JP3048178B2 - 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 good printed matter, first, the original image is faithfully copied onto the offset original plate, the surface of the photoreceptor is easily adapted to 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 it is well compatible with fountain solution, and the non-image portion is sufficiently formed so that stains do not occur even when the number of printed sheets increases. It is necessary to have performance such as maintaining hydrophilicity.

[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 the addition of resin particles containing a hydrophilic group to the 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, there is provided an electrophotographic method comprising providing at least one photoconductive layer containing a photoconductive zinc oxide and a binder resin on a conductive support. In the lithographic printing plate precursor, the binder resin contains at least one of the following resins [A], and the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles in the photoconductive layer. An electrophotographic lithographic printing plate precursor characterized by containing at least one kind of the following non-aqueous solvent-based dispersed resin particles having a particle diameter can be achieved.

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 And 0.5 to 15% by weight of a polymer component having at least one polar group selected from acid anhydride groups:

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: a non-aqueous solvent containing at least one functional group which is soluble in the non-aqueous solvent but insolubilized by polymerization, and which forms a carboxyl group by decomposition. Copolymer resin particles obtained by subjecting at least one of the functional monomers (A) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.

In the present invention, the non-aqueous solvent-based dispersed resin particles may form a higher-order network structure. As the dispersion stabilizing resin in the present invention, a resin containing at least one polymerizable double bond group represented by the following general formula (II) in a polymer chain is particularly preferred. Can be 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 -CONHCOO-, or -CONHCONH- a represents (wherein, p represents an integer of 1 to 4, R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a _3, a
_4, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₅ (R ₅ through -COO-R ₅ or a hydrocarbon group is a hydrogen atom or a substituent Represents a hydrocarbon group which may be present)

[0014]

According to the lithographic printing plate precursor of the present invention, the non-image portion of the photoconductive layer containing at least the photoconductive zinc oxide and the binder resin in the photoconductive layer as the uppermost layer is treated with a desensitizing liquid. This is a printing original plate of a type in which the surface is made hydrophilic by treatment to form a lithographic printing original plate. That is, the photoconductive layer of the present invention,
Photoconductive zinc oxide is made to contain a low molecular weight resin [A] composed of a specific copolymer component as a binder resin and non-aqueous solvent-based dispersed resin particles (hereinafter sometimes abbreviated as resin particles) in combination. It is characterized by the following.

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. When the resin particles undergo a desensitization treatment, a carboxyl group protected by a hydrolysis reaction, a redox reaction, a photolysis reaction, or the like chemically reacts to generate a carboxyl group, and has a hydrophobic to hydrophilic property. Has the property of converting to

In the resin particles having such properties, a protected carboxyl group-containing polymer component which is insoluble in the non-aqueous solvent and a polymer component of a dispersion stabilizing resin which is soluble in the non-aqueous solvent are composed of a physicochemical compound. Adsorbed on the basis of the above formula (I
The dispersion stabilizing resin containing a polymerizable double bond group represented by I) is characterized in that both polymer components are chemically bonded.

Another feature of the present invention is that the binder resin [A] has a weight-average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and comprises a repeating unit represented by the following general formula (I). 30% by weight or more as a coalescing component, -PO ₃ H ₂ , -SO
₃ H, -COOH,

Embedded image And a polymer component having 0.5 to 15% by weight of a polymer component having at least one polar group selected from acid anhydride groups. 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]

In the photoconductive layer of the present invention, the photoconductive zinc oxide particles and the resin [A], which contains the resin particles as a binder resin, are closely affected, and the zinc oxide particles are further reduced to fine particles. and two kinds of particles such above is dispersed uniformly. Furthermore, although usually sensitized using a spectral sensitizing dye, even when the type of spectral sensitizing dye used in the photoconductive layer of the present invention is variously changed, these dyes are used as zinc oxide particles as a photoconductor. Can interact sufficiently. In particular, in the case of dyes used for spectral sensitization for semiconductor laser light, this interaction is insufficient with a known binder resin system, but the system of the present invention is an extremely excellent dye which does not cause such a phenomenon. is there.

This is because the details are unknown, but when dispersed in the presence of zinc oxide, resin [A] and resin particles, spectral sensitizing dyes, etc., a specific polar group is bonded to a specific position. Each of the polar groups of the low-molecular-weight resin [A] and the monodisperse, fine-particle-size resin particles containing a specific polar group are adsorbed on the stoichiometric defect of the photoconductive zinc oxide, and Appropriate coating and adsorption on the surface of zinc oxide compensates for the trapping of the photoconductive zinc oxide and dramatically improves the humidity characteristics, while sufficiently dispersing the photoconductive zinc oxide. it is estimated that shall I 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]. As a result, the electrophotographic characteristics (particularly, 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.

That is, in the present system, if the electrophotographic characteristics do not show excellent performance, background contamination occurs in the non-image portion and the reproducibility of the original in the image portion is deteriorated at the time of forming a copy image. What is important is that the non-image portion is sufficiently hydrophilized by the desensitizing treatment and has high water retention that does not cause ink adhesion during printing. The lithographic printing plate precursor of the present invention is characterized in that, with desensitization of zinc oxide particles by a desensitizing solution, the resin particles undergo a desensitizing treatment, thereby generating a carboxyl group and exhibiting hydrophilicity. It is characterized by having a function of improving the water retention of the non-image portion. By the above-described action, the water retention of the non-image portion of the printing original plate of the present invention is dramatically improved.

Further, as described above , since each particle which is made hydrophilic by the resin [A] is dispersed in an appropriate state in the photoconductive layer, it is easy to make the zinc oxide particles and the resin particles hydrophilic. It proceeds quickly and satisfactorily.

On the other hand, in the resin particles of the present invention, if the resin particles having a particle size larger than the zinc oxide particle size are present, the electrophotographic characteristics are deteriorated (particularly, uniform chargeability cannot be obtained). In the copied image, density unevenness in the image portion, cuts and jumps of characters and thin lines, or fogging 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. In addition, as for the resin particles, the specific surface area increases as the particle diameter decreases, and the above-described favorable effects on the electrophotographic characteristics are obtained. Even if the colloidal particles (0.01 μm or less) are sufficient, the molecular weight becomes too small. 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, in the present invention, if the resin particles form a high-order network structure, the dissolution property in water can be further suppressed, and on the other hand, the water swelling property can be exhibited and the water retention property can be 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.

Hereinafter, the binder resin [A] used in the present invention will be described in more detail. The binder resin [A]
Is a polymer component of a specific repeating unit represented by the following general formula (I) in an amount of 30% by weight or more and a specific polar group of 0.1% or more.
-15% by weight. 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 × 10
⁴ , and the glass transition point of the resin [A] is preferably -2.
0 ° C to 110 ° C, more preferably -10 ° C to 90 ° C.

