JPH04268563A - Original plate for electrophotographic lithographic printing - Google Patents

Abstract

PURPOSE:To obtain excellent printed images and high printing resistance even under severe conditions by utilizing the adequate interaction of zinc oxide, a specific resin and dispersion resin. CONSTITUTION:The resin [A] containing a polar group at one terminal of the main chain of the polymer and the nonaq. solvent type dispersion resin particles having the polar group synthesized by a nonaq. solvent type dispersion polymn. method are used as the resin and resin particles to be incorporated into a photoconductive layer. The resin [A] has 1X10<3> to 2X10<4> weight average mol.wt. and contains >=30wt.% the repeating unit expressed by formula I as a polymer component and 0.5 to 15wt.% polymer component having at least one kind of the polar groups selected from -PO3H2, -SO3H, -COOH, -P(=O)(OH) R1 [R1 is a hydrocarbon group or -OR2 (R2 denotes a hydrocarbon group)] and cyclic acid anhydride group.

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 made by an electrophotographic method, and more particularly to an improvement in a composition for forming a photoconductive layer of the lithographic printing plate.

0002

[Prior Art] Currently, many types of offset original plates for direct plate making have been proposed and put into practical use. A photoreceptor with a photoconductive layer as a component is subjected to a normal electrophotographic process to form a highly oleophilic toner image on the surface of the photoreceptor, and then the surface is treated with a desensitizing liquid called an etchant. A technique for obtaining an offset original plate by selectively making non-image portions hydrophilic is widely used.

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset master plate, and at the same time, the surface of the photoreceptor is easily compatible with the desensitizing treatment liquid, and the non-image areas are made sufficiently hydrophilic. It is water resistant, and the surface conductive layer with the image does not separate during printing, and it is compatible with dampening water, and the non-image area is sufficiently coated to prevent staining even when a large number of sheets are printed. It is necessary to have properties such as maintaining hydrophilicity.

It has become clear that these performances are greatly influenced by the type of binder resin in the photoconductive layer. In particular, as an offset original plate, zinc oxide binder resin that improves desensitization properties is used. Various methods are being considered. In particular, multi-component copolymers containing at least a methacrylate (or acrylate) component are mentioned, for example,
No. 0-31011, JP-A No. 53-4027, JP-A-Sho 5
No. 7-202544, JP-A-58-68046, etc. are known.

Furthermore, the use of resins containing functional groups that generate hydrophilic groups upon decomposition as binder resins has been considered; for example, resins containing functional groups that generate hydroxyl groups upon decomposition (Japanese Patent Laid-Open No. No. 62-195684,
JP-A-62-210475, JP-A-62-21047
No. 6), those containing functional groups that generate carboxyl groups upon decomposition (Japanese Patent Application Laid-Open No. 62-21269), or
Contains a functional group that generates hydroxyl or carboxyl groups upon decomposition, and also prevents scumming and improves printing durability by preventing water solubility and having water swelling properties through cross-linking between polymers ( Japanese Patent Publication No. 1-1911
No. 57, JP-A-1-197765, JP-A-1-191
No. 860, JP-A-1-185667, JP-A-1-17
No. 9052, JP-A No. 1-191158, etc.) are known. However, even if the above-mentioned resin is said to be effective in improving desensitization properties, when actually evaluated, it was still unsatisfactory in terms of scumming and printing durability.

[0006] Furthermore, JP-A-1-232356 and JP-A-1-2
61657 publications state that adding resin particles containing hydrophilic groups to the photoconductive layer is effective in improving water retention. It has been confirmed that the water retention properties can be significantly improved by improving these photoconductive compositions.

[0007]

[Problems to be Solved by the Invention] However, when evaluated in more detail as a lithographic printing original plate, environmental changes (high temperature,
(high humidity or low temperature/low humidity), electrophotographic properties (particularly charge retention in the dark, photosensitivity, etc.) fluctuate, and stable and good copied images may not be obtained. This resulted in deterioration of the printed image of printed matter using this as a printing original plate, or a decrease in the scumming prevention effect.

