing original plate.

The photoconductive layer of the present invention comprises at least a small amount of resin [A] composed of at least photoconductive zinc oxide, a spectral sensitizing dye, a specific copolymer component, and non-aqueous solvent-based dispersed resin particles (hereinafter referred to as resin). (Which may be abbreviated as particle [L]).

The resin particles 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 uniform particle diameter. Is preferred.

The resin particles are bonded to at least a polymer component in which the monofunctional monomer (A) has become insoluble in the non-aqueous solvent by a polymerization reaction, and physicochemically and / or chemically bond during the reaction. And a polymer component of a dispersion stabilizing resin which is soluble in the non-aqueous solvent. In addition, the insoluble polymer component of the resin particles [L] is subjected to a desensitizing treatment, whereby a functional group protected by a hydrolysis reaction, a redox reaction, a photolysis reaction, or the like chemically reacts to form the specific hydrophilic group described above. When formed, the properties of the particles are converted from hydrophobic to hydrophilic.

In the present invention, the binder resin [A] is 1 ×
It has a weight average molecular weight of 10 ^{3 to} 2 × 10 ^{4, and} the repeating unit represented by the above general formula (I) is used as a polymer component in an amount of 3
0 wt% or more _{and, -PO 3 H 2, -SO 3} H, -COO
H,

Embedded image [R ₁ represents a hydrocarbon or —OR ₂ (R ₂ represents a hydrocarbon)] and a cyclic unit containing at least one polar group selected from cyclic acid anhydride-containing groups as a polymer. It is a resin containing 0.5 to 20% by weight as a component.

The photoconductive layer of the present invention contains photoconductive zinc oxide particles, a spectral sensitizing dye, and resin particles [L], and zinc oxide is produced by the action of resin [A] contained as a binder resin. The particles are finely divided and uniformly dispersed, and the resin particles [L] are also uniformly dispersed. Further, the interaction between the zinc oxide particles and the spectral sensitizing dye is sufficiently performed. In particular, even when the type of the dye is variously changed, any of the dyes sufficiently interacts with the zinc oxide particles as the photoconductor. Can be formed.

For example, in the case of using a spectral sensitizing dye for semiconductor laser light, which has attracted particular attention in recent years, this interaction is not sufficient in a known binder resin system, and actual electrophotographic characteristics (for example, dark charge) (Retention rate, light sensitivity, etc.) are remarkably reduced, and the captured copied image is deteriorated to such an extent that it is not practically usable.

Although the details of these phenomena are unknown, in the present invention, when the zinc oxide particles and the spectral sensitizing dye are dispersed in the co-presence of the resin particles [L] and the resin [A], the specific phenomena are determined. The low molecular weight resin [A] comprising a specific polar group bonded to a specific position and the monodisperse fine particle diameter resin particles containing the specific polar group have a stoichiometric amount of photoconductive zinc oxide. In addition, it is possible to absorb photo-conductive zinc oxide and to improve the humidity characteristics by compensating for the trap of photo-conductive zinc oxide and to improve the humidity characteristics dramatically. It is presumed that zinc is sufficiently dispersed to suppress aggregation.

In the lithographic printing plate precursor according to the present invention, the dispersion state of the photoconductive zinc oxide including the spectral sensitizing dye to the microscopic state is controlled only by the appropriate presence of both the resin particles and the resin [A]. Therefore, it is considered that the electrophotographic characteristics (especially the actual image-capturing properties) are improved, and good performance can be stably maintained even under severe conditions of high temperature and high humidity or low temperature and low humidity.

In other words, in the present system, if the electrophotographic characteristics do not show excellent performance, background contamination may occur in a non-image portion during reproduction of a copied image, or the reproducibility of a document in the image portion may deteriorate. What is particularly important is that the non-image portion is sufficiently hydrophilicized by the desensitizing treatment and has high water retention that does not cause ink adhesion at the time of printing, since it is impossible to obtain a product satisfying the image quality. The lithographic printing plate precursor of the present invention is:
With desensitizing by desensitizing solution of the zinc oxide particles, resin particles by desensitizing treatment to further improve the water retention of the photoconductive layer non-image portion by expressing hydrophilicity by specific parent aqueous base It is characterized by having a function. Water retention in the non-image area of the printing plate precursor of the present invention is estimated as also drastically improved by more such action.

Further, as described above, the particles to be hydrophilized are dispersed in the photoconductive layer in an appropriate state by the action of the resin [A], so that the zinc oxide particles and the resin particles can be hydrophilized. It is thought to proceed easily, quickly and sufficiently.

On the other hand, in the resin particles of the present invention, if the resin particles having a particle diameter larger than the zinc oxide particle diameter are present, the electrophotographic characteristics are deteriorated (particularly, uniform chargeability cannot be obtained). In the copied image, density unevenness in the image portion, breakage or jumping of characters and fine lines, or background fog in the non-image portion occurs. Specifically, the maximum particle size of the resin particles of the present invention is 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 diameter, the larger the specific surface area of the resin particles. The resin particles have a good effect on the above-mentioned electrophotographic properties, and the colloidal particles (0.01 μm or less) are sufficient. Since it is similar to the case of dispersion and the effect of the particles for improving the water holding power is weakened, it is preferable to use the particles having a particle diameter of 0.001 μm or more.

In the present invention, the resin particles are obtained by binding a hydrophobic polymer component, that is, a polymer component corresponding to the dispersion stabilizing resin, and the hydrophobic portion is combined with the binder resin of the photoconductive layer. Because of the interaction, it does not elute with the dampening solution at the time of printing due to the anchor effect of this portion, and it is possible to maintain good printing characteristics even when printing a considerably large number of sheets.

Further, when the polymer component of the dispersion stabilizing resin contains a light and / or thermosetting functional group, it is possible to further suppress elution by chemical bonding.

Further, in the present invention, if the resin particles form a high-order network structure, the dissolution property in water is further suppressed, while the water swelling property is exhibited, and the water retention property is further improved. In the present invention, the resin particles that do not form a higher-order network structure as described above or the resin particles that form a higher-order network structure (hereinafter simply referred to as “network resin particles”) are 100% by weight of photoconductive zinc oxide. It is preferably used in an amount of 0.01 to 10% by weight based on parts. If the amount of the resin particles or the network resin particles is less than 0.01% by weight, the hydrophilicity of the non-image portion is not sufficient, and if it is more than 10% by weight, the hydrophilicity of the non-image portion is further improved, but severe. The electrophotographic characteristics under the conditions deteriorate, and the copied image deteriorates.

Next, the photoconductive layer of the electrophotographic photosensitive material of the present invention will be described. The photoconductive layer of the present invention is characterized by containing at least one of the following resins [A] as a binder resin. The resin [A] comprises a specific polymer component represented by the following general formula (I) in an amount of 30% by weight or more and -PO
_{3 H 2, -SO 3 H,} -COOH,

Embedded image [R ₁ is a hydrocarbon group or -OR ₂ group (R ₂ is a hydrocarbon group), at least containing a 0.5 to 20% by weight of the polymer component containing a polar group selected from a cyclic acid anhydride-containing group It is a low molecular weight resin. General formula (I)

Embedded image [In the formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ₃ represents a hydrocarbon group.]

In the resin [A], the weight average molecular weight is 1
× 10 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 1
0 is ^4, the glass transition point of the resin (A) is preferably -
30 ° C to 110 ° C, more preferably -20 ° C to 90 ° C.

When the molecular weight of the resin [A] is smaller 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 larger than 2 × 10 ⁴ , even if the resin of the present invention is used, especially in photoreceptors using near infrared to infrared spectral sensitizing dyes, high temperature and high humidity, variation in the dark decay retention and photosensitivity in harsh conditions of the low-temperature and low humidity becomes somewhat large, stable The effect of the present invention that a copied image can be obtained is weakened.

The proportion of the polymer component corresponding to the repeating unit of the general formula (I) in the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the polar group-containing copolymer component. Is 0.5 to 20% by weight, preferably 1 to 10% by weight.
% By weight. If the content of the polar group-containing component in the resin [A] is less than 0.5% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, when the content of the polar group-containing component is more than 20% by weight, the dispersibility of the low molecular weight compound is reduced, and the background smear increases when used as an offset master.

Next, the repeating unit represented by the above formula (I), which is contained in the resin [A] in an amount of 30% by weight or more, will be further described. In the general formula (I), a ₁ and a ₂ are preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), —COO—R _{3 '} Or -COO via a hydrocarbon group
—R _{3 ′} (R _{3 ′} 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, represents a represents) the same contents as those described below R _3. Examples of the hydrocarbon in the —COO—R _{3 ′} group via the hydrocarbon include a methylene group, an ethylene group, and a propylene group. R ₃ represents a hydrocarbon group, specifically, an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring.
That is, R ₃ is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a 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.), and may have 2 to 18 carbon atoms. An alkenyl group (eg, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, naphthyl group) Methyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), having 5 to 8 carbon atoms
Optionally substituted cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.),
An aryl group which may be substituted (for example, a phenyl group,
Tolyl, xylyl, mesityl, naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl Group, cyanophenyl group, etc.).

In the repeating unit of the general formula (I) which is a methacrylate component having such a substituent R ₃ ,
More preferably, a polymer component corresponding to the repeating unit represented by the following general formula (Ia) and / or general formula (Ib) is exemplified. General formula (Ia)

Embedded image General formula (Ib)

Embedded image [In the formulas (Ia) and (Ib), T ₁ and T ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom,
And —COR ₄ and —COOR ₅ (R ₄ and R ₅ each represent a hydrocarbon group having 1 to 10 carbon atoms). L ₁ , L
₂ represents a direct bond or a linking group having 1 to 4 linking atoms, each linking -COO- and a benzene ring]

In the formula (Ia), preferred T ₁ and T
_{As 2} independently independently of each other a hydrogen atom and a halogen atom , a C1 to C10 hydrocarbon group, preferably a C1 to C4 alkyl group (for example, a methyl group, an ethyl group,
A propyl group, a butyl group, etc., an 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 - benzyl) and aryl groups (e.g. phenyl group, a tolyl group, a silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₄ and -COOR ₅ (preferably R ₄ and R ₅ is the above-mentioned carbon number 1 to 10 respectively
And the preferred hydrocarbon groups described above can be mentioned).

In the formulas (Ia) and (Ib), L ₁ and L ₂ each represent a direct bond connecting —COO— to a benzene ring or — (CH ₂ ) _n1 — (n ₁ represents an integer of ₁ to 3) _{), - CH 2 OCO -,} - CH 2 CH 2 OCO -, -
_{(CH 2) m1 - (m} 1 represents an integer of 1 or 2), - C
H ₂ CH ₂ O-such as a such as linking atoms 1-4 linking groups, more preferably it may be mentioned direct bond or bond atoms 1-2 linking groups.

The formula (I) used in the resin [A] of the present invention
Specific examples of the repeating unit represented by a) or (Ib) are shown below. However, the scope of the present invention is not limited to this. In the following (a-1) to (a-20), n is an integer of 1 to 4, m is 0 or an integer of _{1 to} 3, and p ₁
Is an integer of 1 to 3, R ₈ to R ₁₁ are both -C _n H _{2n + 1} or _{- (CH 2) m -C 6} H 5 ( except, n, m are as defined above), X ₁ and X ₂ may be the same or different and represents a hydrogen atom, -Cl, -Br, or -I. (A-1)

Embedded image (A-2)

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Embedded image (A-18)

Embedded image (A-19)

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Next, the polar group-containing component of the low molecular weight resin [A] will be described. Polar group, -PO ₃ H _2, -S
O ₃ H, -COOH,

Embedded image It is preferable that at least one selected from cyclic acid anhydride-containing groups is used.