When the molecular weight of the resin [A] is less than 10 ³ , the film-forming ability is reduced and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even if the resin of the present invention is used, In photoreceptors using near-infrared to infrared spectral sensitizing dyes, fluctuations in dark decay retention and photosensitivity under severe conditions of high temperature and high humidity and low temperature and low humidity are slightly larger, and stable copy images are obtained. , The effect of the present invention in that

The content of the polymer component corresponding to the repeating unit of the general formula (I) of the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and the content of the polar group bonded to the terminal of the main chain. Is 0.5 to 15% by weight, preferably 1 to 10% by weight.
% By weight. The polar group content in the resin [A] is 0.
If it is less than 5% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, if the content of the polar group is more than 15% by weight, the dispersibility of even a low molecular weight substance is reduced, and the background stain is increased when used as an offset master.

As the low molecular weight resin [A], the resin represented by the general formula (Ia) or (Ib)
A resin having a methacrylate component having a benzene ring having a specific substituent at the 2-position and / or a specific substituent having an unsubstituted naphthalene ring at the 2- and 6-positions and having a polar group bonded to the terminal [A (Hereinafter, this low-molecular-weight product is referred to as resin [A ']). Resin [A ']
In the formula (Ia) and / or the formula (Ib), the proportion of the methacrylate copolymer component corresponding to the repeating unit is 30% by weight or more, preferably 50 to 97% by weight, and the polarity bonded to the terminal of the polymer main chain. The proportion of the groups is determined by the resin [A '].
It is 0.5 to 15% by weight, preferably 1 to 10% by weight based on 100 parts by weight.

Next, the repeating unit represented by the above general 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 ₈ Or -COO via a hydrocarbon group
-R ₈ (R ₈ 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, specifically, the following represents a represents) the same contents as those described for R _3. Examples of the hydrocarbon in the —COO—R ₈ group via the above hydrocarbon include a methylene group, an ethylene group, and a propylene group. R ₃ has 1 to 18 carbon atoms
An optionally substituted alkyl group (for example, a methyl group,
Ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl , 2-methoxyethyl group, 2-Etokishie ethyl group, 3
-Hydroxypropyl group or the like), an alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group,
An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxy group) A benzyl group, an ethoxybenzyl group, a methoxybenzyl group, etc.), an optionally substituted cycloalkyl group having 5 to 8 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc.), an optionally substituted aryl group ( For example, phenyl, tolyl, xylyl, mesityl, naphthyl, methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl , Ethoxycarbo Butylphenyl group, a cyano phenyl group) and the like.

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

Embedded image General formula (Ib)

Embedded image [In the formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, halogen, —COR ₆ or —COOR ₇ (R ₆ and R ₇ are Each represents 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 connecting -COO- and a benzene ring] In the formula (Ia), preferred T ₁ and T ₂ are each independently a hydrogen atom or a halogen, In addition to the atoms, the hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and an aralkyl group having 7 to 9 carbon atoms. (E.g., benzyl, phenethyl, 3-phenylpropyl, chlorobenzyl,
Dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group) and aryl group (for example, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group) ), And -CO
R ₉ and —COOR ₉ (preferable R ₉ include those described above as preferred hydrocarbon groups having 1 to 10 carbon atoms). In the formulas (Ia) and (Ib), L ₁ and L ₂ are each-
A direct bond connecting COO- and a benzene ring or-(CH
_{2) n1} - (n ₁ represents an integer of 1~3), - CH ₂ OC
_{O -, - CH 2 CH 2} OCO -, - (CH 2) m1 - (m
₁ represents an integer of 1 or 2), a connecting group having 1 to 4 connecting atoms such as —CH ₂ CH ₂ O— and the like, more preferably a direct bonding or a connecting group having 1 to 2 bonding atoms. Can be mentioned.

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

Embedded image (A-2)

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Embedded image (A-18)

Embedded image (A-19)

Embedded image (A-20)

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Next, the specific polar group-containing polymer component contained in the low molecular weight resin [A] will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH,

Embedded image And at least one selected from cyclic acid anhydride-containing groups.

[0034]

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 22 aliphatic groups (e.g., methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, 2-chloroethyl,
Methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc. ) Or an optionally substituted aryl group (eg, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl, fluorophenyl, bromophenyl, chloro-methyl-phenyl, dichlorophenyl, methoxyphenyl) ,
Cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.), and R ₂ has the same content as R ₁ .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. Examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Things. Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring, and a cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic anhydride ring, 2,3-bicyclo [2,2
2] octadicarboxylic anhydride rings and the like; these rings include, for example, chlorine atoms, halogen atoms such as bromine atoms,
An alkyl group such as a methyl group, an ethyl group, 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, a thiophene-dicarboxylic anhydride ring, and the like. Are, for example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (as an alkoxy group,
For example, a methoxy group, an ethoxy group, etc.) may be substituted.

These polar groups may be directly bonded to the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but for example, if specifically mentioned,

Embedded image (D ₁ and d ₂ may be the same or different and each represents a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, etc.), an OH group,
Cyano group, alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group,
Phenethyl group etc.), phenyl group etc.),

Embedded image (D ₃ and d ₄ represent the same contents as d ₁ and d ₂ ),

Embedded image

Embedded image -O-, -S-,

Embedded image [D ₅ represents a hydrogen atom or a hydrocarbon group (specifically, as a hydrocarbon group, a hydrocarbon group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group) Group, decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group ))), -C
O-, -COO-, -OCO-,

Embedded image

Embedded image _{-SO 2 -, - NHCONH -,} - NHCOO -, - N
HSO _2- , -CONHCOO-, -CONHCONH
-, A heterocyclic ring (a 5- to 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom or a condensed ring thereof may be used; for example, a thiophene ring, a pyridine ring,
Furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or

Embedded image (D ₆ and d ₇ may be the same or different and represent a hydrocarbon group or —Od ₈ (d ₈ is a hydrocarbon group). These hydrocarbon groups are the same as those exemplified for d ₅ And the like, or a linking group constituted by a combination thereof.

Further, preferably, in the binder resin [A], the copolymer component represented by the above general formula (I) [the general formula (Ia)
Or (Ib)), and -PO ₃ H _2- , -SO
₃ H-, -COOH-,

Embedded image It is preferable to contain 0.5 to 10% by weight of a copolymer component containing at least one polar group selected from the group consisting of a cyclic acid anhydride and a group containing a cyclic acid anhydride, in order to further improve electrostatic properties.

The copolymer component containing a polar group of the present invention comprises:
For example, any vinyl compound containing the polar group which can be copolymerized with a monomer corresponding to the repeating unit represented by formula (I) (including formulas (Ia) and (Ib)) may be used. For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-form -Fluoro, α-tributylsilyl, α-cyano, β-chloro, β-bromo, α-chloro-β-methoxy, α, β-dichloro), methacrylic acid, itaconic acid, itacone Acid half-esters, itaconic half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid Examples include a half ester derivative of a vinyl group or an allyl group, an ester derivative of a carboxylic acid or a sulfonic acid thereof, and a compound containing the polar group in a substituent of an amide derivative.