[0008] Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate used as a digital direct lithographic printing original plate, it takes a longer time than when the entire surface is simultaneously exposed using visible light. Furthermore, since there are restrictions on the exposure intensity, higher performance is required in terms of electrostatic properties, particularly dark charge retention properties, and photosensitivity.

On the other hand, with the above-mentioned known original plates, the electrophotographic characteristics deteriorate, and the actual copied images tend to have background fog, as well as skipping of thin lines and blurring of letters.
As a result, when printed as a lithographic printing original plate, the image quality of the printed matter deteriorated, and the effect of preventing scumming by improving the hydrophilicity of the non-image portion of the binder resin was lost.

The present invention is intended to improve the problems of the conventional electrophotographic lithographic printing original plates as described above.

That is, the first object of the present invention is to improve the electrostatic properties (
In particular, it has excellent dark charge retention properties and photosensitivity), reproduces copied images that are faithful to the original, and, as an offset master, does not cause not only uniform background smudges on the entire surface but also dotted smudges. An object of the present invention is to provide a lithographic printing original plate having excellent properties.

[0012] A second object of the present invention is to provide a lithographic printing original plate that has a clear and high-quality image even when the environment during the formation of a copy 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 original plate that is not easily affected by the type of sensitizing dye that can be used in combination and has excellent electrostatic properties even when used in a scanning exposure method using semiconductor laser light.

[0014]

[Means for Solving the Problems] The present invention achieves the above object by providing an electrophotographic image forming apparatus comprising at least one photoconductive layer containing photoconductive zinc oxide and a binder resin on a conductive support. In the lithographic printing original plate, the photoconductive layer contains at least one of the following resins [A] as the binder resin,
Electrophotography characterized in that the photoconductive layer further contains at least one of the following non-aqueous solvent-based dispersed resin particles having a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. This is accomplished by using a lithographic printing plate.

Resin [A]: 1×103 to 2×104
It has a weight average molecular weight of 30% by weight or more as a polymer component of repeating units represented by the following general formula (I), and -PO3 H2 , -S at one end of the polymer main chain.
O3 H, -COOH, -P(=O)(OH)R1 [
R1 represents a hydrocarbon group or -OR2 (R2 represents a hydrocarbon group)] and a cyclic acid anhydride-containing group.

[0016]

[C4]

[However, in the above formula (I), a1,
a2 each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R3 represents a hydrocarbon group] [The above -P(=O)(OH)R1 is

[0018]

[C5]

[0019] is shown. ] Non-aqueous solvent-based dispersed resin particles: particles that are soluble in a non-aqueous solvent but become insolubilized by polymerization;
carboxyl group, sulfo group, sulfino group, phosphono group, -P(=O)(OH)R0 [R0 represents a hydrocarbon group or -OR10 (R10 represents a hydrocarbon group)],
A monofunctional monomer containing at least one polar group selected from a hydroxyl group, a formyl group, an amide group, a cyano group, an amino group, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterocyclic group ( Copolymer resin particles obtained by subjecting C) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.

That is, the lithographic printing original plate of the present invention contains at least zinc oxide particles and a specific copolymer component in the photoconductive layer, and has a low molecular weight compound in which a specific polar group is bonded to one end of the polymer main chain. [A] and non-aqueous solvent-based dispersed resin particles (hereinafter sometimes abbreviated as resin particles) containing a specific polar group. As mentioned above, the technique of containing hydrophilic resin particles in the photoconductive layer and the technique of using a resin containing a polar group as a binder resin of an electrophotographic photoreceptor are both known. By using particles, water retention was improved compared to before, but it was still not satisfactory.