Embedded image In the group, R ₁ represents a hydrocarbon group or an —OR ₂ group (R ₂ represents a hydrocarbon group), and specifically, R ₁ has ₁ carbon atom.
To 6 optionally substituted hydrocarbon groups (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-
Chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxy, ethoxymethyl group, 2-ethoxyethyl group) and the like, and R ₂ is the same as R ₁ It is. Also,
The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the contained cyclic acid anhydride include an aliphatic dicarboxylic anhydride and an aromatic dicarboxylic anhydride. Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, a cyclopentane-1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic acid. An anhydride ring, a cyclohexene-1,2-dicarboxylic anhydride ring, a 2,3-bicyclo [2,2,2] octadicarboxylic anhydride ring and the like are mentioned, and these rings are, for example, a chlorine atom, a bromine atom Such as halogen atom, methyl group, ethyl group,
An alkyl group such as a butyl group and a hexyl group may be substituted. Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, and a thiophene-
Dicarboxylic anhydride rings and the like, these rings are, for example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group,
An alkyl group such as an ethyl group, a propyl group, and a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (an alkoxy group such as a methoxy group and an ethoxy group) may be substituted.

The copolymer component containing a polar group of the resin [A] is, for example, copolymerized with a monomer corresponding to a repeating unit represented by the general formula (I) (including the general formulas (Ia) and (Ib)). Any vinyl compound containing the polar group that can be polymerized may be used. For example, “Polymer Data ・
Handbook [Basic Edition], Baifukan (1986) and the like. Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy, α-acetoxymethyl, α- (2-amino) methyl, α-
Chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro-β-methoxy, α, β-dichloro, etc. ), Methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, -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, dicarboxylic acid Half-ester derivatives of vinyl or allyl groups, and ester derivatives of these carboxylic or sulfonic acids,
Compounds containing the polar group in the substituent of the amide derivative are exemplified.

Examples of the copolymer component containing a polar group are described below. Here, b ₁ represents H or CH ₃ , b ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₃ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and c represents 1 to
3 represents an integer, d represents an integer of 2 to 11, and e represents 1 to
11 represents an integer of 11, f represents an integer of 2 to 4, and g represents 2 to
Indicates an integer of 10. (B-1)

Embedded image (B-2)

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Further, the low molecular weight resin [A] may be used together with the above-mentioned monomers of the general formulas (I), (Ia) and / or (Ib) and the monomer containing the polar group, and other resins. Other monomers may be contained as a copolymer component.

Examples of such other copolymerization components include methacrylates, acrylates and crotonates having substituents other than those described in the general formula (I), and α-olefins. , Vinyl carboxylate or acrylic acid esters (for example, carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (for example, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, Le naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

The resin [A] has a weight average molecular weight of 1 × 10
These are random copolymers having a low molecular weight of ^{3 to} 2 × 10 ⁴ , and these polymerization methods are easily synthesized by a conventionally known method such as radical polymerization or ionic polymerization by selecting polymerization conditions. be able to. A radical polymerization reaction is advantageous and preferred from the viewpoint of purification, equipment, reaction method, etc., based on the monomer to be polymerized, the polymerization solvent, the reaction set temperature, and the like.

Specifically, examples of the polymerization initiator include generally known azobis-based initiators and peroxides.
In particular, as a feature of synthesizing a low molecular weight compound, a known method such as increasing the amount of the initiator used or increasing the set polymerization temperature may be applied. Specifically, the amount of the initiator used is 0.1 to 100 parts by weight of the total amount of the monomers.
In the range of 20 parts by weight, the polymerization set temperature is 30 ° C. to 200 ° C.
Perform within the range.

Further, a method in which a chain transfer agent is used in combination is also known. For example, a mercapto compound, a halogenated compound, or the like is used in an amount of 0.01 to 10 based on 100 parts by weight of the total amount of the monomers.
When used in the range of parts by weight, it can be adjusted to a desired weight average molecular weight.

The resin [A] having a low molecular weight as described above is preferably used in combination with the above-mentioned known resin for photoconductive zinc. The ratio of the low molecular weight resin to the other resin is 5 to 5.
50/95 to 50 (weight ratio) is preferred. Other resins used in combination include a weight average molecular weight of 3 × 10 ⁴ to 1 × 1.
0 ^6, preferably from 5 × 10 ⁴ ~ high molecular weight in the to 5 × 10 ^5. The glass transition point of the resin used in combination is -1.
The temperature is from 0 ° C to 120 ° C, preferably from 0 ° C to 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), 9th
Page, edited by Koichi Nakamura, "Practical technology of binders for insulating materials"
Chapter 10, C.I. H. C. Publishing (1985), DD
Tatt, SC Heidecker, Tappi, 49 (No. 10),
439 (1966), ES Baltazzi, RG Blanclo
tte et al, Phot. Sci. Eng. 16 (No. 5), 354
(1972), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, Journal of the Institute of Electrophotography 18 (No. 2), 28 (198)
0), JP-B-50-31011, JP-A-53-5402.
7, 54-20735, 57-202544, 5
The materials disclosed in JP-A-8-68046 and the like are listed.

Further, as a resin of a medium to high molecular weight, which is a preferable resin to be used in combination, a resin which satisfies the above-mentioned physical properties and preferably contains a polymer component of a repeating unit represented by the following general formula (III) in an amount of 30% by weight or more. Coalescence. General formula (III)

Embedded image [In the formula (III), V represents -COO-, -OCO-,-(CH
_{2) h -OCO -, - (} CH 2) h -COO -, - O-
Or -SO ₂ - represents a. Wherein h represents an integer of 1 to 4] In the general formula (III), b ₃ and b ₄ represent 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, a methyl group,
Ethyl group, propyl group, butyl group, etc. ) . R ₁₄ is
An optionally substituted alkyl group having 1 to 18 carbon atoms (for example, 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-
A hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group and the like, an optionally substituted alkenyl group having 2 to 18 carbon atoms (for example, a vinyl group, an allyl group, an isopropenyl group, Butenyl group,
A hexenyl group, a heptenyl group, an octenyl group and the like, an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-
A naphthylethyl group, a methoxybenzyl group, an ethoxybenzyl group, a methylbenzyl group, etc., an optionally substituted cycloalkyl group having 5 to 8 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc.), Aryl groups (eg, phenyl, tolyl, xyl, mesityl, naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl,
Difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, nitrophenyl group, etc.).

Examples of the medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (III) include, for example, a resin of a random copolymer containing the polymer component represented by the formula (III). (Japanese Unexamined Patent Publication Nos. 63-49817 and 63-22014)
9, 63-220148, etc.), and a resin used in combination with the random copolymer and a crosslinkable resin (JP-A 1-2117)
66, JP-A-1-102573, etc.) and copolymers containing a polymer component represented by the formula (III) and partially crosslinked in advance (JP-A-2-34860, JP-A-2-40660). And a graft-type block copolymer obtained by polymerization of a monofunctional macromonomer composed of a polymer component having a specific repeating unit and a monomer corresponding to the component represented by the formula (III) (Japanese Patent Application No. 63-203933, 63-20
7317, JP-A-1-163796 and JP-A-12-21299
4, No. 1-229379 and No. 1-189245), and the like.

In the present invention, the resin [A] is a low-molecular-weight copolymer containing a methacrylate copolymer component having a specific substituent and a polymer component containing a specific polar group, and the polar group is a photopolymer. Since it is adsorbed on the stoichiometric defect of the photoconductor of the conductive layer and is a low molecular weight material, the trapping of the photoconductor is improved by improving the covering property of the surface of the photoconductor, and the temperature is improved. It was found that while the properties were dramatically improved, the photoconductor was sufficiently dispersed and aggregation was suppressed. As a result, it has been found that the electrophotographic properties of the electrophotographic photoreceptor are excellent, and particularly, even when a spectral sensitizing dye for semiconductor laser light is used, extremely excellent performance is exhibited.

When the resin [B] having a medium to high molecular weight is used in combination, the high performance of the electrophotographic properties due to the use of the resin [A] is not impaired at all, and the photoconductive property is higher than that of the resin [A] alone. It was found that the mechanical strength of the conductive layer could be sufficiently improved.
That is, the interaction between the adsorption and coating of the photoconductor and the binder resin is appropriately performed, and the film strength of the coated conductive layer is maintained. This is considered to be due to the following effects of the binder resin according to the present invention. That is, in the present invention, the resin [A] and the resin [B] are used in combination as the binder resin, and the weight average molecular weight Mw of each resin and the content of the polar group in the resin are specified, whereby the photoconductor and the resin are used. The strength of the interaction with the resin can be changed. Thereby, the resin [A] having a stronger interaction is selectively and appropriately adsorbed to the photoconductor, and the resin [B] having a weaker interaction than the resin [A] is
A polar group bonded to a specific position with respect to the polymer main chain in the resin slowly interacts with the photoconductor so as not to inhibit the electrophotographic properties, and has a long molecular chain length and a graft molecular chain length. It is considered that both the electrophotographic properties and the mechanical strength of the film were significantly improved as described above by having the interaction between the molecular chains of the resins [B].

Next, the resin particles [L] of the present invention will be described in detail. The functional group used in the present invention, which decomposes to form at least one hydrophilic group such as a thiol group, a phosphono group, a sulfo group, or an amino group (hereinafter sometimes simply referred to as a hydrophilic group-forming functional group). explain in detail. Although the hydrophilic group-forming functional group of the present invention generates at least one hydrophilic group by decomposition, one or two or more hydrophilic groups may be generated from one functional group.

Hereinafter, the functional group that generates at least one thiol group by decomposition (thiol group-forming functional group) will be described in detail. According to one preferred embodiment of the present invention, the thiol group-forming functional group-containing monomer is a compound represented by general formula (IV) - the [S-L ^A] functional group represented by at least
It contains species. Formula (IV): [- S-L ^A] wherein, L ^A is

Embedded image However, R ^A _1, R ^A ₂ and R ^A ₃ may be the same or different, each represents a hydrocarbon group or -O-R ^AI (R ^AI is a hydrocarbon group), R ^A _4, R ^A ₅ , ^RA ₆ ,
_{^{R A 7, R A 8,}} R A 9 and _{^{R A 10, R A 11,}} R A 12,
R ^A ₁₃ each independently represents a hydrocarbon group.

[0055] functional group of the general formula [-S-L ^A] is degraded by, is intended to generate a thiol group, is described below in more detail. L ^A is

Embedded image In case of representing a, R ^A _1, R ^A ₂ and R ^A ₃ may be the same as or different from each other, preferably a hydrogen atom, an unsubstituted or good C1-18 linear or branched alkyl group ( For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, chloroethyl group, methoxyethyl group,
A methoxypropyl group, etc.), an optionally substituted alicyclic group (eg, cyclopentyl group, cyclohexyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, chlorobenzyl group, A methoxybenzyl group) or an optionally substituted aromatic group (eg, phenyl, naphthyl, chlorophenyl, tolyl, methoxyphenyl, methoxycarbonylphenyl, dichlorophenyl, etc.) or —O—R ^AI (R ^AI represents a hydrocarbon group. Specifically, R ^A ₁ , R ^A ₂ , R
Substituents of the hydrocarbon group for ^A ₃ may be mentioned as examples).