Examples of the copolymer component containing a polar group are described below. Here, e ₁ represents H or CH ₃ , e ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₅ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and c 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)

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Embedded image

Further, the low molecular weight resin [A] of the present invention
(Including [A ']) are represented by the general formulas (I) and (I
Along with the monomer (a) and / or (Ib) and the monomer containing the polar group, other monomers other than these may be contained as a copolymerization component.

Examples of such other copolymerization components include methacrylates, acrylates, 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.). 30% by weight of these other monomers in the resin [A]
It is desirable not to exceed.

The resin [A] has a weight average molecular weight of 1 × 10
These are 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. Specific examples of the polymerization initiator include azobis-based initiators and peroxides which are generally known. 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 in the range of 0.1 to 20 parts by weight and the set temperature of polymerization is in the range of 30 to 200 ° C. based on 100 parts by weight of the total amount of the monomers.

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 low molecular weight resin [A] as described above
(Including [A ']) is preferably used in combination with a known resin for conventional photoconductive zinc. The ratio of the low molecular weight resin to the other resin is 5-50 / 95-50 (weight ratio).
Is preferred.

The other resin used in combination may have a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ , preferably 5 × 10 ^{4 to} 5
× 10 ⁵ medium to high molecular weight. The glass transition point of the resin used in combination is from -10 ° C to 120 ° C, preferably 0 ° C.
９０90 ° C. For example, Ryuji Shibata and Jiro Ishiwatari, Polymer, Vol. 17, p. 278 (1968), Harumi Miyamoto,
Hidehiko Takei, Imaging, 1973 (No. 8) Page 9,
Koichi Nakamura, Ed., "Practical Technology of Binders for Recording Materials" First
Chapter 0, C.I. H. C. Publishing (1985), D. Tatt,
SC Heidecker, Tappi, 49 (No. 10), 439
(1966), ES Baltazzi, RG Blanclotte et
al, Phot. Sci. Eng. 16 (No. 5), 354 (19
72), Nguyen Chan K, Isamu Shimizu, Eiichi Inoue, Journal of the Institute of Electrographic Photography 18 (No. 2), 22 (1980), Japanese Patent Publication No. 50-51011, Japanese Patent Application Laid-Open No. 53-54027, 54.
And JP-A-20735 / 57-202544. Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and its derivatives, Polymers and copolymers, butadiene-styrene copolymer, isoprene-styrene copolymer, butadiene-unsaturated carboxylic acid ester copolymer, acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, Acrylic acid ester polymer and copolymer, methacrylic acid ester polymer and copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, itaconic acid diester polymer and copolymer, maleic anhydride Acid copolymer, acrylamide copolymer, methacrylamide copolymer, water Group-modified silicone resin, polycarbonate resin, ketone resin, amide resin, hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylate copolymer, cyclized rubber-acrylate copolymer A copolymer containing a heterocycle containing no nitrogen atom (for example, as a heterocycle, a furan ring,
Tetrahydrofuran ring, thiophene ring, dioxane ring,
Dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resin and the like.

Further, as the resin of the medium to high molecular weight used in combination, the above-mentioned physical properties are satisfied, and preferably, the following general formula (II)
Polymers containing 30 parts by weight or more of the polymer component of the repeating unit represented by I) are exemplified. 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), f ₃ and f ₄ represent the same contents as a ₁ and a ₂ in the formula (I). R ₁₆ represents the same content as R ₃ in the formula (I). Examples of the medium to high molecular weight binder resin (hereinafter referred to as resin [B]) containing the polymer component represented by the general formula (III) include, for example, a random copolymer containing the polymer component represented by the formula (III). Polymeric resin (Japanese
-49817, 63-220149, 63-220
148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-102573, etc.), and a graft copolymer (JP-A-2-53064, JP-A-2-5655).
8 publications, etc.), medium to high molecular weight compounds described in each specification.

Next, the non-aqueous solvent-based dispersed resin particles used in the present invention will be described in more detail. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. First, the monofunctional monomer (A) which is soluble in a non-aqueous solvent but is insolubilized by polymerization and contains at least one functional group which generates a carboxyl group by decomposition will be described.

First, the functional group used in the present invention, which decomposes to form at least one carboxyl group (hereinafter, may be simply referred to as a carboxyl group-forming functional group) will be described in detail. The carboxyl group-forming functional group of the present invention generates a carboxyl group by decomposition, but the number of carboxyl groups generated from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the carboxyl-forming functional group-containing monomer has the general formula (IV)
It is a monomer containing at least one functional group represented by [-COO-L _3]. In the general formula (IV) [—COO-L ₃ ], L ₃ is

Embedded image

Embedded image -N = CH-Q _1,

Embedded image -NH-OH

Embedded image Or

Embedded image Represents However, R ₁₇ and R ₁₈ may be the same or different and represent a hydrogen atom or an aliphatic group, X ₃ represents an aromatic group, Z represents a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group,- CN, -NO _2, -SO
₂ R ₁₇ ′ (where R ₁₇ ′ represents a hydrocarbon group), —CO
OR ₁₈ ′ (where R ₁₈ ′ represents a hydrocarbon group) or —O
—R ₁₉ ′ (where R ₁₉ ′ represents a hydrocarbon group), and n ′ and m ′ represent 0, 1 or 2. Where n ',
When both m 'are 0, Z is not a hydrogen atom. R ₁₉ , R
₂₀ and R ₂₁ may be the same or different from each other, and represent a hydrocarbon group or —O—R ₂₀ ′ (where R ₂₀ ′ represents a hydrocarbon group)
And M represents Si, Sn or Ti. Q ₁ , Q
₂ represents a hydrocarbon group. Y ₁ represents an oxygen atom or a sulfur atom, R ₂₂ , R ₂₃ , and R ₂₄ may be the same or different, each represents a hydrogen atom or a hydrocarbon group, and p ′ represents an integer of 3 or 4. Y ₂ represents an organic residue forming a cyclic imide group.