In contrast, the present invention uses a resin [A] containing a polar group at one end of the polymer main chain as the resin and resin particles to be contained in the photoconductive layer, and a resin synthesized by a non-aqueous dispersion polymerization method. Surprisingly, by using non-aqueous solvent-based dispersed resin particles containing polar groups, the above-mentioned problems that were unresolved by the above-mentioned known techniques alone can be solved, that is, water retention and printing durability can be improved. It was found that there was a dramatic improvement. In addition, in a printing original plate in which the non-image area of the photoconductive layer containing at least photoconductive zinc oxide and a binder resin is treated with a desensitizing liquid to make the surface hydrophilic and the lithographic printing original plate is made hydrophilic. Compared to known technologies that coexist with synthetic resin particles, the technology of the present invention achieves both faithful reproduction of copied images and excellent water retention in non-image areas even under harsh environmental conditions of high temperature and humidity. It is possible.

Although the details are unknown, this means that when dispersed in the presence of zinc oxide, resin [A], and resin particles, a specific polar group is bonded to one end of the polymer main chain. Each of the polar groups of the low molecular weight resin [A] and the monodispersed, microscopic resin particles containing a specific polar group is adsorbed to the stoichiometric defects of the photoconductive zinc oxide, and , proper coating and adsorption of the surface of zinc oxide compensates for trapping of photoconductive zinc oxide and dramatically improves humidity characteristics, while sufficient dispersion of photoconductive zinc oxide is achieved. It is presumed that this suppresses aggregation.

[0023] As a result, the hydrophilization reaction of zinc oxide by the desensitization treatment liquid and the retention of the hydrophilization product (chelate compound) on the membrane surface part can be achieved by the membrane formed by the interaction of the above three components. It is considered that the situation is very suitable. Furthermore, since the resin particles are particles that inherently have hydrophilic properties, they play an important role in promoting the hydrophilization reaction during desensitization treatment and improving the hydrophilicity of the surface portion after hydrophilization. considered to be a thing. It is presumed that the above-described effects dramatically improve the water retention properties of the non-image areas of the printing master plate of the present invention. In addition to exhibiting good water retention, this method also requires excellent electrophotographic properties to cause background smudges to occur in non-image areas and deteriorate original reproducibility in image areas when copying images are formed. As a result, it becomes impossible to obtain printed matter with satisfactory image quality.

On the other hand, in the lithographic printing original plate of the present invention, the resin particles and the resin [A
] Only by the proper presence of both can the dispersion state down to the microscopic state of photoconductive zinc oxide be controlled, which improves not only water retention but also electrophotographic properties (especially actual imaging properties). temperature, high humidity, low temperature,
It has become possible to stably maintain good performance even under harsh conditions of low humidity. Furthermore, in the present invention, the non-aqueous solvent-based dispersed resin particles may form a higher-order network structure. In the present invention, resin particles forming a high-order network structure can further suppress dissolution in water, exhibit water-swelling properties, and further improve water retention.

In the present invention, the resin particles that do not form a high-order network structure as described above or the resin particles that do form a high-order network structure (hereinafter simply referred to as network resin particles) are photoconductive oxidized resin particles. It is preferably used in an amount of 0.01 to 10% by weight based on 100 parts by weight of zinc. If the amount of resin particles or network resin particles is less than 0.01% by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 10% by weight, the hydrophilicity of the non-image area can be further improved, but it is difficult. The electrophotographic characteristics under these conditions deteriorate, resulting in a deteriorated copy image. Furthermore, the above-mentioned dispersion stabilizing resin in the present invention includes:
Particularly preferred are those containing at least one polymerizable double bond group represented by the following general formula (II) in the polymer chain.

[0026]

[C6]

[In general formula (II), V0 is -O
-, -COO-, -OCO-, -(CH2)p -O
CO-, -(CH2)p-COO-, -SO2-
, -CON-R01-, -SO2 N-R01-, -C
6 H4 -, -CONHCOO-, or -CONHC
represents ONH- (where p represents an integer from 1 to 4,
R01 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b1 and b2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R02 or a carbide group. -COO- via hydrogen group
R02 (R02 represents a hydrogen atom or a hydrocarbon group that may be substituted)] The resin particles used in the present invention have an average particle diameter that is the same as the maximum particle diameter of the photoconductive zinc oxide particles, or It is smaller than that and has a narrow particle size distribution and uniform particle size.