L ^A

Embedded image Or in the case of representing the _{^{-S-R A 8, R A}} 4,
_{^{R A 5, R A 6,}} R A 7, R A 8 are each preferably having 1 to 12 carbon atoms which may be substituted linear or branched alkyl group (e.g. methyl group, trichloromethyl group, trifluoromethyl Group, methoxymethyl group, ethyl group, propyl group, n-butyl group, hexyl group, 3-chloropropyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-i -Propyl group, octyl group, decyl group, etc., and optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.) ), An optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl, Toxiphenyl, butoxyphenyl, chlorophenyl, dichlorophenyl, trifluoromethylphenyl, etc.).

L ^A

Embedded image In case of representing a, R ^A ₉ and R ^A ₁₀ may be the same or different from each other, the preferred examples R ^A ₄ ~
Represent preferred and the substituents R ^A _8.

L ^A is

Embedded image In the formula, Y ₁ represents an oxygen atom or a sulfur atom. ^{_{R A 11, R A 12,}} R A 13 may be the same or different, each preferably represents a hydrogen atom, an unsubstituted or a good 1-12 carbon linear or branched alkyl group.
Preferred examples are the same contents as the R ^A ₄ ~R ^A _8. P ₁ represents an integer of 5 or 6.

Another preferred thiol group-forming functional group-containing monomer of the present invention contains at least one thiirane ring represented by the general formula (V) or (VI). General formula (V)

Embedded image General formula (VI)

Embedded image In formula (V), R ^A ₁₄ and R ^A ₁₅ may be the same or different, each represents a hydrogen atom or a hydrocarbon group.
Preferably represents a hydrogen atom or a substituent and preferred R ^A ₄ ~R ^A _7. In the formula (VI), X ^A represents a hydrogen atom or an aliphatic group. The aliphatic group preferably represents an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

Still another preferred thiol group-forming functional group-containing monomer of the present invention is a monomer containing at least one sulfur atom-containing heterocyclic group represented by the general formula (VII). General formula (VII)

Embedded image In formula (VII), Y ^A represents an oxygen atom or -NH- group. ^RA ₁₆ , ^RA ₁₇ and ^RA ₁₈ may be the same or different and each represent a hydrogen atom or a hydrocarbon group. Preferably represents a hydrogen atom or a substituent and preferred R ^A ₄ ~R ^A _7. R ^A ₁₉ and R ^A ₂₀ may be the same or different, a hydrogen atom, a hydrocarbon group or -O-R
^AII (R ^AII represents a hydrocarbon group). Preferably represents a substituent and preferred by the R ^A ₁ ~R ^A _3.

According to still another preferred embodiment of the present invention, the thiol group-forming functional group-containing monomer is a form in which at least two thiol groups located sterically close to each other are simultaneously protected by one protecting group. Is a monomer containing at least one functional group having Examples of the functional group having at least two thiol groups at positions sterically close to each other in a form protected simultaneously by one protective group include those represented by the following general formulas (VIII), (IX) and (X). Can be mentioned. General formula (VIII)

Embedded image General formula (IX)

Embedded image General formula (X)

Embedded image In the formulas (VIII) and (IX), Z ^A represents a carbon-carbon bond or a chemical bond directly connecting CS bonds which may be via a hetero atom (provided that the number of atoms between sulfur atoms is 4 ). Furthermore one - (Z ^A ··· C) -
The bond represents a mere bond, and may be, for example, as described below.

Embedded image In the formula (IX), ^RA ₂₁ and ^RA ₂₂ may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or -OR.
^AII ( ^RAII represents a hydrocarbon group). The formula (I
In X), R ^A ₂₁ and R ^A ₂₂ preferably may be the same or different, a hydrogen atom, a carbon number 1 to 12
An optionally substituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a 2-methoxyethyl group, an octyl group, etc.) and an optionally substituted aralkyl group having 7 to 9 carbon atoms ( For example, a benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, a chlorobenzyl group, etc., an alicyclic group having 5 to 7 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, etc.) or an aryl group which may be substituted (for example, Phenyl group, chlorophenyl group,
Methoxyphenyl group, a methylphenyl group, cyanophenyl group) or -O-R ^AII (R ^AII has the same meaning as the hydrocarbon group for _{^{R A 21, R A 22)}} . In formula (X), representative of the _{^{R A 23, R A 24,}} R A 25, R A 26 may be the same or different, each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above R ^A ₂₁ , R ^A ₂₂
Represents the same meaning as the above-mentioned preferred hydrocarbon group.

The monomer (A) containing at least one of the functional groups represented by the above general formulas (IV) to (X) used in the present invention is described, for example, in "Reactivity by Yoshio Iwakura and Keisuke Kurita" Polymers, pp. 230-237 (Kodansha: 1977), edited by The Chemical Society of Japan, "New Experimental Chemistry Course, Vol. 14, Synthesis and Reaction of Organic Compounds [III]", Chapter 8, pages 1700-1.
713 pages (Maruzen Co., Ltd., published in 1978), JFWMcOm
ie Protective Groups in Organic Chemistry 7
Chapter (Plenum Press. 1973), S. Patai "The Ch
emistry of the thiol group Part 2 ", Chapter 12, Chapter 1
The method described in Chapter 4 (John Wiley & Sons, 1974) or the like can be applied.

More specifically, examples of the monomer (A) having a functional group represented by any of the general formulas (IV) to (X) include the following compounds. (1)

Embedded image (2)

Embedded image (3)

Embedded image (4)

Embedded image (5)

Embedded image (6)

Embedded image (7)

Embedded image (8)

Embedded image (9)

Embedded image (10)

Embedded image (11)

Embedded image (12)

Embedded image (13)

Embedded image (14)

Embedded image (15)

Embedded image (16)

Embedded image (17)

Embedded image (18)

Embedded image (19)

Embedded image (20)

Embedded image (21)

Embedded image (22)

Embedded image (23)

Embedded image (24)

Embedded image (25)

Embedded image (26)

Embedded image (27)

Embedded image (28)

Embedded image (29)

Embedded image (30)

Embedded image (31)

Embedded image (32)

Embedded image (33)

Embedded image (34)

Embedded image (35)

Embedded image (36)

Embedded image (37)

Embedded image (38)

Embedded image (39)

Embedded image (40)

Embedded image (41)

Embedded image (42)

Embedded image (43)

Embedded image (44)

Embedded image (45)

Embedded image

Next, the functional group which forms at least one phosphono group, for example, a group represented by the following general formula (XI) or (XII) upon decomposition will be described in detail. General formula (XI)

Embedded image General formula (XII)

Embedded image In the formula (XI), R ^B is a hydrocarbon group or —Z ^B ₂ —R
^BI (where R ^BI represents a hydrocarbon, and Z ^B ₂ represents an oxygen atom or a sulfur atom). Q ^B ₁ represents an oxygen atom or a sulfur atom. Z ^B ₁ represents an oxygen atom or a sulfur atom. In the formula (XII), Q ^B ₂ , Z ^B ₃ and Z ^B
₄ each independently represents an oxygen atom or a sulfur atom. Preferably, R ^B is an optionally substituted alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group) or —Z ^B ₂ —R ^BI (where Z ^B ₂ is oxygen .R ^BI representing the atom or sulfur atom represents R ^B. represents the same content _{^{as) Q B 1, Q B 2}} , Z B 1, Z B 3, Z B 4 each independently represent an oxygen atom or a sulfur atom .

By the decomposition as described above, the compound represented by the formula (XI) or (XII)
Examples of the functional group that generates a phosphono group represented by are the functional groups represented by general formulas (XIII) and / or (XIV). General formula (XIII)

Embedded image General formula (XIV)

Embedded image In formulas (XIII) and (XIV), Q ^B ₁ , Q ^B ₂ , Z ^{B
_{1, Z B 3, Z B}} 4 and R ^B represent the content as defined by the respective formulas (XI) and (XII). L ^B _1, L ^B ₂ and L ^B ₃ are each independently of one another

Embedded image Represents L ^B ₁ ~L ^B ₃ is

Embedded image In case of representing a, R ^B ₁ ~R ^B ₂ may be the same or different, each represents a hydrogen atom, a halogen atom (e.g. a chlorine atom, a bromine atom, a fluorine atom) or a methyl group. X ^B ₁ and X ^B _{2 each} represent an electron-withdrawing group (here, the electron-withdrawing group is a substituent having a positive Hammett's substituent constant, such as a halogen atom,

Embedded image And the like), preferably a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), -CN, -
CONH ₂ , —NO ₂ or —SO ₂ ^RBII ( ^RBII is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group,
Represents a hydrocarbon group such as a mesityl group). n is 1
Or 2 is represented. Further, when X ^B ₁ is a methyl group, R
^B ₁ and R ^B ₂ represents n = 1 with a methyl group.

L ^B _{1 to} L ^B ₃

Embedded image In the case of representing, R ^B ₃ , R ^B ₄ and R ^B ₅ may be the same or different from each other, and are preferably a hydrogen atom,
A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group , A methoxyethyl group, a methoxypropyl group, etc.), an alicyclic group which may be substituted (for example, a cyclopentyl group, a cyclohexyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl, phenethyl, chlorobenzyl, methoxybenzyl, etc.), an optionally substituted aromatic group (e.g., phenyl, naphthyl, chlorophenyl, A toryl group, a methoxyphenyl group, a methoxycarbonylphenyl group, a dichlorophenyl group, etc.) or ^-ORBIII ( ^RBIII
Represents a hydrocarbon group, and specifically, R ^B ₃ ,
Represents a R ^B _4, substituents such R ^B ₅ can be cited as an example).

L ^B _{1 to} L ^B ₃ are

Embedded image In case of representing ^{_{a, R B 6, R B 7}} , R B 8, R B 9
And R ^B ₁₀ each independently represents a hydrocarbon group. Preferably, an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl group, 2,2,2- Trifluoroethyl group, ethyl group,
Propyl group, hexyl group, t-butyl group, hexafluoro-i-propyl group, etc.),
9 aralkyl groups (for example, benzyl group, phenethyl group,
A methylbenzyl group, a trimethylbenzyl group, a heptamethylbenzyl group, a methoxybenzyl group, etc., an aryl group having 6 to 12 carbon atoms which may be substituted (for example, a phenyl group,
Tolyl, xylyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl, methoxyphenyl, butoxyphenyl, chlorophenyl, dichlorophenyl, trifluoromethylphenyl, etc.).

[0068] further L ^B ₁ ~L ^B ₃

Embedded image In the formula, Y ^B ₁ and Y ^B ₂ represent an oxygen atom or a sulfur atom.

The functional group used in the present invention has at least one functional group.
The seed-containing monomer can be synthesized by introducing a protecting group according to a conventionally known method. The same synthetic reaction can be used as a method for introducing a protecting group. Specifically, JFWMcOmie “Protective groups
in Organic Chemistry ", Chapter 6 (Plenum Press, 197
Or the hydroxyl group described in “New Experimental Chemistry Lecture Vol. 14, Synthesis and Reaction of Organic Compounds [V]” edited by The Chemical Society of Japan, page 2497 (published by Maruzen Co., Ltd., 1978). Synthetic reaction similar to the method of introducing a protecting group into S. Patai, or `` The Chemistry of the Triol
Group Part 2 ”Chapters 13 and 14 (Wiley-Intersci
ence 1974), TWGreene "Protective group
s in Organic Synthesis ", Chapter 6 (Wiley-Interscien
1981) and the like, and can be produced by the same synthetic reaction as the method for introducing a protecting group into a thiol group.