The functional group of the general formula (IV) [—COO-L ₃ ] generates a carboxyl group by decomposition, and will be described in more detail below. L ₃ is,

Embedded image In the formula, R ₁₇ and R ₁₈ may be the same or different from each other, and are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (for example, methyl group, ethyl group). Group, propyl group, chloromethyl group,
Dichloromethyl group, trichloromethyl group, trifluoromethyl group, butyl group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-chloropropyl group, etc., and X ₃ is preferably phenyl which may be substituted Represents a group or a naphthyl group (eg, phenyl group, methylphenyl group, chlorophenyl group, dimethylphenyl group, chloromethylphenyl group, naphthyl group, etc.), and Z is preferably a hydrogen atom, a halogen atom (eg, chlorine atom, fluorine atom, etc. ), A trihalomethyl group (eg, a trichloromethyl group, a trifluoromethyl group, etc.), a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, a methyl group, a chloromethyl group, a dichloromethyl group) , Ethyl group,
Propyl group, butyl group, hexyl group, tetrafluoroethyl group, octyl group, cyanoethyl group, chloroethyl group, _{etc.), - CH, -NO 2,} -SO 2 R 17 ' [R _17' is an aliphatic group (e.g., carbon atoms 1 to 12 optionally substituted alkyl groups: specifically, a methyl group, an ethyl group, a propyl group,
An aralkyl group having 7 to 12 carbon atoms which may be substituted, such as a butyl group, a chloroethyl group, a pentyl group, and an octyl group:
Specifically, a benzyl group, a phenethyl group, a chlorobenzyl group, a methoxybenzyl group, a chlorophenethyl group, a methylphenethyl group, etc.) or an aromatic group (for example, a phenyl group or a naphthyl group which may contain a substituent): Represents a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a methoxyphenyl group, an acetylphenyl group, an acetamidophenyl group, a methoxycarbonylphenyl group, a naphthyl group, etc.), -COOR ₁₈ ′
(R ₁₈ ′ has the same meaning as R ₁₇ ′) or —O—R ₁₉ ′
(R ₁₉ ′ has the same meaning as R ₁₇ ′). n ',
m 'represents 0, 1 or 2. (However, when n 'and m' are both 0, Z is not a hydrogen atom.)

L ₃ described above is

Embedded image More specifically, the following examples of substituents can be given. For example, β,
β, β-trichloroethyl group, β, β, β-trifluoroethyl group, hexafluoro-i-propyl group, —CH
_{2 - (CF 2 CF 2)} n "-H group (n" denotes 1 to 5), 2-cyanoethyl, 2-nitroethyl group, 2-
Methanesulfonylethyl group, 2-ethanesulfonylethyl group, 2-butanesulfonylethyl group, benzenesulfonylethyl group, 4-nitrobenzenesulfonylethyl group, 4-cyanobenzenesulfonylethyl group, 4-methylbenzenesulfonylethyl group, substitution Benzyl group which may contain a group (for example, benzyl group, methoxybenzyl group, trimethylbenzyl group, pentamethylbenzyl group,
Nitrobenzyl group, etc.), phenacyl group which may contain a substituent (for example, phenacyl group, promofenacyl group, etc.), and phenyl group which may contain a substituent (for example, phenyl group, nitrophenyl group, cyanophenyl group) Methanesulfonylphenyl group, trifluoromethylphenyl group, dinitrophenyl group, etc.).

Also, L ₃ is

Embedded image In the formula, R ₁₉ , R ₂₀ and R ₂₁ may be the same or different from each other, and are preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted [the aliphatic group is an alkyl group, an alkenyl group, an aralkyl group]. A substituent or alicyclic group, and examples of the substituent include a halogen atom, a —CN group, a —OH group, and —O—
Q ′ (Q ′ represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group) and the like], and an optionally substituted aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a tolyl group, chlorophenyl group, a methoxyphenyl group, acetamidophenyl group, a naphthyl group), or -O-R ₂₀ '(R
₂₀ ′ is an alkyl group having 1 to 12 carbon atoms which may be substituted;
An alkenyl group having 2 to 12 carbon atoms which may be substituted, an aralkyl group having 7 to 12 carbon atoms which may be substituted, and 5 carbon atoms;
To 18 substituted or unsubstituted alicyclic groups and 6 to 18 carbon atoms which may be substituted).

M represents each atom of Si, Ti or Sn, more preferably Si atom.

L ₃ is -N = CH-Q ₁ or

Embedded image In the formula, Q ₁ and Q ₂ are each preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted (the aliphatic group includes an alkyl group, an alkenyl group, an aralkyl group,
Represents an alicyclic group, examples of the substituent include a halogen atom,
And a substituted or unsubstituted aryl group having 6 to 18 carbon atoms (e.g., phenyl, methoxyphenyl, tolyl, chlorophenyl, and naphthyl).

L ₃ is

Embedded image In the formula, Y ₁ represents an oxygen atom or a sulfur atom. R ₂₂ , R ₂₃ and R ₂₄ 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, a methyl group, an ethyl group, A propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, a chloroethyl group, a methoxyethyl group, a methoxypropyl group, etc., an alicyclic group which may be substituted (for example, a cyclobentyl group, a cyclohexyl group) Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), an optionally substituted aromatic group (e.g., phenyl group,
Naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, a methoxycarbonylphenyl group, dichlorophenyl group), or _{-O-R 21 '(R 21} ' represents a hydrocarbon group, the specifically R _22, R ₂₃ , R ₂₄ represents the same substituents as the hydrocarbon group). p 'represents an integer of 3 or 4.

L ₃ is

Embedded image In the formula, Y ₂ represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by the general formula (V) or (VI). General formula (V)

Embedded image General formula (VI)

Embedded image In the formula (V), R ₂₅ and R ₂₆ may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom or the like), or an optionally substituted alkyl group having 1 to 18 carbon atoms [ For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Hexadecyl, octadecyl, 2-chloroethyl, 2-methoxyethyl, 2-cyanoethyl, 3-
Chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.];
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 an optionally substituted alkenyl group (e.g. allyl, 3-methyl-2-propenyl group, 2-hexenyl, 4-propyl-2-Penteniiru group, 12-octadecenyl group, etc.), - S-R ₂₂ ' (R ₂₂ ′ represents the same content as the alkyl group, aralkyl group and alkenyl group of R ₂₅ or R ₂₆ ), and optionally substituted aryl group (for example, phenyl group, tolyl group, chlorophenyl group, bromophenyl group, Methoxyphenyl group, ethoxyphenyl group,
Ethoxycarbonylphenyl group) or —NHR ₂₃ ′
(R ₂₃ ′ represents the same content as R ₂₂ ′). R ₂₅ and R ₂₆ may represent a ring-forming residue [eg, a 5- to 6-membered monocyclic ring (eg, a cyclopentyl ring, a cyclohexyl ring), or a 5- to 6-membered bicyclo ring (eg, a bicyclo ring). heptane ring, Bishikurohepuchin ring, bicyclooctane ring, bicyclooctene ring), and further these rings may not be substituted, the substituent R _25,
Including the same as the contents described above in R _26]. q represents an integer of 2 or 3. In the formula (VI), R ₂₇ and R ₂₈ may be the same or different and represent the same as R ₂₅ and R ₂₆ . Further, R ₂₇ and R ₂₈ may represent an organic residue which continuously forms an aromatic ring (for example, a benzene ring, a naphthalene ring, etc.).