[0028] The resin film formed by coating the resin particles dissolved in any soluble solvent has a contact angle (measured with a goniometer) with distilled water of 50 degrees or less, preferably 40 degrees. A hydrophilic polymer component having the following values and having such properties, consisting of a specific polar group that is insoluble in the non-aqueous solvent, and a dispersion stabilizing resin that is soluble in the non-aqueous solvent. In the case of a dispersion stabilizing resin which is formed by physicochemically adsorbing a polymer component of It is characterized by consisting of the following. On the other hand, in the resin particles of the present invention, if the resin particles have a flow diameter larger than the zinc oxide particle diameter, the electrophotographic properties will deteriorate (particularly, uniform charging properties will not be obtained), and as a result, in the copied image. Density unevenness in the image area,
Characters and thin lines may be cut or skipped, or background fog may occur in non-image areas.

Specifically, the resin particles of the present invention have a maximum particle size of 2 μm or less, preferably 0.5 μm or less. The average particle diameter of the particles is 0.8 μm or less, preferably 0.5 μm or less. A: The smaller the particle size of the resin particles, the larger the specific surface area, which brings about good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, molecules It will be similar to the case of dispersion, and the effect of particles on improving water retention capacity will be weakened, so 0
．． It is preferable to use a thickness of 0.001 μm or more. Further, in the present invention, the resin particles are a hydrophobic polymer component, that is, a dispersion stabilizing resin is bonded to a polymer component represented by the formula (II), and this hydrophobic portion serves as a binding agent for the photoconductive layer. Since it interacts with the binder resin, the anchor effect of this part prevents it from being eluted by dampening water during printing, and good printing characteristics can be maintained even when printing a large number of sheets.

The resin [A] contains at least one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). (resin [A
′]) is preferred.

[0031]

[C7]

[However, in the above formulas (Ia) and (Ib), T1 and T2 each independently represent a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, -COR4
or -COOR5 (R4 and R5 each have 1 carbon number
~10 hydrocarbon groups), L1 and L2
each represents a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring] When resin [A'] is used, the electrophotographic properties ( Especially V10, D.R.R., E1 /
10) can be achieved and the resulting image is good. The reason for this is unknown, but one reason is that the planarity of the benzene ring or naphthalene ring, which is the ester component of methacrylate, allows these polymer molecular chains to be properly aligned at the zinc oxide interface in the film. This is thought to be due to the fact that

[0033] The binder resin [A
] will be explained in more detail. In weight [A],
The weight average molecular weight is 1x103 to 2x104, preferably 3x103 to 1x104, and the glass transition point of the resin [A] is preferably -20°C to 110°C, more preferably -10°C to 90°C. It is ℃. If the molecular weight of the resin [A] is less than 103, the film forming ability will decrease and sufficient film strength cannot be maintained, while if the molecular weight is more than 2 x 104, even if the resin of the present invention is For photoreceptors using infrared spectral sensitizing dyes, fluctuations in dark decay retention and photosensitivity become somewhat larger under harsh conditions of high temperature and high humidity, and low temperature and low humidity, making it possible to obtain stable copied images. The effect of the present invention will be diminished.

The proportion of the polymer component corresponding to the repeating unit of general formula (I) in the resin [A] is 30% by weight or more;
Preferably, the proportion of the polymer component containing a specific polar group is 50 to 97% by weight, and 0.5 to 15% by weight, preferably 1 to 10% by weight. If the polar group content in the resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the polar group content is more than 15% by weight, the dispersibility decreases no matter how low the molecular weight, and furthermore, background smudge increases when used as an offset master.

[0035] As the low molecular weight resin [A], resins having specific substituents at the 2-position and/or at the 2- and 6-positions, as shown in the general formulas (IIIa) and (IIIb) above, can be used. Contains a methacrylate component with a specific substituent having a benzene ring or an unsubstituted naphthalene ring,
Resin [A] (hereinafter, this low molecular weight material will be referred to as resin [A']) is preferable. The formula for resin [A'] (
The proportion of the methacrylate copolymer component corresponding to the repeating unit of IIIa) and/or formula (IIIb) is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the specific polar group-containing polymer component is Resin [A'] 10
0.5 to 15% by weight, preferably 1 to 15% by weight based on 0 parts by weight
It is 10% by weight.