The formula (XIII) used in the present invention and / or
Alternatively, the following examples can be given as specific examples of the compound which can be a repeating unit of a polymerization component containing a functional group capable of forming a phosphono group of (XIV). (1)

Embedded image (2)

Embedded image (3)

Embedded image (4)

Embedded image (5)

Embedded image (6)

Embedded image (7)

Embedded image (8)

Embedded image (9)

Embedded image (10)

Embedded image (11)

Embedded image (12)

Embedded image (13)

Embedded image (14)

Embedded image (15)

Embedded image (16)

Embedded image (17)

Embedded image (18)

Embedded image

Next, an amino group such as —NH
Examples of the functional group that forms _two groups and / or a —NHR ^C group include groups represented by the following general formulas (XV) to (XVII). General formula (XV)

Embedded image General formula (XVI)

Embedded image General formula (XVII)

Embedded image In the formulas (XV) and (XVII), R ^C ₀ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, hexyl, octyl) Group, decyl group, dodecyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group,
2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-methoxycarbonylethyl group, 3-
A methoxypropyl group, a 6-chlorohexyl group, etc.), an alicyclic group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), an aralkyl group which may be substituted having 7 to 12 carbon atoms (eg, benzyl group, Phenethyl group, 3-
Phenylpropyl group, 1-phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group,
An optionally substituted aryl group having 6 to 12 carbon atoms (e.g., phenyl, chlorophenyl, dichlorophenyl, tolyl, xylyl, mesityl, chloromethyl, chlorophenyl, methoxyphenyl); Ethoxyphenyl group, chloromethoxyphenyl group, etc.). When R ^C ₀ represents the hydrocarbon group, hydrocarbon groups having 1 to 8 carbon atoms are preferred.

In the functional group represented by the formula (XV), R ^C
₁ represents an aliphatic group having 2 to 12 carbon atoms which may be substituted, and more specifically, R ^C ₁ represents a group represented by the following formula (XVIII). Formula (XVIII)

Embedded image In the formula (XVIII), a ₆ and a ₇ each represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or the like) or a carbon atom having 1 to 12 carbon atoms.
Which may be substituted (for example, methyl, ethyl, propyl, butyl, hexyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2
-Chloroethyl group, 3-bromopropyl group, cyclohexyl group, benzyl group, chlorobenzyl group, methoxybenzyl group, methylbenzyl group, phenethyl group, 3-phenylpropyl group, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl A methoxyphenyl group, a dichlorophenyl group, a chloromethylphenyl group, a naphthyl group, etc.), and Y ^C is a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms. (E.g., methyl, ethyl, propyl,
Butyl group, etc.), and an aromatic group which may contain a substituent (for example, phenyl group, tolyl group, cyanophenyl group, 2,6-
Dimethylphenyl group, 2,4,6-trimethylphenyl group, heptamethylphenyl group, 2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2-propylphenyl group, 2-butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group, etc.) or -SO ₂
-R ^C ₆ (R ^C ₆ is Y represent similar content and ^C hydrocarbon group) and the like. n represents 1 or 2.

More preferably, when Y ^C is a hydrogen atom or an alkyl group, a ₆ and a ₇ on carbon adjacent to the oxygen atom of the urethane bond represent a substituent other than a hydrogen atom.
When Y ^C is not a hydrogen atom or an alkyl group, a ₆ and a ₇ may be any of the groups described above. That is,

Embedded image In the above, it is preferable to form a group containing at least one or more electron-withdrawing groups or a case where carbon adjacent to an oxygen atom of a urethane bond forms a sterically bulky group. is there.

R ^C ₁ is an alicyclic group such as a monocyclic hydrocarbon group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclohexyl group, 1-methylcyclobutyl group, etc.) Or a bridged cyclic hydrocarbon group (bicyclooctane group, bicyclooctene group,
Bicyclononane group, tricycloheptane group, etc.).

In the general formula (XVI), R ^C ₂ and R ^C ₃
May be the same or different, each represents a hydrocarbon group having 1 to 12 carbon atoms, specifically, representing the same contents as the aliphatic group or an aromatic group in Y ^C of formula (XV). In the general formula (XVII), X ^C ₁ and X ^C ₂ may be the same or different and each represent an oxygen atom or a sulfur atom.
R ^C ₄ and R ^C ₅ may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms.
It represents an aliphatic group or an aromatic group in Y ^C of V).

Specific examples of the functional groups of formulas (XV) to (XVII) are shown below. As specific monomers containing these functional groups
Is a thiol group or phosphono group
In specific examples of the monomer containing a functional group, the thiol group
Unit instead of a functional group or phosphono group functional group
And the like. (1)

Embedded image (2)

Embedded image (3)

Embedded image (4)

Embedded image (5)

Embedded image (6)

Embedded image (7)

Embedded image (8)

Embedded image (9)

Embedded image (10)

Embedded image (11)

Embedded image (12)

Embedded image (13)

Embedded image (14)

Embedded image (15)

Embedded image (16)

Embedded image (17)

Embedded image (18)

Embedded image (19)

Embedded image (20)

Embedded image (21)

Embedded image (22)

Embedded image (23)

Embedded image (24)

Embedded image (25)

Embedded image (26)

Embedded image (27)

Embedded image

The functional group used in the present invention to generate an amino group (for example, a —NH ₂ group and / or a —NHR group) by decomposition, for example, a functional group selected from the group of the above general formulas (XV) to (XVII) Monomers containing at least one compound are described, for example, in "Nippon Kagaku Koza Koza Vol. 14, Synthesis and Reaction of Organic Compounds [V]", page 2555 (published by Maruzen Co., Ltd.), JFW McOmie, "Protective groups in Organic". C
hemistry ”Chapter 2 (PlenumPress 1973),“ P
rotective groups in Organic Sinthesis ", Chapter 7 (Joh
n Wiley & Sons, 1981) and the like.

Further, examples of the functional group that forms at least one sulfo group upon decomposition include a functional group represented by the general formula (XIX) or (XX). Formula _{(XIX) -SO 2 -O-R} D 1 formula _{(XX) -SO 2 -S-R} D 2 formula (XIX) Medium R ^D ₁ is

Embedded image Or an -NHCOR ^D _7. In the formula (XX), R ^D ₂ is
Represents an optionally substituted aliphatic group having 1 to 18 carbon atoms, or an optionally substituted aryl group having 6 to 22 carbon atoms.

The functional groups of the general formulas (XIX) and (XX) generate a sulfo group by decomposition, and will be described in more detail below. R ^D ₁

Embedded image In the formula, R ^D ₃ and R ^D ₄ may be the same or different, and represent a hydrogen atom, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group). Y ^D has 1 to 1 carbon atoms
18 optionally substituted alkyl groups (for example, methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, trifluoromethyl group, methanesulfonylmethyl group, cyanomethyl group, 2-methoxyethyl group, ethoxymethyl group, Chloromethyl group, dichloromethyl group, trichloromethyl group, 2-methoxycarbonylethyl group, 2-
Propoxycarbonylethyl group, methylthiomethyl group,
Ethylthiomethyl group, etc.), an alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group, etc.),
An aryl group which may have a substituent having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, a nitrophenyl group,
Dinitrophenyl, cyanophenyl, trifluoromethylphenyl, methoxycarbonylphenyl, butoxycarbonylphenyl, methanesulfonylphenyl, benzenesulfonylphenyl, tolyl, xylyl, acetoxyphenyl, nitronaphthyl, etc.) or

Embedded image (R ^D ₈ represents an aliphatic group or an aromatic group, and specifically represents the same as the above-mentioned substituent of Y ^D ). n
Represents 0, 1 or 2. More preferably, the substituent:

Embedded image In the above, a functional group containing at least one electron-withdrawing group is exemplified. Specifically, when n is 0 and Y ^D is a hydrocarbon group containing no electron-withdrawing group as a substituent,

Embedded image Contains at least one halogen atom. Further, n is 0, 1 or 2, and Y ^D contains at least one electron-withdrawing group. Further, when n = 1 or 2,

Embedded image And the like.

Another preferred substituent is -SO
_{In 2-} O- ^RD , the carbon atom adjacent to the oxygen atom is substituted by at least two hydrocarbon groups, or n =
When 0 or 1 and Y ^D is an aryl group, the aryl group may have a substituent at the 2-position and the 6-position.

R ^D ₁ is

Embedded image In the case of, Z ^D represents an organic residue forming a cyclic imide group. Preferably, the formula (XXI) or (XXI)
Represents an organic residue represented by I). General formula (XXI)

Embedded image General formula (XXII)

Embedded image Wherein _{^{(XXI), R D 9,}} R D 10 may be the same or different and each are each a hydrogen atom, a halogen atom (e.g. a chlorine atom,
A bromine atom etc., an alkyl group which may be substituted and has 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3
-Chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.), having 7 to 7 carbon atoms.
12 aralkyl groups which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group,
Chlorobenzyl group, bromobenzyl group, etc.), having 3 to 3 carbon atoms
18 optionally substituted alkenyl groups (e.g., allyl, 3-methyl-2-propenyl, etc.),

R ^D ₁

Embedded image In the case of representing, R ^D ₅ and R ^D ₆ are each a hydrogen atom,
(R ^D ₃ in particular, R ^D represents a identical to that of the content of ₄₎ aliphatic group or an aryl group (in particular R ^D _3, R ^D ₄
Represents the same content as that of. However, R ^D ₅ and R ^D ₆ never both represent hydrogen atoms. R ^D ₁ is-
When representing the NHCOR ^D _7, R ^D ₇ represents an aliphatic group or an aryl group, in particular represent respectively identical contents of R ^D _3, R ^D _4. Formula (XX) in, R ^D ₂ from 6 aliphatic group or a carbon atoms which may be substituted having 1 to 18 carbon atoms
Represents an aryl group which may have 22 substituents. More specifically, it has the same contents as the aliphatic group or the aryl group in Y ^D represented by the formula (XIX).

The general formula [—SO ₂ —O used in the present invention]
-R ^D ₁₎ or (monomer contains at least one functional group selected from -SO ₂ -O-R ^D _2] group, it can be synthesized based on the knowledge of the conventionally known organic reactions . For example, JFWMcOmie, "Protective Groups in Organic C
hemistry "; PlenumPress (1973), TWGreen
e, `` Protective Groups in Organic Sinthesis '' John
It can be synthesized in the same manner as in the carboxyl group protection reaction of Wiley & Sons (1980).

More specifically, the compound represented by the general formula (XIX) -SO ₂ -O-
Mention may be made of the following as an example as R ^D ₁ or the general formula _{(XX) -SO 2 -O-R} D 2 functional groups, but the scope of the present invention is not limited thereto.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

The resin particles [L] of the present invention can be obtained from the monomer (A)
Further, it may be polymerized in the presence of another monomer. The other monomer may be any as long as it can be copolymerized with the monomer (A) and the copolymer becomes an insoluble polymer in the non-aqueous solvent. Other monomers copolymerizable with these monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl esters, allyl esters such as allyl propionate, and acrylic acid. Esters or amides of unsaturated carboxylic acids such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, styrene, vinyltoluene, styrene derivatives such as α-methylstyrene, α-olefins, acrylonitrile, Examples include vinyl group-substituted heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone. These other monomers account for 60 parts by weight or less, preferably 5 parts by weight, of 100 parts by weight of the total polymer component to be insolubilized.
0 parts by weight or less. If the amount of the other monomer exceeds 60 parts by weight, the effect of improving the water retention as an offset printing original plate is reduced.