In another preferred embodiment of the present invention,
Formula (VII) - of at least one you containing monomer functional group represented by [CO-L _4] can be mentioned. General formula (VII)
In [-CO-L ₄ ], L ₄ is

Embedded image Or

Embedded image Represents Here, R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ each represent a hydrogen atom or an aliphatic group. The aliphatic group, preferably the same meaning as the _{R 22, R 23, R 24} .
R ₃₀ and R ₃₁ and R ₃₂ and R ₃₃ represent an organic residue which may combine to form a condensed ring. Preferably, a 5- to 6-membered monocyclic ring (for example, a cyclopentyl ring, a cyclohexyl ring, etc.) or a 5- to 12-membered aromatic ring (for example, a benzene ring,
Naphthalene ring, thiophene ring, pyrrole ring, pyran ring,
Quinoline ring).

[0058] Further, other preferred aspect of the present invention, Ru monomers include at least one containing oxazolone ring represented by the following general formula (VIII). General formula (VIII)

Embedded image In the general formula (VIII), R ₃₄ and R ₃₅ may be the same or different and each represents a hydrogen atom or a hydrocarbon group, or R ₃₄ and R ₃₅ may form a ring together. .
Preferably, R ₃₄ and R ₃₅ may be the same or different from each other, and each may be a hydrogen atom or an optionally substituted C 1 -C 1.
2 linear or branched alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, 3-hydroxypropyl group Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, 4-chlorobenzyl group, 4-acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), and optionally substituted Good alkenyl groups having 2 to 12 carbon atoms (eg, ethylene group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), and optionally substituted 5- to 7-membered alicyclic group (eg, cyclopentyl group,
A cyclohexyl group, a chlorocyclohexyl group, etc., an aromatic group which may be substituted (for example, phenyl group, chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group, nitrophenyl group, naphthyl group, butylphenyl group) , Dimethylphenyl group, etc.), or R ₃₄ and R ₃₅ may together form a ring (eg, tetramethylene group, pentamethylene group, hexamethylene group, etc.).

The formulas (IV) to (VII) used in the present invention
The monomer containing at least one functional group selected from the group of functional groups represented by I) can be easily synthesized by a conventionally known organic synthesis reaction. For example, The Chemical Society of Japan, “New Experimental Chemistry, Vol. 14, Synthesis and Reaction of Organic Compounds (V)”
Page 2535 (published by Maruzen Co., Ltd.), Yoshio Iwakura: Keisuke Kurita, "Reactive Polymers", page 170 (published by Kodansha), JFW M
cOmie, "ProtectiveGroups in Organic Chemistry"
183 (Plenum Press, 1973) and the like.

The oxazolone ring-containing monomer represented by the general formula (VIII) can be produced by a dehydration ring-closure reaction of N-acyloyl-α-amino acids containing a polymerizable unsaturated bond. Specifically, it can be produced by the method described in Yoshio Iwakura: Keisuke Kurita, "Reactive Polymers", Chapter 3 (published by Kodansha).

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

As described above, the monomer (A) containing a functional group represented by any of the general formulas (IV) to (VIII) used in the method for producing a desired monomer will be described more specifically. And a component represented by the general formula (IX). However, it is not limited to these monomers. General formula (IX)

Embedded image In the formula (IX), X ′ represents —O—, —CO—, —COO—,

Embedded image Represents an aromatic group or a heterocyclic group [provided that d ₉ , d ₁₀ ,
d ₁₁ and d ₁₂ are each a hydrogen atom, a hydrocarbon group, or the formula (IX)
Wherein b ₁ and b ₂ may be the same or different, and represent a hydrogen atom, a hydrocarbon group or a compound of the formula (IX)
Represents-[Y'-W], and l represents an integer of 0 to 18]. Y 'represents a carbon-carbon bond which may be connected via a hetero atom connecting the bonding group X' and the bonding group [W] (hetero atoms are oxygen, sulfur and nitrogen atoms);

Embedded image (In which b ₃ , b ₄ , and b ₅ have the same meanings as b ₁ and b ₂ , respectively). W represents a functional group represented by any of formulas (IV) to (VIII). a ₁ ′ and a ₂ ′ may be the same or different and include a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, a hydrocarbon group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, Methoxycarbonyl group,
An ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted such as a butoxycarbonylmethyl group, a benzyl group, An aralkyl group such as a phenethyl group, an aryl group such as a phenyl group, a tolyl group, a silyl group, or a chlorophenyl group) or the formula (IX)
Having 1 to 1 carbon atoms which may be substituted with a substituent containing a -W group.
18 represents an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, or an aromatic group. Also, [-X'- in the formula (IX)
Y'-] bonding residue is

Embedded image You may connect a part and -W directly. W is the general formula (IV)
Represents the symbolic content represented by (VIII).

Specific examples of the functional group represented by the general formulas (IV) to (VIII) [W group in the formula (IX)] of the present invention are described below. However, the scope of the present invention is not limited to these. (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 (C-31)

Embedded image (C-32)

Embedded image (C-33)

Embedded image (C-34)

Embedded image (C-35)

Embedded image (C-36)

Embedded image (C-37)

Embedded image (C-38)

Embedded image (C-39)

Embedded image (C-40)

Embedded image (C-41)

Embedded image (C-42)

Embedded image (C-43)

Embedded image (C-44)

Embedded image (C-45)

Embedded image (C-46)

Embedded image (C-47)

Embedded image (C-48)

Embedded image (C-49)

Embedded image (C-50)

Embedded image (C-51)

Embedded image (C-52)

Embedded image

When the resin particles [L] are copolymers, the polymer component containing a carboxyl group-forming functional group in the resin particles [L] of the present invention is 10 to 10% of the total copolymer.
It is preferably 95% by weight, particularly preferably 20 to 90% by weight.

The resin particles [L] of the present invention are further characterized in that at least a part thereof is crosslinked. Resin particles [L] in which at least a portion of the polymer has been previously crosslinked
(Resin having a crosslinked structure in the polymer) is hardly soluble or insoluble in an acidic or alkaline aqueous solution when the carboxyl group-forming functional group contained in the resin generates a carboxyl group by decomposition. Is preferred.

In addition to the polar group-containing monomer (A) as described above, other copolymerizable monomers other than these may be contained as a polymer component. Examples of the other monomer include a monomer corresponding to a repeating unit represented by the following general formula (X) or a monomer copolymerized with a monomer corresponding to a component represented by the formula (X).

As the polymerization component in the resin, monomer (A)
Is 30% by weight or more, preferably 50% by weight or more, and when containing other copolymerizable monomers,
It is at most 20% by weight or less. This in a non-aqueous solvent important as a polymerization component as a insoluble may be one hydrophilic represented by the contact angle to distilled water as the object of after generating a carboxyl group can satisfy the following 50 degrees.

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 3 × 10 ³ to 5 × 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 (X). General formula (X)

Embedded image In formula (X), X ₄ has the same content as V ₀ in formula (II), and details are described in the description of V _{0 in} formula (II).