Next, the repeating unit represented by the general formula (I), which is contained in the resin [A] in an amount of 30% by weight or more, will be further explained. In general formula (I), a1 and a2 are preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-R8, or a hydrocarbon group. - through the group
COO-R8 (R8 is a hydrogen atom or a carbon number of 1 to 1
8 represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as explained for R3 below) .

The hydrocarbon in the -COO-R8 group via the above hydrocarbon includes a methylene group, an ethylene group,
Examples include propylene group. R3 has 1 to 1 carbon atoms
18 optionally substituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc.), optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group,
allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7-12
optionally substituted aralkyl group (benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.) having 5 to 8 carbon atoms; optionally substituted cycloalkyl groups (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, (ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.).

More preferably, in the copolymer component corresponding to the repeating unit of the general formula (I), the copolymer component corresponding to the repeating unit of the general formula (II)
Ia) and/or a copolymer component (resin [A']) represented by a methacrylate component containing a specific aryl group represented by the general formula (IIIb). Formula (I
In a), preferable T1 and T2 are, independently of each other, in addition to a hydrogen atom, a chlorine atom and a bromine atom,
The hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), an aralkyl group having 7 to 9 carbon atoms (
For example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group,
chloro-methyl-benzyl) and aryl groups (e.g. phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl, dichlorophenyl), and -COR4 and -COOR5
(Preferably R4 and R5 have the above-mentioned carbon numbers of 1 to
10 preferred hydrocarbon groups can be mentioned.

In formulas (Ia) and (Ib), L1
and L2 are each a direct bond connecting -COO- and a benzene ring, or -(CH2)n1- (n1 represents an integer of 1 to 3), -CH2 OCO-, -CH2 CH2 O
A linking group having 1 to 4 linking atoms such as CO-, -(CH2O)m1- (m1 represents an integer of 1 or 2), -CH2CH2O-, and more preferably a direct bond or bond. A linking group having 1 to 2 atoms can be mentioned. Formula (Ia) or (I
Specific examples of copolymer components corresponding to the repeating unit b) are listed below. However, the scope of the present invention is not limited thereto. In (a-1) to (a-20) below, n is 1 to
4 integer, m is 0 or an integer from 1 to 3, p is an integer from 1 to 3, R10 to R13 are all -Cn H2n+1 or -
(CH2)m-C6H5 (where n and m are the same as above), X1 and X2 may be the same or different and represent a hydrogen atom, -Cl, -Br, or -I.

[0040]

[Chemical formula 8]

[0041]

[Chemical formula 9]

[0042]

[Chemical formula 10]

[0043]

[Chemical formula 11]

[0044]

[Chemical formula 12]

[0045]

[Chemical formula 13]

[0046]

[Chemical formula 14]

[0047]

[Chemical formula 15]

[0048]

[Chemical formula 16]

[0049]

[Chemical formula 17]

Next, the polar group bonded to one end of the polymer main chain of the low molecular weight resin [A] will be explained. The polar group is -PO3 H2, -SO3 H, -COOH, -P
(=O)(OH)R1 and at least one selected from cyclic acid anhydride-containing groups.

-P(=O)(OH)R1 group means that R1 above represents a hydrocarbon group or -OR2 group (R2 represents a hydrocarbon group), specifically, R1 has 1 to 2 carbon atoms.
2 aliphatic groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group) , allyl group,
crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (e.g. Phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group , butoxyphenyl group, etc.), and R2 is R
The content is the same as 1.

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

Examples of aliphatic dicarboxylic anhydrides include:
Succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring acid anhydride ring, 2
, 3-bicyclo[2,2,2]octadicarboxylic anhydride rings, etc., and these rings include, for example, halogen atoms such as chlorine atoms and bromine atoms, methyl groups, ethyl groups, butyl groups, hexyl groups, etc. The alkyl group, etc. may be substituted.