Next, the dispersion stabilizing resin of the present invention will be described. It is important that the dispersion stabilizing resin is solvated and soluble with a non-aqueous solvent, and is responsible for the dispersion stabilizing effect in so-called non-aqueous dispersion polymerization.Specifically, with respect to 100 parts by weight of the solvent, At least 5 at 25 ° C
Any substance that dissolves by weight% may be used.

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

The dispersion stabilizing resin of the present invention may be any polymer as long as it is a polymer soluble in the non-aqueous solvent.
KEJ Barrett `` Dispersion Polymerization in Or
ganic Media "John Wiley and Sons (1975), R. Dowpenco, DP Hart, Ind. Eng. Chem. Pr.
od. Res. Develop. 12 , (No. 1), 14 (197
3), Tokichi Tange, Journal of the Adhesion Society of Japan 23 (1), 26
(1987), DJ Walbridge, NATO. Adv. Study I
nst. Ser. E. No. 67, 40 (1983), Y. Sasakia
nd M. Yabuta, Proc, 10th, Int. Conf. Org. Coat. S
Review articles such as ci. Technol, 10 , 263 (1984) include each polymer of the reference.

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

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

Embedded image In formula (XXIII), X ₃ has the same content as V ₀ in formula (II), and details are described in the description of V _{0 in} formula (II).

R ₁₅ is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, dosaconyl group, 2- (N, N-dimethylamino) ethyl group, 2
-(N-morpholino) ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2- (α-thienyl) ethyl group, 2-carboxyethyl group, 2-methoxycarbonylethyl group,
A 2,3-epoxypropyl group, a 2,3-diacetoxypropyl group, a 3-chloropropyl group, a 4-ethoxycarbonylbutyl group and the like, an alkenyl group having 3 to 22 carbon atoms which may be substituted (for example, an allyl group, Hexenyl group, octenyl group, dodecenyl group, dodecenyl group, tridecenyl group,
An octadecenyl group, an oleyl group, a linoleyl group, etc.), an optionally substituted aralkyl group having 7 to 22 carbon atoms (eg, a benzyl group, a phenethyl group, a 3-phenylpropyl group,
2-naphthylmethyl group, 2- (2'-naphthyl) ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
A methoxybenzyl group, a dimethoxybenzyl group, a butylbenzyl group, a methoxycarbonylbenzyl group, etc., an alicyclic group having 4 to 12 carbon atoms which may be substituted (for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a chloro group) Cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.)
22 optionally substituted aromatic groups (for example, phenyl group,
Tolyl, xylyl, mesityl, naphthyl, anthranyl, chlorophenyl, bromophenyl, butylphenyl, hexylphenyl, octylphenyl, decylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, Octyloxyphenyl group, ethoxycarbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N, N-dibutylaminophenyl group, N
-Methyl-N-dodecylphenyl group, thienyl group, hydranyl group and the like). c ₁ and c ₂ represent the same contents as a ₃ and a ₄ in the formula (II) .
Described in the description of a ₃ and a ₄ .

As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the components described above. Other polymer components include those represented by the general formula (XXIII)
Any copolymerizable monomer may be used as long as it copolymerizes with a monomer corresponding to the component represented by the following formula. Examples of the corresponding monomer include α-olefins, acrylonitrile, methacrylonitrile, and vinyl-containing heterocycles (heterocycles). As the ring, for example, a pyran ring, a pyrrolidone ring, an imidazole ring, a pyridine ring, etc.), a carboxylic acid containing a vinyl group (eg, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc.), a carboxamide containing a vinyl group (Eg acrylamide, methacrylamide, crotonic amide,
Itaconamide, itaconic half-amide, itaconic diamide and the like).

In the dispersion stabilizing resin of the present invention, the polymer component represented by the general formula (XXIII) is the total polymer 1 of the resin.
The amount is at least 30 parts by weight, preferably at least 50 parts by weight in 00 parts by weight.

Further, it is preferable that the dispersion stabilizing resin of the present invention contains at least one polymerizable double bond group represented by the general formula (II) in the polymer chain. Hereinafter, the polymerizable double bond group portion will be described. General formula (II)

Embedded image In the general formula (II), V ₀ represents -O-, -COO-,-
_{OCO -, - (CH 2)} p -OCO -, - (CH 2) p
-COO -, - SO ₂ -,

Embedded image Represents -CONHCOO- or -CONHCONH- (p represents an integer of 1 to 4).

Here, R ₆ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, 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-
A methoxyethyl group, a 3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) Or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl) Group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl Group, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

V ₀ is

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

A ₃ and a ₄ may be the same or different from each other, and are preferably 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, COOR ₇ (R ₇ via the butyl group) -COO-R ₇ or hydrocarbons, hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, fat Represents a cyclic group or an aryl group, which may be substituted;
Specifically, represent represent) the same contents as those described above R _6.

The hydrocarbon in the —COOR ₇ group via the above hydrocarbon includes a methylene group, an ethylene group, a propylene group and the like. More preferably, the compound represented by the general formula (I
In I), V ₀ represents -COO-, -OCO-, -C
_{H 2 OCO -, - CH 2} COO -, - O -, - CONH
_{-, - SO 2 NH -,} - CONHCOO- or

Embedded image A ₃ and a ₄ may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COOR ₇ or -CH
Represents ₂ COOR _7, (R ₇ is 1 a hydrogen atom or carbon atoms
6 represents an alkyl group (for example, represents a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Even more preferably, one of a ₃ and a ₄ always represents a hydrogen atom.

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

Embedded image

Embedded image And the like.

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

Embedded image Represents a divalent aliphatic group or a divalent aromatic group, or an organic residue composed of a combination of these divalent residues, which may have a bonding group selected from the group consisting of: Where d
₁ to d ₅ represents the same meaning as R ₆ in formula (II).

As the divalent aliphatic group, for example,

Embedded image {E ₁ and e ₂ which include may be the same or different, each represents a hydrogen atom, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom) or an alkyl group (e.g. methyl group having 1 to 12 carbon atoms , Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). Q
Is -O -, - S- or -NR ₁₆ - represents, R ₁₆ is an alkyl group having 1 to 4 carbon atoms, -CH ₂ Cl or -CH ₂ Br
｝.

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

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

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

Embedded image (C-2)

Embedded image (C-3)

Embedded image (C-4)

Embedded image (C-5)

Embedded image (C-6)

Embedded image (C-7)

Embedded image (C-8)

Embedded image (C-9)

Embedded image (C-10)

Embedded image (C-11)

Embedded image (C-12)

Embedded image (C-13)

Embedded image (C-14)

Embedded image (C-15)

Embedded image (C-16)

Embedded image (C-17)

Embedded image (C-18)

Embedded image (C-19)

Embedded image (C-20)

Embedded image (C-21)

Embedded image (C-22)

Embedded image (C-23)

Embedded image (C-24)

Embedded image (C-25)

Embedded image (C-26)

Embedded image (C-27)

Embedded image (C-28)

Embedded image (C-29)

Embedded image (C-30)

Embedded image

Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group in a side chain in a polymer, and the synthesis of this polymer can be carried out by a conventionally known method. For example, a method of copolymerizing a monomer containing two polymerizable double bond groups having different polymerization reactivity in a molecule,
After polymerizing a monofunctional monomer containing a reactive group such as a carboxyl group, a hydroxy group, an amino group, or an epoxy group in the molecule to obtain a polymer, the reactive group in the polymer side chain is obtained. A method of conducting a reaction with an organic low-molecular compound containing a polymerizable double bond group containing another reactive group capable of chemically bonding with, for example, a method of introducing the compound by a so-called polymer reaction, and the like, are commonly known methods. Can be

As the above-mentioned method, for example,
185962. As the above method, specifically, Yoshio Iwakura and Keisuke Kurita, “Reactive Polymers” Kodansha (1977), Ryohei Oda “Polymer Fine Chemicals” Kodansha (1976),
This is described in detail in the specification and the like filed as Japanese Patent Application No. 1-43757 and Japanese Patent Application No. 1-149305.

For example, a polymer reaction by a combination of a functional group of Group A and a functional group of Group B shown in Table 1 below is a well-known method. In Table 1, R ₁₇ and R ₁₈
Is a hydrocarbon group and has the same contents as R ₆ in the above formula (II).

[Table 1]

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

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

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

As described above, the dispersed resin particles of the present invention are copolymer resin particles obtained by dispersion-polymerizing the polar group-containing monofunctional monomer (A) in the presence of the dispersion stabilizing resin. It is. Further, when the dispersed resin particles of the present invention have a network structure, the polymer component having the above-mentioned polar group-containing monofunctional monomer (A) as a main component [abbreviated as polymer component (A)] is used. The polymers are bridged to form a higher-order network structure.

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

The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, (a) a method of crosslinking a polymer containing the polymer component (A) with various crosslinking agents or curing agents, and (b) a method of containing at least a monomer corresponding to the polymer component (A). A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups when performing a polymerization reaction by It can be carried out by a method such as a method of cross-linking the united component (A) with a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction.

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

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

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

Embedded image And the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

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

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

Further, when a chemical bond is formed by a reaction between reactive groups between polymers in the above method (c) to form a bridge between the polymers, the reaction between the ordinary organic low-molecular compound and The same can be done. Specifically, it can be synthesized according to the same method as described in the synthesis method of the dispersion stabilizing resin. In dispersion polymerization, monodisperse particles having a uniform particle diameter are obtained, and fine particles of 0.5 μm or less are easily obtained. (B) is preferred. As described above, the network-dispersed resin particles of the present invention are protected.
A repeating unit containing a polar group, and contains a polymer component soluble in the nonaqueous solvent, and between molecular chains are particles of a polymer having a bridged structure in order.

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

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle diameter of the resin particles can be easily reduced to 1 μm or less, and the particle diameter distribution is very narrow and the monodispersed particles are dispersed. It can be. Specifically, KEJ Barrett "Dispersion Polymerization i
n Organic Media "John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto and Toyoyoshi Tange, Journal of the Adhesion Society of Japan 9 , 183 (1973),
Tokichi Tange, Journal of the Adhesion Society of Japan 23 , 26 (1987), D.
J. Walbridge, NATO. Adv. Study. Inst. Ser. E. N
o. 67, 40 (1983), UK Patent 89342
9, No. 934038, U.S. Pat. No. 11,223
97, 3900412, 46068989, JP-A-60-179751, 60-185963
The method is disclosed in each publication.