R ₃₆ 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).
_1, are described in the description of a _2.

As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the components described above. The other polymer component may be any as long as it copolymerizes with a monomer corresponding to the component represented by the general formula (X). As the corresponding monomer, for example,
α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (for example, a heterocyclic ring such as a pyran ring, a pyrodrine ring, an imidazole ring, and a pyridine ring), and vinyl group-containing carboxylic acids (for example, acrylic acid, methacrylic acid, Crotonic acid, itaconic acid, maleic acid, etc.), vinyl group-containing carboxamides (eg acrylamide, methacrylamide, crotonic amide,
Itaconamide, itaconic half-amide, itaconic diamide and the like).

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

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 ₄ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , Hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
A methoxyethyl group, a 3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, 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 (eg, a chlorine atom or a bromine atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, COOR ₅ (R ₅ via a butyl group) -COO-R ₅ 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 _4.

Examples of the hydrocarbon in the —COOR ₅ group via the above hydrocarbon include 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 ₅ or -CH
Represents ₂ COOR _5, (R ₅ is 1 to hydrogen atom or a 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.

[0081] That is, the polymerizable double bond Gomoto containing moiety represented by the formula (II), specifically,

Embedded image

Embedded image And the like.

These polymerizable double bond group-containing portions are directly bonded to the main chain of the polymer chain or bonded by an arbitrary connecting 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
₁₃ to d ₁₇ are the same meaning as R ₄ in formula (II).

As the divalent aliphatic group, for example,

Embedded image ｛E ₃ and e ₄ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (eg, a methyl group , Ethyl, propyl, chloromethyl, bromomethyl, butyl, hexyl, octyl, nonyl, decyl, etc.). Q
Is -O -, - S- or -NR ₃₇ - represents, R ₃₇ 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 polymerizable double bond group-containing portion as described above is specifically randomly bonded in a polymer chain.
Alternatively, it is bonded only to one end of the main chain of the polymer chain. Preferably, a polymer in which a polymerizable double bond group-containing portion is bonded to only one end of a polymer chain main chain (hereinafter, 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 ₅ represents a -Cl or -Br, n ₂ represents an integer of 2 to 12, m ₂ is 1
Shows an integer of ~ 4. (D-1)

Embedded image (D-2)

Embedded image (D-3)

Embedded image (D-4)

Embedded image (D-5)

Embedded image (D-6)

Embedded image (D-7)

Embedded image (D-8)

Embedded image (D-9)

Embedded image (D-10)

Embedded image (D-11)

Embedded image (D-12)

Embedded image (D-13)

Embedded image (D-14)

Embedded image (D-15)

Embedded image (D-16)

Embedded image (D-17)

Embedded image (D-18)

Embedded image (D-19)

Embedded image (D-20)

Embedded image (D-21)

Embedded image (D-22)

Embedded image (D-23)

Embedded image (D-24)

Embedded image (D-25)

Embedded image (D-26)

Embedded image (D-27)

Embedded image (D-28)

Embedded image (D-29)

Embedded image (D-30)

Embedded image

Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group in a side chain of a polymer, and the polymer can be synthesized by a conventionally known method. For example, a method of copolymerizing a monomer containing two polymerizable double bond groups having different polymerization 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 can be mentioned as a well-known method. In Table 1, R ₃₈ and R ₃₉
Is a hydrocarbon group and has the same contents as R ₄ in the above formula (II).

[Table 1]

A 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.

[0091] 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 distance between the polymers of the polar group-containing monofunctional monomer (A) [abbreviated as the polymer component (A)] is reduced. It is bridged and forms a higher-order network structure.

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

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

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

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

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

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

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

Examples of the monomer or oligomer having a different polymerizable functional group include, for example, a carboxylic acid 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 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 contain a repeating unit having a protected carboxyl group and a polymer component soluble in the non-aqueous solvent, and have a high molecular weight between the molecular chains. Polymer particles having a bridged structure.

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

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

The dispersion resin of the present invention comprises at least one of the monomer (A) and the dispersion stabilizing resin. When forming a network structure, the polyfunctional monomer (D) may be used, if necessary. ) Coexist, and the important thing in any case is
If the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin 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 10 ⁴
５5 × 10 ⁵ .

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

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

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

The inorganic photoconductive material used in the present invention is a photoconductive zinc oxide. Further, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, and the like may be used in combination as other inorganic photoconductors. 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 is such that 1 part of the binder resin is 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 can be used in combination as a spectral sensitizer, if necessary. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8) No. 12
Page, CJ Young et al .: RCA Review 15 , p. 469 (1954); Kohei Kiyota: IEICE Transactions J6
3-C (No. 2) p. 97 (1980), Yuji Harazaki et al., Industrial Chemistry Magazines 66 , 78 and 188 (1963), Tadaaki Tani, Photographic Society of Japan 35 , p. 208 (1972). Carbonium dye, diphenylmethane dye,
Triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metals), and the like. .

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

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include FM Harmmer “The Cyanine Dyes”. and Related
Compounds "and the like, and more specifically, US Pat. Nos. 3,047,384 and 3,110.
591, 312008, 3125447, 31
28179, 3132942 and 3622317, British Patent Nos. 1226892 and 130927
4, the specifications of 1405898, JP-B-48-781
And the dyes described in JP-A-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. 361,954 and 4,175,956, "Research Disclosure", 1982, 21.
6, pages 117 to 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 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 practical application of photoconductive materials and photoconductors" Chapters 4 to 6: Japan Science Information Co., Ltd. Publishing Division (1986) Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like described in the above-cited references.

The amounts of these various additives are not particularly limited, but are usually 0.0
01 to 2.0 parts by weight.

The thickness of the photoconductive layer is 1 to 100 μm, especially 1
0 to 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 1 μm.
0.5μ is preferred.

Examples of the charge transport 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 needed on the surface layer of the support, and a base conductive plastic on which Al or the like has been deposited on paper. Laminated ones can be used. Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11 (1)
975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing Association (1975), MF Hoover, J. Macromol. Sci. Ch.
em. A-4 (6), pp. 1327-1417 (197
0) etc. are used.

In order to actually prepare the lithographic printing plate precursor of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives and the like are added on a conductive support in a conventional manner by volatile carbonization having a boiling point of 200 ° C. or less. It can be manufactured by dissolving or dispersing in a hydrogen solvent, and applying and drying this to form an electrophotographic photosensitive layer (photoconductive layer). As the organic solvent used,
Specifically, dichloromethane, chloroform, 1,2
-Having 1 to 3 carbon atoms, such as dichloroethane, tetrachloroethane, dichloropropane or trichloroethane;
Halogenated hydrocarbons are preferred. Other solvents used in the coating composition, such as aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride; Can also be used.