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

[0055] These polar groups may be bonded directly to the terminal end of the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but specific examples include -[C(d1)(d2
)] - (d1 and d2 may be the same or different, and each represents a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.),
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 (representing a group, etc.),
-(CH(d3)-CH(d4))]-(d3, d
4 represents the same content as d1 and d2), -C6 H
10-, -C6 H5, -O-, -S-, -N(d5
)-[d5 represents a hydrogen atom or a hydrocarbon group (the hydrocarbon group specifically includes a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, Octyl group, decyl group, dodecyl group, 2
-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorofer group, methoxyphenyl group, butylphenyl group)],
-CO-, -COO-, -OCO-, -(d5)CO
N-, -SO2 N(d5)-, -SO2 -, -N
HCONH-, -NHCOO-, -NHSO2-,-
CONHCOO-, -CONHCONH-, heterocycle (any 5- to 6-membered ring containing at least one type of O, S, N, etc. as a hetero atom, or a condensed ring thereof; for example, a thiophene ring, a pyridine ring, (furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or -Si(d6)(d7)-(d6, d7
may be the same or different, and may be a hydrocarbon group or -Od8
(d8 is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones listed for d5) alone or in combination.

Furthermore, preferably, the binder resin [A] is a copolymer component represented by the above general formula (I) [general formula (Ia)
or (Ib)], and as polymer components copolymerized therewith, -PO3 H2, -S
Contains 0.5 to 10% by weight of a copolymer component containing at least one polar group selected from O3H, -COOH, -P(=O)(OH)R1, and a cyclic acid anhydride-containing group. is preferable in terms of further improving electrostatic properties.

These specific polar groups represent the same content as the polar group bonded to one end of the polymer main chain described above. In the resin [A], the proportion of the polar groups contained as copolymer components and the polar groups bonded to one end of the polymer main chain is different from that of other binder resins constituting the photoconductive layer of the present invention. , resin particles, spectral sensitizing dye, chemical sensitizer, or other additives, and it is preferable to adjust the ratio arbitrarily. What is important is that the total amount of both polar groups is used within the range of 0.5 to 15% by weight.

[0058] The copolymerization component containing these polar groups is
For example, any vinyl compound containing a polar group that can be copolymerized with a monomer corresponding to a repeating unit represented by general formula (I) [including general 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 and Technology, Baifukan (published in 1986). Specifically, acrylic acid, α and/or β
Substituted acrylic acid (e.g. α-acetoxy, α-acetoxymethyl, α-(2-amino)methyl, α-chloro, α-bromo, α-fluoro, α-tributylsilyl, α-cyano body, β-chloro body, β-bromo body,
α-chloro-β-methoxy form, α,β-dichloro form, etc.)
, methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 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, vinyl benzenesulfonic acid,
Vinyl sulfonic acid, vinyl phosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester dielectrics and amide derivatives of these carboxylic acids or sulfonic acids, compounds containing the polar group in the substituent, etc. It will be done.

Examples of copolymerizable components containing polar groups are shown below. Here, e1 represents H or CH3, and e2
represents H, CH3 or CH2COOCH3, R
14 represents an alkyl group having 1 to 4 carbon atoms, R15 represents an alkyl group having 1 to 6 carbon atoms, a benzyl group, or a phenyl group, c represents an integer of 1 to 3, and d represents an integer of 2 to 11. , e represents an integer of 1 to 11, f represents an integer of 2 to 4, and g represents an integer of 2 to 10.