The dispersion resin particles of the present invention comprise at least one of each of the monomer (A) and the dispersion stabilizing resin. When forming a network structure, a polyfunctional monomer ( D) coexist, and in any case the important thing is
If the resin synthesized from these monomers is insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, it is preferable to use 1 to 50% by weight, more preferably 2 to 30% by weight of the dispersion stabilizing resin based on the monomer (A) to be insolubilized. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ to 10 ⁶ , preferably 1 to 10.
0 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersed resin particles used in the present invention as described above, generally, the monomer (A), the dispersion stabilizing resin, and the polyfunctional monomer (D) are mixed with a non-aqueous solution. What is necessary is just to heat-polymerize in a solvent in presence of a polymerization initiator, such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of a monomer (A), a dispersion stabilizing resin and a polyfunctional monomer (D), and (ii) a method of adding a polymerization initiator to a non-aqueous solvent. And a method in which a mixture of the above-mentioned polymerizable compound and polymerization initiator is added dropwise or arbitrarily, and the like.

The total amount of the polymerizable compound is about 5 to 80 parts by weight based on 100 parts by weight of the non-aqueous solvent, preferably 10 to 80 parts by weight.
５０50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compound. The polymerization temperature is 30
To 180 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

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

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Further, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, or the like may be used in combination as another inorganic photoconductor. However, these other photoconductive materials comprise up to 40% by weight of the photoconductive zinc oxide, preferably up to 20% by weight. If the amount of the 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.

The total amount of the binder resin used for the inorganic photoconductive material was such that 1 part of the binder resin was used for 100 parts by weight of the photoconductor.
It is used in a proportion of 0 to 100 parts by weight, preferably in a proportion of 15 to 50 parts by weight.

In the present invention, various dyes are appropriately used alone or in combination as spectral sensitizers. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8) No. 12
RCA Review 15 , 469 (195)
4), Kohei Kiyota: IEICE Transactions J63-C
(No. 2), p. 97 (1980), Yuji Harasaki et al., Industrial Chemistry Magazine 66 , 78 and 188 (1963), Tadaaki Tani, Photographic Society of Japan 35 , p. 208 (1972), etc. Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g. oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (including metals) And the like).

More specifically, examples of those mainly using a carbonium-based dye, a triphenylmethane-based dye, a xanthene-based dye, and a phthalein-based dye include JP-B-51-4.
52, JP-A-50-90334 and 50-11422
7, 53-39130, 53-82353, U.S. Pat. Nos. 3,052,540, 4,054,450, and JP-A-57-16456. No.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include FM Harmmer “The Cyanine Dyesand Relais”.
tedCompounds '' etc. can be used,
More specifically, US Pat.
0591, 312008, 312547, 3
128179, 3132942, 3622,317
Each specification, British Patent Nos. 1226892 and 13092
74, 1405898, JP-B-48-78
14, 55-18892, and the like.

Further, as a polymethine dye for spectrally sensitizing the near-infrared to infrared light region having a long wavelength of 700 nm or more, JP-A No.
7-840, 47-44180, JP-B-51-410
61, JP-A-49-5034, JP-A-49-45122, JP-A-57-46245, JP-A-56-35141, and JP-A-57-15-15
Nos. 7254, 61-26044 and 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956.
Each specification, "Research Disclosure
1982, 216, pp. 117-118 and the like. The photoreceptor of the present invention is also excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye.

Further, if necessary, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination. For example, the review mentioned above : Imaging 1
973 (No. 8), page 12, etc., as electron-accepting compounds (for example, halogen, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent development and commercialization of photoconductive materials and photoconductors", Chapters 4 to 6: Japan Science Information Publishing Co., Ltd. (1986) Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like described in the above-cited references.

The amount of these various additives is not particularly limited, but is usually 0.00.0 parts by weight based on 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight.

The thickness of the photoconductive layer is 1 to 100 μm, especially 10 μm.
~ 50μ is preferred.

When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 μm, particularly 0.05 to 0 μm. .
5μ is preferred.

Examples of the charge transporting material for the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm. As the resin used for forming the charge transport layer,
Typical ones are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-co-copolymer resin, polyacryl resin, polyolefin resin, urethane resin, polyester resin, epoxy Resins, melamine resins, thermoplastic resins such as silicone resins, and curable resins are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a base material such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. A substrate that has been subjected to a conductive treatment, for example, by applying a conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further has at least one layer coated for the purpose of preventing curling,
A substrate provided with a water-resistant adhesive layer on the surface of the support, a substrate provided with at least one or more pre-coat layers as necessary on the surface layer of the support, or a substrate conductive plastic on which Al or the like is deposited on paper. Laminated ones can be used.
Specifically, as an example of a conductive substrate or a conductive material,
Yukio Sakamoto, Electrophotography, 14, (No. 1), pp. 2-11
(1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing Association (1975), MF Hoover, J. Macromol. Sc
i. Chem. A-4 (6), pp. 1327-1417 (1
970).

The printed matter using the electrophotographic printing master of the present invention is prepared by forming a copy image on the electrophotographic master having the above-described structure by a conventional method, and then subjecting the non-image portion to desensitization processing. Is done. Desensitizing to be used in the present invention, the resin particles of the present invention, a method of hydrolyzing by passing a treatment liquid, a thiol group by decomposing the like by methods or light irradiation treatment degrades in a redox reaction, Phosphono
A method of generating a group, an amino group or a sulfo group , or a method of desensitizing zinc oxide with a desensitizing solution together with a hydrophilic treatment of resin particles. In the latter case,
Perform desensitization reaction of zinc oxide particles and resin particles simultaneously, decompose resin particles after desensitizing zinc oxide particles, perform desensitization reaction of zinc oxide particles after decomposing resin particles, etc. This procedure can also be used.

As the method for desensitizing zinc oxide, any of conventionally known treatment solutions can be used. For example,
Using a ferrocyanide compound as the main agent of desensitization,
JP-A-61-239158, JP-A-62-292492, JP-A-63-99993, JP-A-63-9994, JP-B-40-7
334, 45-33683, JP-A-57-10788
9. JP-B 46-21244, 44-9045, 4
7-32681, 55-9315, JP-A-52-10
No. 1102, and the like. However, the following treatment liquids are preferred from the viewpoint of the safety of the treatment liquid. For example, JP-B-43-28 using a phytic acid-based compound as a main ingredient
408, 45-24609, JP-A-51-10350
1, 54-10003, 53-83805, 5
3-83806, 53-127002, 54-44
901, 56-2189, 57-2796, 57
JP-B-38-9656 and JP-B-39-2226, each using a water-soluble polymer capable of forming a metal chelate as described in JP-B-20394 and JP-B59-207290.
3, 40-763, 43-28404, 47-2
9642, JP-A-52-126302 and JP-A-52-134.
Nos. 501, 53-49506, 53-59502 and 53-104302, and JP-A-53-10430 using a metal complex compound as a main agent.
1, JP-B-55-15313 and JP-B-54-41924, or JP-B-39-13702, JP-B-40-13, using inorganic and organic acid compounds as main agents.
-10308, 46-26124, JP-A-51-11
8501, 56-1111695, and the like.

The method for desensitizing resin particles, that is, the method for decomposing the protected specific functional group of the present invention, is as follows.
It is arbitrarily selected according to the decomposition reactivity of the protected specific functional group of the present invention. acidic conditions of pH 1-6, pH
Hydrolysis with an aqueous solution under alkaline conditions of 8 to 12 may be mentioned. These pH adjustments can be easily performed using known compounds. Alternatively, a method based on a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and as these compounds, known compounds can be used, for example, hydrous hydrazine, sulfite, lipoic acid, hydroquinones, formic acid, Thiosulfate, hydrogen peroxide, persulfate, quinones and the like.

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

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

The scope of the present invention is not limited to the specific compound examples described above. The processing conditions are temperature 15 ~
The immersion time at 60 ° C. is preferably 10 seconds to 5 minutes. Further, as a method of decomposing a specific functional group by light irradiation, a step of irradiating light with "chemically active light" may be inserted between any of the steps after obtaining a toner image in plate making. That is, after the electrophotographic development, light irradiation may be performed also to fix the toner image at the time of fixing, or after fixing by other conventionally known fixing methods, for example, heat fixing, pressure fixing, solvent fixing, etc. Irradiation is performed. The “chemically active light” used in the present invention may be any of visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α-ray, etc., and preferably includes ultraviolet light. More preferably, it can emit light in the wavelength range of 310 nm to 500 nm, and generally a high-pressure or ultra-high-pressure mercury lamp or the like is used. Light irradiation treatment is usually 5cm ~
Irradiation for 10 seconds to 10 minutes from a distance of 50 cm can be performed sufficiently.

[0145]

EXAMPLES Examples of the present invention will be described below, but the content of the present invention is not limited to these examples. Synthesis Example 1 of Binder Resin [A]: [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 stream of nitrogen, and 6.0 g of AIBN was added. Allowed to react for hours. Further, 2 g of AIBN was added and reacted for 2 hours. Mw of the obtained copolymer [A-1] was 8,500.

Synthesis Examples 2 to 28 of Binder Resin [A]: [A-
2] to [A-28] Resins [A-2] to [A-28] in Table 2 below were synthesized in the same manner as in the polymerization conditions of Synthesis Example 1 for Resin [A].

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

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-dodecylmercaptan and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream, and 2 g of AIBN was added and reacted for 4 hours. AI
Add 0.5 g of BN and 2 hours, then 0.5 g of AIBN
And reacted for 3 hours. After cooling, methanol / water (9 /
Was reprecipitated in a mixed solution of 2l of 1), the precipitate was collecting capturing by decantation and dried under reduced pressure. The yield of the obtained waxy copolymer was 78 g, and Mw was 6.3 × 10 ³ .

Production Example 1 of Dispersion Stabilizing Resin [P-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and stirred for 4 hours, and 0.5 g of AIBN was further added and stirred for 4 hours. Next, methacrylic acid 5 was added to the reaction mixture.
g, N, N-dimethyldodecylamine (1.0 g) and t-butylhydroquinone (0.5 g) were added, and the mixture was stirred at 110 ° C. for 8 hours. After cooling, it was reprecipitated in methanol 2l, after slightly collector capturing a brown oil Pounds, and dried. Yield 7
The weight average molecular weight (Mw) of 3 g was 3.6 × 10 ⁴ . [P-1]

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

50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate, 150 g of tetrahydrofuran
And a mixed solution of 8 g of dicyclohexylcarbondiimide (DCC), 0.2 g of 4- (N, N-dimethylamino) pyridine and 20 g of methylene chloride was added dropwise at a temperature of 25 to 30 ° C. Stirred for hours. Next, 5 g of formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated in 1 liter of methanol, and the oily substance was collected by filtration. Further, the oil was dissolved in tetrahydrofuran 200 g, and reprecipitated again one liter of methanol The insoluble material was filtered off, and was then current capturing an oil drying. Mw 4.2 × 10 ⁴ with a yield of 32 g
Met. [P-2]

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Production Example 3 of Dispersion Stabilizing Resin: [P-3] A mixed solution of 96 g of butyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate and N, N-dimethyldodecylamine were added to the reaction solution.
0 g and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 l of methanol to obtain 82 g of an oily substance.
The number average molecular weight of the polymer was 5,600. [P-3]

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Production Example 4 of dispersion stabilizing resin: [P-4] A mixed solution of 107 g of n-butyl methacrylate, 4 g of β-mercaptopropionic acid and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. did. A.
1 g of IBN was added and reacted for 6 hours. After cooling the reaction mixture and setting the temperature at 25 ° C., 10 g of 2-hydroxyethyl methacrylate, 8 g of dicarboxylcarboxylic diimide (DCC), 0.2 g of 4- (N, N-dimethylamino) pyridine and 20 g of methylene chloride were added. The mixed solution was added dropwise at a temperature of 25 to 30 ° C., and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added to the reaction mixture, and the mixture was stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated in 1 liter of methanol, and the oily substance was collected by filtration. Further, this oily substance was dissolved in 200 g of tetrahydrofuran, and the insoluble substance was separated by filtration and then reprecipitated again in 2 liters of methanol. The oily substance was collected and dried. Mw 6.6 × 10 ³ with a yield of 68 g.
Met. [P-4]