A printing plate using the lithographic printing plate precursor of the present invention is prepared by forming a copy image on the electrophotographic printing plate having the above-described structure by a conventional method, and then subjecting the non-image portion to desensitization treatment. Is done. The desensitizing treatment provided in the present invention performs a desensitizing reaction simultaneously with zinc oxide particles and resin particles,
The desensitization of the zinc oxide particles may be followed by decomposing the resin particles, or the resin particles may be decomposed and then subjected to a desensitization reaction of the zinc oxide particles.

As a method for desensitizing zinc oxide, any of conventionally known treatment solutions can be used. For example,
Using a ferrocyanide compound as the main agent of desensitization,
JP-A-62-239158, JP-A-62-292492, JP-A-63-99993, JP-A-63-9994, JP-B-40-7
334, 45-33683, JP-A-57-10788
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.

[0125] desensitizing method of the resin particles or as a method of decomposing a protected carboxyl group is arbitrarily selected by the decomposition reaction of the protected carboxyl group. So
One of the methods is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 and alkaline conditions of pH 8 to 12. Adjustment of these pH can be easily performed by a known compound. Alternatively, a method by a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and as these compounds, known compounds can be used, for example, hydrous hydrazine, sulfite, lipoic acid, hydroquinones, formic acid, Thiosulfate, hydrogen peroxide, persulfate, quinones and the like.

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

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

The scope of the present invention is not limited to the specific compound examples described above. The condition of the treatment is a temperature of 15 ° C.
The immersion time at ６０60 ° C. is preferably 10 seconds to 5 minutes. Further, when a protective group that generates a carboxyl group by photolysis is contained, it can be achieved, for example, by irradiating light under a low-pressure or high-pressure mercury lamp, a halogen lamp or the like for 1 minute to 10 minutes.

[0129]

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 nitrogen stream, and 6.0 g of AIBN was added thereto for 4 hours. Reacted. 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 matter was collected by filtration. Further, the oil was dissolved in tetrahydrofuran 200 g, it was reprecipitated insolubles in filtered again after methanol 1l, and then collecting capturing an oil drying. The Mw was 4.2 × 10 ⁴ in a yield of 32 g.
[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]

Embedded image

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 70 ° C. while stirring under a nitrogen stream. . 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 matter was collected by filtration. Further, the oil was dissolved in tetrahydrofuran 200 g, and reprecipitated again into methanol 2l The insoluble material was filtered off, and was then current capturing an oil drying. The yield was 68 g and Mw was 6.6 × 10 ³ .
[P-4]

Embedded image

Production Examples 5-12 of Dispersion Stabilizing Resins: [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 Dispersion Stabilizing Resins 13-16: [P
In -13] - [P-16] Preparation Example 4, 2- the table below in place of the hydroxy methacrylate - except for using the compound corresponding to 4 were prepared each resin and operating similarly to Production Example 4 . The Mw of each resin was in the range of 6 × 10 ^{3 to} 7 × 10 ³ .

[Table 8]

Production Example 1 of Resin Particles: [L-1] Dispersion stabilizing resin [P-1] 8.0 g (as solid content), monomer (M-1) having the following structure 35 g, methyl methacrylate 15 g, A mixed solution of 1.0 g of diethylene glycol dimethacrylate and 250 g of n-heptane was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 2,
2'-azobis (isovaleronitrile) (abbreviation AIV
N.) was added and reacted for 6 hours. Initiator (AIV
N.) Twenty minutes after the addition, the homogeneous solution began to become cloudy and the reaction temperature rose to 90 ° C. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. Average particle size 0.25μ
m latex. (Monomer M-1)

Embedded image

Production Examples 2-11 of Resin Particles: [L-2]-
[L-11] In Production Example 1 of resin particles, the monomer ( M
Resin particles were produced in the same manner as in Production Example 1, except that the monomers shown in Table 5 below were used instead of -1 ) .

[Table 9]

[Table 10]

Production Example 12 of Resin Particles: [L-12] 30 g of the following monomer ( M-12 ), 5 g of AB-6 (manufactured by Toagosei Co., Ltd .: monofunctional macromonomer composed of butyl acrylate unit), A mixed solution of 3 g of ethylene glycol diacrylate, 80 g of ethyl acetate and 70 g of n-hexane was heated to 60 ° C. under a nitrogen stream. AIV
N. 0.05 g was added and reacted for 4 hours to obtain a white dispersion. After cooling, the dispersion obtained through a 200 mesh nylon cloth had an average particle size of 0.35 μm. (Monomer M-12)

Embedded image

Production Examples of Resin Particles 13 to 23: [L-1
3] to [L-23] A mixed solution of 6 g (as a solid content) of each of the dispersion stabilizing resins [P] shown in Table 6 below and 100 g of methyl ethyl ketone was heated to a temperature of 60 ° C while stirring under a nitrogen stream. To this solution, a mixed solution of 30 g of each monomer (M) in Table 6 below, 5 g of ethylene glycol dimethacrylate, 0.3 g of AIVN, and 150 g of methyl ethyl ketone was added dropwise over 1 hour. After stirring for 1 hour as it was, 0.2 g of AIVN was added and reacted for 3 hours. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. The average particle size of each obtained latex was in the range of 0.20 μm to 0.30 μm.

[Table 11]

[Table 12]

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.
The mixture was dispersed at a frequency of 0 ³ rpm for 10 minutes. To this, 4 g (as a solid content) of dispersed resin particles [L-5] was added, and the mixture was further dispersed at 1 × 10 ³ rpm for 1 minute. The dispersion for forming a photosensitive layer was dried on a paper treated with a conductive material so that the dry adhesion amount was 25 g /
m ² with a wire bar, and 3
Dried for minutes. Then, the mixture was allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours to produce 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-5] were omitted.

Comparative Example B In Example 1, 6 g of resin [A-3] and resin [B-
1] An electrophotographic photosensitive material was prepared 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 the desensitization treatment) and printing of these photosensitive materials. The sex was examined. The printability of the lithographic plate obtained by exposing and developing 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 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-7.

[Table 13]

The embodiments of the evaluation items described in Table 7 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 for one day. 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 desensitizing treatment when the photosensitive material was used as a printing original plate was examined under the following forced conditions. Each light-sensitive material itself 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
I was soaked for 3 minutes in a solution of molar monoethanolamine diluted in 1 liter of distilled water. Next, these plates were printed using a Hamada Star 8005X manufactured by Hamada Star Co., Ltd.
The presence / absence of background stain on the 50th printed matter from the start of printing was visually evaluated.

Note 5) Background 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, it was immersed in an aqueous solution containing molar ethanolamine of Note 4) for 3 minutes 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.

As shown in Table 7, the present invention and Comparative Example A
The light-sensitive material had good photoconductive layer smoothness and electrostatic properties, and the actual copied image was free of background fog and the copied image quality was clear.

Next, when used as an offset master master, a photosensitive material not to be plate-made was diluted with a desensitizing solution, subjected to desensitizing treatment under severe conditions, and actually printed to check the water retention. The prints of the present invention exhibited good water retention without any background stains from the start of printing, and 10,000 clear prints free of background stains were obtained even by using an actual plate. 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 the start of printing, and was not eliminated by printing.

In Comparative Example B, the electrostatic characteristics were remarkably reduced, 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, and even when printing is performed on an original that has been subjected to hydrophilization under ordinary desensitizing conditions, the printed image is significantly stained, and the copied image cannot be obtained on the original after plate making. The printed matter was deteriorated and a satisfactory printing original plate was not obtained from printing.

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 (as solid content) of resin [A-7], 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 Methine dye [II]

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. Electrostatic characteristics (30 ° C., 80% RH); V ₁₀ : −600 V DRR: 82% E _1/10 : 35 erg / cm ² Image pickup I (20 ° C., 65% RH); Good II (30 ° C., 80%) RH); good water retention; 良好 good printing durability; as in 10,000 or more, both electrophotographic properties and printability were good.

Examples 3 to 18 Resins [A] shown in Table 8 below (5 g each (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 Methine dye [III]

Embedded image

In the same manner as in Example 1, electrostatic characteristics and printability of each photosensitive material were examined. The results are shown in Table-8.

[Table 14]

The electrostatic characteristics were as shown in Table 8 at 30 ° C.
Very good results were shown under severe conditions of 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 4 g of resin [A-1], resin [B-4] having the following structure:
5 g, 4.5 g of resin particles [L-18], 200 of zinc oxide
g, uranine 0.02 g, rose bengal 0.04 g,
Bromphenol blue 0.03 g, phthalic anhydride 0.
A mixture of 20 g and 300 g of toluene was dispersed in a homogenizer at a rotation speed of 1 × 10 ³ rpm for 10 minutes to prepare a photosensitive layer-formed product, which was dried on a conductive treated paper so that the dry adhesion amount was 22 g / m ^2. Apply with wire bar, 11
Dry at 0 ° C. for 1 minute. Then, at 20 ° C, 65% R in the dark
Each of the electrophotographic photosensitive materials shown in Table 9 below was prepared by being left under the condition of H for 24 hours. Resin [B-4]

Embedded image

Comparative Example C In Example 19, 4 g of resin [A-1] and resin [B
-4] instead of 31.5 g but only resin [B-4].
An electrophotographic photosensitive material was produced in the same manner as in Example 19 except that 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-9.

[Table 15]

In the above measurement, the same operation as in Example 1 was carried out, except that the following operations were performed for the electrostatic characteristics and the image pickup properties.

Note 6) Measurement method of 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 surface of the photoconductive layer was illuminated at 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).

As shown in Table 9, all the photosensitive materials exhibited good electrostatic characteristics and good image-capturing properties.
In both cases, the electrostatic characteristics were good, and a copy image of clear image quality could be obtained. When used as an offset master master, the present invention had good water retention and printing durability of up to 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 has an electrostatic property,
Both printing characteristics could be maintained with excellent performance.

Examples 20 to 27 In Example 19, 5 g of resin [A] shown in Table 10 below was used.
Each photosensitive material was produced in the same manner as in Example 19, except that (as the solid content) and 4 g of the resin particles [L] (as the solid content).

[Table 16]

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, 31.5 g of the binder resin shown in Table 11 below was used in place of 5.5 g of the resin [A-1] and 31.5 g of the resin [B-4]. Other than that was carried out similarly to Example 19, and produced each electrophotographic photoreceptor.

[Table 17]

[0170] 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) rigors smell of fogging even in A clear image free of generation and fine line skipping was provided. 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 33 In Example 19, instead of 4.5 g of the resin particles [L-18], the resin particles [L-15] (Example 32) or the resin particles [L-16] (Example 33) were used. ) Was used in the same manner as in Example 19 except that 4.5 g (as a solid content) of each electrophotographic photoreceptor was prepared. When the electrostatic characteristics and the image-capturing properties of each photoconductor were examined in the same manner as in Example 19, all were good.

Next, the original plate produced in the same manner as in Example 19 was subjected to a photosensitizing desensitization treatment under the following conditions. Photolysis conditions: The entire surface was irradiated with light under a 400 W high-pressure mercury lamp at a distance of 30 cm for 3 minutes. Next, these plates were passed through an etching machine once with a desensitizing solution of ELP-EX. When this printing original plate was printed in the same manner as in Example 1, 10,000 prints of clear image quality free of background stain were obtained.

Examples 34 to 37 Each of the photoreceptors shown in Table 12 below was subjected to plate making to prepare an 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 18]

Examples 38 to 43 Each of the photoreceptors shown in Table 13 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 having the following formulation for 3 minutes to desensitize the resin.

Resin particle desensitizing liquid 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.

[Table 19]

When these were printed in the same manner as in Example 1, 10,000 or more prints of clear image quality with no background smear were obtained for each master.

[0177]

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.

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Claims (4)

(57) [Claims] An electrophotographic lithographic printing plate precursor comprising at least one photoconductive layer containing a photoconductive zinc oxide and a binder resin on a conductive support, wherein the binder resin Contains at least one of the following resins [A],
Electrophotography, wherein the photoconductive layer further contains at least one of the following nonaqueous solvent-based dispersed resin particles having a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. A lithographic printing original plate. 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 And a polymer component having 0.5 to 15% by weight of a polymer component having at least one polar group selected from acid anhydride groups: general formula (I): [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: In a non-aqueous solvent, a functional group which is soluble in the non-aqueous solvent but insolubilized by polymerization, and which forms a carboxyl group by decomposition. Copolymer resin particles obtained by subjecting at least one kind of the monofunctional monomer (A) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. 2. The electrophotographic lithographic printing plate precursor according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 3. The method according to claim 1, wherein the dispersion stabilizing resin is
2. The electrophotographic lithographic printing plate precursor according to claim 1, wherein the lithographic printing plate precursor 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 represents -O-, -COO-,
_{-OCO -, - (CH 2)} p -OCO -, - (CH 2)
_{p -COO -, - SO 2 -} , ## STR4 ## -CONHCOO-, or -CONHCONH- a represents (wherein, p represents an integer of 1 to 4, R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a _3, a
_4, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₅ - or -COO-R ₅ via a hydrocarbon group (R ₅ is a hydrogen atom or a substituent Represents a hydrocarbon group which may be 4. 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 original plate for electrophotographic lithographic printing according to claim 1 or 2, wherein the original plate contains at least one. General formula (Ia) General formula (Ib) [However, in the above general formulas (Ia) and (Ib), T
₁ and T ₂ each independently represent a hydrogen atom, a carbon number of 1 to 1;
0 hydrocarbon group, halogen, -COR ₆ or -COOR
₇ (R ₆ and R ₇ 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