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

[Table 7]

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

[Table 8]

Production Example 17 of dispersion stabilizing resin: [P-1
7] A mixed solution of 97 g of octyl methacrylate, 3 g of glycidyl methacrylate and 200 g of benzotrifluoride was heated to a temperature of 75 ° C. while stirring under a nitrogen stream.
1.0 g of AIBN was added and reacted for 4 hours. Further AI
0.5 g of BN was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction mixture, and the mixture was stirred at 110 ° C. for 8 hours. Reprecipitated in methanol in a 2 liter After cooling, after <br/> current slightly capturing a brown oil Pounds, and dried. Weight average molecular weight (Mw) with a yield of 73 g
It was 3.6 × 10 ⁴ . [P-17]

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Production Example 18 of dispersion stabilizing resin: [P-1
8] A mixed solution of 85 g of butyl methacrylate, 15 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN)
Was added, and the mixture was reacted for 4 hours. Then, 0.4 g of AIVN was further added and reacted for 4 hours. After the reaction was cooled to a temperature of 25 ° C., 4 g of methacrylic acid was added, and 6 g of DCC was added with stirring.
A mixed solution of 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 further stirred for 3 hours. Then water 10g was added, the insoluble material was filtered off which was stirred for 1 hour to precipitate, the filtrate was collecting capturing the reprecipitated with oil in 1 liter of methanol. Further, this oil was dissolved in benzene 150 g, was then current capturing the reprecipitated with oil dried insolubles filtered off again after 1 liter of methanol to. The yield was 56 g and the Mw was 8 × 10 ³ . [P-18]

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Production Examples of Dispersion Stabilizing Resins 19 to 25: [P
-19] to [P-25] By performing the reaction as shown in Production Example 18, the following dispersion-stabilizing resins in Table 5 were synthesized. The Mw of each resin ranged from 6 × 10 ^{3 to} 9 × 10 ³ .

[Table 9]

[Table 10]

Production Example 1 of Resin Particles: [L-1] A mixed solution of 10 g of dispersion stabilizing resin [P- 18 ] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this, the following monomer [A-1] 40
g, ethylene glycol dimethacrylate 10 g, AI
A mixed solution of 0.5 g of VN and 240 g of methyl ethyl ketone was added dropwise over 2 hours, and the mixture was reacted for 2 hours. Further
0.5 g of AIVN was added and reacted for 2 hours. After cooling, 2
A white dispersion was obtained through a 00 mesh nylon cloth.
The latex had an average particle size of 0.20 μm. (CA
PA-500, manufactured by HORIBA, Ltd., particle size measurement). Monomer [A-1]

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Production Examples 2-12 of Resin Particles: [L-2]-
[L-12] In the same manner as in Production Example 1 except that the compounds of Production Example 1 of the resin particles were replaced with the compounds shown in Table 6 below in place of the resin [P-18] and the monomer [A-1], respectively. To produce resin particles. The average particle size of each particle was in the range of 0.15 to 0.30 μm.

[Table 11]

[Table 12]

Production Examples of Resin Particles 13 to 23: [L-1
3] to [L-23] In the same manner as in Production Example 1 except that the polyfunctional compound shown in Table 7 below was used instead of ethylene glycol dimethacrylate in Production Example 1 of the resin particles, 13]
To [L-23]. The polymerization rate of each particle is 95-
At 98%, the average particle size was 0.15 to 0.25 µm.

[Table 13]

Production Example 24 of Resin Particles: [L-24] A mixed solution of 8 g of dispersion stabilizing resin [P-21] and 130 g of methyl ethyl ketone was stirred at 60 ° C. under a nitrogen stream.
Was heated. To this, 45 g of the following monomer [A-13],
5 g of diethylene glycol dimethacrylate, AIVN
A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour, and 0.25 g of AIVN was further added to obtain a solution.
Reacted for hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.25 μm. Monomer [A-13]

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Production Example 25 of Resin Particles: [L-25] A mixed solution of 7.5 g of dispersion stabilizing resin [P-12] and 230 g of methyl ethyl ketone was stirred for 6 hours under a nitrogen stream.
Warmed to 0 ° C. Thereto, single-mer [A-12] 25 g,
A mixed solution of 15 g of acrylamide, 0.5 g of AIVN and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the mixture was further reacted for 1 hour. In addition, AIVN 0.25
After reacting for 2 hours, the mixture was cooled and the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.1 mm.
It was 25 μm.

Production Example 26 of Resin Particles: [L-26] 42 g of the following monomer [A-14], 8 g of ethylene glycol diacrylate, and 8 g of dispersion stabilizing resin [P-23]
And 230 g of dipropyl ketone in a nitrogen stream at a temperature of 60 ° C.
Was heated. This was dropped into a solution of 200 g of dipropyl ketone over 2 hours with stirring. After reacting for 1 hour, 0.3 g of AIVN was further added and reacted for 2 hours. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.20 μm. Monomer [A-14]

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Production Examples of Resin Particles 27 to 36: [L-2
7] to [L-36] In Resin Particle Production Example 26, the dispersion stabilizing resin [P-
Each particle was produced in the same manner as in Production Example 26 except that each dispersion stabilizing resin shown in Table 8 below was used instead of [23]. The average size of each particle ranged from 0.20 μm to 0.25 μm.

[Table 14]

Production Examples of Resin Particles 37 to 42: [L-3
7] to [L-42] In Production Example 25 of the resin particles, a monomer [A-12],
Production Example 2 except that each of the compounds shown in Table 9 below was used instead of acrylamide, the reaction solvent, and methyl ethyl ketone
Each particle was produced in the same manner as in No. 5 . The average particle size of each particle ranged from 0.15 μm to 0.30 μm.

[Table 15]

[Table 16]

Example 1 and Comparative Example A Example 1 6 g of resin [A-3] (as solid content), 30 g of resin [B-1] having the following structure (as solid content), 200 g of photoconductive zinc oxide, Methine dye of structure [I] 0.018
g, 0.15 g of salicylic acid and 300 g of toluene were mixed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 7 × 1.
0 ³ was rpm dispersed in rpm for 10 minutes. 4 g (as solid content) of dispersed resin particles [L-1], 0.05 g of phthalic anhydride and 0.003 g of o-chlorophenol were added thereto, and the mixture was further dispersed at 1 × 10 ³ rpm for 1 minute. This dispersion for forming a photosensitive layer was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² ,
Dry at 0 ° C. for 3 minutes. Then, at 20 ° C, 65% R in the dark
The mixture was allowed to stand for 24 hours under the condition of H to prepare an electrophotographic photosensitive material. [B-1]

Embedded image

Comparative Example A An electrophotographic photosensitive material was produced in the same manner as in Example 1, except that 4 g of the resin particles [L-1] were omitted.

Comparative Example B In Example 1, 6 g of the resin [A-3] and the resin [B-
1] An electrophotographic photosensitive material was produced in the same manner as in Example 1, except that 36 g of the resin [B-1] alone was used instead of 30 g.

The film properties (surface smoothness), electrostatic properties, desensitization property of the photoconductive layer (expressed by the contact angle of the photoconductive layer with water after desensitization treatment) and printing of these photosensitive materials. The sex was examined. The 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.) using a developer ELP-T to form an image and performing desensitization processing was used. The examination was performed using a printing plate. (The printing machine used was Hamadastar 800SX manufactured by Hamadastar Co., Ltd.) The above results are summarized in Table-10.

[Table 17]

The embodiments of the evaluation items shown in Table 10 are as follows. Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured.

Note 2) Electrostatic characteristics: In a dark room at a temperature of 20 ° C. and a relative humidity of 65%, each photosensitive material was subjected to -20 kV at −6 kV using a paper analyzer (Paper Analyzer-SP-428, manufactured by Kawaguchi Electric Co., Ltd.). After a corona discharge for 2 seconds, the device was left for 10 seconds, and the surface potential at this time was measured as V ₁₀ . Next, the potential V ₁₂₀ after standing still in the dark for 120 seconds was measured, and the potential retention after dark decay for 120 seconds, that is, the dark decay retention rate [DRR (%)]
Was determined by [(V ₁₂₀ / V ₁₀ ) × 100 (%)]. After charging the surface of the photoconductive layer to −500 V by corona discharge, irradiation with monochromatic light having a wavelength of 780 nm was performed, and the time required for the surface potential (V ₁₀ ) to decrease to 1/10 was determined. Calculate _1/10 (erg / cm ² ). Further, after charging to -500 V by corona discharge as in the E _1/10 measurement,
Irradiation with monochromatic light having a wavelength of 780 nm results in a surface potential (V ₁₀ ) of 1 /
The time required to decay to 100 is calculated, and the exposure
Calculate _1/100 (erg / cm ² ). Environmental conditions at the time of imaging are I
(20 ° C, 65% RH) and II (30 ° C, 80% RH)
It was carried out in.

Note 3) Image-capturing property: Each photosensitive material was left under environmental conditions I or II all day and night. Next, it is charged at -5 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 78
0 nm), a pitch of 25 μm and a scanning speed of 330 m / cm ^{2 at} an irradiation dose of 50 erg / cm ² on the surface of the photosensitive material.
sec speed exposure, ELP-T as liquid developer
(Fuji Photo Film Co., Ltd.) was used to develop and fix the copy image obtained, and the fog and image quality of the image were visually evaluated.

Note 4) Raw plate water retention: The degree of hydrophilization due to desensitization treatment when the photosensitive material was used as a printing plate was examined under the following forced conditions. Each light-sensitive material itself was used as a desensitizing solution E (manufactured by Fuji Photo Film Co., Ltd.).
Using an aqueous solution obtained by diluting LP-EX five times with distilled water,
The etching machine was passed once. In addition, 0.5
It was immersed in a solution (E-1) obtained by diluting mol monoethanolamine in 1 liter of distilled water for 3 minutes. Next, these plates were printed using a Hamadastar 8005X manufactured by Hamadastar Co., Ltd., and the fiftyth printed matter from the start of printing was visually evaluated for the presence or absence of background stain.

As shown in Table 10, the photosensitive materials of the present invention and Comparative Example A had good smoothness and electrostatic properties of the photoconductive layer, no actual fogged image, and clear image quality. Was. Next, when used as an offset master master,
Diluting the photosensitive material that is not made into a plate with a desensitizing solution, desensitizing under severe conditions, actually printing and examining the water retention, the present invention is good in that there is no background stain from printing. It showed excellent water retention and produced 10,000 clear prints without background stains even when the original plate was actually made. On the other hand, Comparative Example A, to which no resin particles for promoting hydrophilicity were added, had insufficient water retention, and the background stain of the printed matter was generated from printing, and was not eliminated by printing.

In Comparative Example B, the electrostatic characteristics were remarkably deteriorated, and a satisfactory copied image could not be obtained in the actual imaging performance. On the other hand, the water retention as an offset original plate was markedly stained with ink and markedly stained. This is due to the fact that hydrophilization is not sufficiently performed.Even when printing is performed on an original plate that has been subjected to hydrophilization treatment under normal desensitizing conditions, the printed image is significantly stained and the copied image is not obtained on the original plate after plate making. The printed matter was deteriorated and a satisfactory printing original plate was not obtained from printing.

Note 5) Smear of printed matter: After making each photosensitive material in the same operation as in the above note 3), EL was applied.
After passing through the etching machine once using P-EX, the aqueous solution containing molar ethanolamine (E-1) of Note 4)
And then washed with water. These offset master masters were printed using ELP-FX (fountain solution manufactured by Fuji Photo Film Co., Ltd.) as a fountain solution, and the number of printed sheets until the background stain on the printed material could be visually discriminated was examined.

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-10] (as solid content), 30 g of resin [B-2] having the following structure, and resin particles [L-12] 4.
5 g (as solid content), methine dye [II] having the following structure
An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except for 0.02 g. Resin [B-2]

Embedded image The electrophotographic properties and printability of the obtained photosensitive material were measured in the same manner as in Example 1, and the following results were obtained. As described above, both electrophotographic characteristics and printability were good.

Examples 3 to 18 Resins [A] shown in Table 6 below, each 5 g (as solid content), resin particles [L] 4 g (as solid content), 31 g of resin [B-3] having the following structure and methine dye [III] 0.018 g
Other than the above, each photosensitive material was prepared in the same manner as in Example 1. Resin [B-3]

Embedded image In the same manner as in Example 1 for each of the photosensitive material, the electrostatic characteristics,
Printability was examined. The results are shown in Table-11.

[Table 18]

As shown in Table 11, the electrostatic characteristics were 30
Very good results were obtained even under severe conditions of ℃ and 80% RH. The actual image-capturing properties were also good, the water retention of these masters for offset masters was good, and the printing durability was able to print up to 10,000 sheets.

Example 19 and Comparative Example C 6.0 g of resin [A-1] and resin [B-5] 2 having the following structure
9.5 g, 4.5 g of resin particles [L-24], zinc oxide 2
00g, Uranine 0.02g, Rose Bengal 0.04
g, bromophenol blue 0.03 g, phthalic anhydride 0.20 g and toluene 300 g were dispersed in a homogenizer at a rotation speed of 6 × 10 ³ rpm for 10 minutes, and further dispersed in 3,3 ′, 5,5′-benzophenone tetrachloride. 0.08 g of carboxylic dianhydride was added, and the number of rotations was 1 × 10 ³ rp
m. for 1 minute to prepare a photosensitive layer-formed product, which was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 22 g / m ^2, and dried at 110 ° C. for 20 seconds. Further heating was performed at 120 ° C. for 2 hours. Then at 20 ° C, 6 in the dark
Each of the electrophotographic photosensitive materials shown in Table 12 below was prepared by being left for 24 hours under the condition of 5% RH. Resin [B-5]

Embedded image

Comparative Example C In Example 19, 6.0 g of the resin [A-1] and 29.5 g of the resin [B-5] were replaced with only the resin [B-5].
An electrophotographic photosensitive material was produced in the same manner as in Example 19 except that 5.5 g was used. The characteristics of each photoreceptor were examined in the same manner as in Example 1, and the results are shown in Table-12.

[Table 19] In the above measurement, the same operation as in Example 1 was performed, except that the following operation was performed for the electrostatic characteristics and the image capturing property.

Note 6) Method for measuring E _1/10 and E _1/100 of electrostatic characteristics: After charging the surface of the photoconductive layer to −400 V by corona discharge, the illuminance of the photoconductive layer was 2.0 lux. And the time required for the surface potential (V ₁₀ ) to attenuate to 1/10 or E _1/100 was determined, and the exposure amount E _1/10 or E
Calculate _1/100 (looks per second).

Note 7) Image-capturing property After leaving each photosensitive material for one day and night under the following environmental conditions, a fully automatic plate making machine EPL-404V (Fuji Photo Film Co., Ltd.)
The fogging and image quality of the copied image obtained by making a plate using EPL-T as a toner were evaluated by visual inspection. Environmental conditions during imaging were 20 ° C. and 65% RH (I) and 30 ° C. and 80% RH (II).

Note 8) Water retention and printing durability In notes 4) and 5), the desensitizing solution (E-1)
Was carried out in the same manner as in Example 1 except that the following (E-2) was used instead of Desensitizing solution: E-2 55 g of boric acid Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 6 g of tetrahydrofuran 80 g is dissolved in distilled water to make the total volume 1.0 liter, and then adjusted to pH 11.0 with potassium hydroxide. did.

In both Example 19 and Comparative Example C of the present invention, a copied image having good electrostatic characteristics and clear image quality could be obtained. Furthermore, when used as offset master plate precursor, the present invention is water retention is good, printing durability was possible until 10,000 sheets. However, Comparative Example C, from which the resin particles were removed, did not have sufficient water-retention due to the hydrophilization, which is a forced condition, and when it was made insensitive under actual conditions and printed, the background stain on the non-image area was reduced. Unprinted printed matter was up to 5,000 sheets. From the above, only the photosensitive material of the present invention was able to maintain excellent performance in both electrostatic characteristics and printing characteristics.

Examples 20 to 27 In Example 19, 5 g of resin [A] shown in Table 13 below
Each photosensitive material was prepared in the same manner as in Example 19, except that (as a solid content), 4 g of resin particles [L] (as a solid content) and 31 g of resin [B].

[Table 20]

The light-sensitive materials of the present invention are all excellent in chargeability, dark charge retention, and photosensitivity, and actual copied images can be subjected to severe conditions of high temperature and high humidity (30 ° C., 80% RH). A clear image without generation of fine lines and skipping of fine lines was given. Further, when printing was performed as an offset master plate, a printed matter of clear image quality free of background smear was obtained even after printing 10,000 sheets.

Examples 28 to 31 In Example 19, 5.5 g of resin [ A-1]
[B-1] Same as Example 19 except that 31.5 g was used.
Thus, an electrophotographic photosensitive member was prepared (Example 28). Further
5.5 g of the resin [A-1] in Example 19, and
Example 1 except that 31.5 g of the binder resin shown in Table 14 was used.
Each electrophotographic photoreceptor was prepared in the same manner as in Example 9.
29-31) .

[Table 21]

[0190] sensitive material Any chargeable present invention, dark charge retention rate, excellent light sensitivity, the actual copy image is also high temperature and high humidity (30 ℃, 80% RH) of the harsh conditions odor land be fog A clear image without generation of fine lines and skipping of fine lines was given. Further, when printing was performed as an offset master plate, a printed matter of clear image quality free of background smear was obtained even after printing 10,000 sheets.

Examples 32 to 35 Each of the photoreceptors shown in Table 15 below was subjected to plate making to prepare an original plate of ELP-
After immersion in EX for 4 minutes to make it desensitized, printing was performed in the same manner as in Example 1. As a result, 10,000 prints of clear image quality free of background smear were obtained.

[Table 22]

Examples 36 to 41 Each of the photoreceptors shown in Table 16 below was subjected to plate making to prepare an original plate of ELP-
After passing through the etching machine once using EX, it was immersed in a resin particle desensitizing solution (E-3) having the following formulation for 3 minutes to perform desensitization treatment. Resin particle desensitizing solution: E-3 Diethanolamine 80 g Newcol BSN (manufactured by Nippon Emulsifier Co., Ltd.) 6 g Benzyl alcohol 100 g is dissolved in distilled water to make the total volume 1 liter, and then adjusted to pH 10.5 with potassium hydroxide. Aqueous solution.

[Table 23]

When this was printed in the same manner as in Example 1,
In each of the masters, 10,000 or more prints of clear image quality free of background stain were obtained.

Examples 42 to 45 In Example 19, the binder resin particles of the present invention [L-2
4] In place of 4.5 g, each of the particles [L] in Table 17 below was 4
Each photosensitive material was prepared in the same manner as in Example 19 except that g was used.

[Table 24]

After the respective photoreceptors were plate-produced in the same manner as in Example 19, these plate-making photosensitive materials were irradiated with light for 5 minutes at a distance of 10 cm from a 400 W high-pressure mercury lamp as a light source. After that, desensitization treatment was performed by passing through an etching processor once using ELP-FX (manufactured by Fuji Photo Film Co., Ltd.). When these printing original plates were printed in the same manner as in Example 19, the water retention was good and the printing durability was able to be printed up to 10,000 sheets.

[0196]

According to the present invention, an electrophotographic lithographic printing plate precursor having excellent printed images and high printing durability can be obtained even under severe conditions. Further, the lithographic printing original plate of the present invention is effective for a scanning exposure method using a semiconductor laser beam.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI G03G 13/28 G03G 13/28 (58) Fields investigated (Int.Cl. ⁶ , DB name) G03G 5/00

Claims (4)

(57) [Claims] 1. The method according to claim 1, wherein at least one layer is formed on the conductive support.
In an electrophotographic lithographic printing plate precursor provided with a photoconductive layer containing a photoconductive zinc oxide, a spectral sensitizing dye and a binder resin, the binder resin contains at least one of the following resins [A] as the binder resin. The photoconductive layer further comprises at least one kind of the following non-aqueous solvent-based dispersed resin particles having a particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles. Electrophotographic lithographic printing original plate. Resin [A]: having a weight-average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing at least 30% by weight of a repeating unit represented by the following general formula (I) as a polymer component, and -PO ₃ H ₂ ,- SO ₃ H, -C
OOH, embedded image [R ₁ represents a hydrocarbon group or —OR ₂ (R ₂ represents a hydrocarbon group)] and a cyclic unit containing at least one polar group selected from cyclic acid anhydride-containing groups as a substituent. A copolymer containing 0.5 to 20% by weight as a polymer component, represented by the general formula (I): [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 ₃ represents a hydrocarbon group.] Non-aqueous solvent-based dispersed resin particles: In an aqueous solvent, a thiol group, a phosphono group, an amino group, a sulfo group, A monofunctional monomer (A) containing at least one functional group selected from functional groups that form a group [R ₁ represents a hydrocarbon group or an —OR ₂ group (R ₂ represents a hydrocarbon group)] a),
Copolymer resin particles obtained by performing a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. 2. The resin [A] is a copolymer component represented by the general formula (I), which is selected from aryl group-containing methacrylate components represented by the following general formulas (Ia) and (Ib). The electrophotographic lithographic printing plate precursor according to claim 1, wherein the lithographic printing plate precursor comprises at least one. General formula (Ia) General formula (Ib) [However, in the above formulas (Ia) and (Ib), T ₁ and T ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, —COR ₄ or —COOR
₅ (R ₄ and R ₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent a single bond or a connecting atom having 1 to 4 atoms connecting —COO— and a benzene ring. Represents a linking group of 3. The non-aqueous solvent-based dispersed resin particles form a high-order network structure.
The electrophotographic lithographic printing original plate described in the above. 4. The method according to claim 1, wherein the dispersion stabilizing resin is
2. The electrophotographic lithographic printing plate precursor according to claim 1, which contains at least one polymerizable double bond group represented by the following general formula (II). General formula (II) [In the general formula (II), V ₀ is (However, p represents an integer of 1 to 4, R ₆ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a ₃ , a ₄
May be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₇ (R ₇ through -COO-R ₇ or a hydrocarbon group is a hydrogen atom or a substituent Represents a good hydrocarbon group).