[0060]

[Chemical formula 18]

[0061]

[Chemical formula 19]

[0062]

[C20]

[0063]

[C21]

[0064]

[C22]

[0065]

[C23]

[0066]

[C24]

[0067]

[C25]

[0068]

[C26]

[0069]

[C27]

[0070]

[C28]

[0071]

[C29]

[0072]

[C30]

[0073]

[Chemical formula 31]

[0074]

[C32]

[0075]

[Chemical formula 33]

[0076]

[C34]

[0077]

[C35]

[0078]

[C36]

[0079]

[C37]

[0080]

[C38]

[0081]

[C39]

[0082]

[C40]

[0083]

[C41]

[0084]

[C42]

[0085]

[C43]

Furthermore, the low molecular weight resin [A] of the present invention ([A
']) refers to the monomers of general formulas (I), (Ia) and/or (Ib) described above and the monomers containing the polar group, as well as other monomers other than these. It may be contained as a polymerization component. Other such copolymerization components include:
For example, in addition to methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those explained in general formula (I), α-olefins, vinyl carboxylates, or acrylic esters (e.g., carboxylic esters) acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (e.g. dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides , styrenes (e.g. styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocycles Vinyls (e.g. vinylpyrrolidone, vinylpyridine,
(vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.)
etc.

It is desirable that the amount of these other monomers does not exceed 30% by weight in the resin [A]. In resin [A], the method of bonding the polar group to one end of the polymer main chain is as follows:
A method of reacting various reagents with the ends of living polymers obtained by conventionally known anionic polymerization or cationic polymerization (method using ionic polymerization method), a method of reacting a polymerization initiator and/or a chain transfer agent containing a specific polar group in the molecule, etc. A reactive group (e.g., an amino group, a halogen atom, an epoxy group, an acid halide, etc.) is obtained at the terminal by a method of radical polymerization (method using a radical polymerization method), or by an ionic polymerization method or a radical polymerization method as described above. It can be easily produced by a synthetic method such as a method in which a polymer is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P. Dreyfuss, R.
P. Quirk, Encycle. Polym, Sci.
Eng, 7, 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dye and Medicine", 30, 232 (1985), Akira Ueda,
It can be produced by the method described in the review article of Susumu Nagai, "Science and Industry" 60, 57 (1986) and the literature cited therein.

Specifically, the chain transfer agent used is:
For example, mercapto compounds (such as thioglycolic acid, thiomalic acid, thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-
[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]
Propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-butanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, 4-(2-methyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphonoic anhydride, 2
-Mercaptoethylphosphonoic anhydride monomethyl ester, or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropane) sulfonic acid, etc.).

Specific examples of the polymerization initiator containing the polar group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid) and 4,4'-azobis(4-cyanovaleric acid).
cyanovaleric acid chloride), 2,2'-azobis(2-
cyanopropanol), 2,2'-azobis(2-cyanopentanol), 2,2'-azobis[2-methyl-
N-(2-hydroxyethyl)-propioamide], 2
, 2'-azobis{2-methyl-N-1,1-bis(hydroxymethyl)-2-hydroxyethyl]propioamide}, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2 -imidazolin-2-yl]propane}, 2,2'-azobis[2-(2-imidazoline-2
-yl)propane], 2,2'-azobis[2-(4,
5,6,7-tetrahydro-1H-1,3-diazopin-2-yl)propane] and the like.

The amount of these chain transfer agents or polymerization initiators is 0.5 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers. The low molecular weight resins [A] (including [A']) as described above are preferably used in combination with known resins for conventional photoconductive zinc. The ratio of the low molecular weight resin [A] to other resins is preferably 5-50/95-50 (weight ratio). Other resins used in combination have a weight average molecular weight of 3 x 104 ~ 1 ~
106, preferably a medium to high molecular weight substance of 5 x 104 to 5 x 105. Further, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C.

For example, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) p. 9, edited by Koichi Nakamura, ""Practical Technology of Binders for Recording Materials" Chapter 10, C. H. C. Publishing (1985), D. Tatt,
S. C. Heidecker, Tappi, 49 (No.
．． 10), 439 (1966), E. S. Baltaz
ziR. G. Blanclotte etal,
Photo. Sci. Eng. , 16 (No. 5), 3
54 (1972), Nguyen Tran Khe, Isamu Shimizu, Eiichi Inoue, Journal of the Electrophotography Society 18 (No. 2), 22 (
1980), JP 50-51011, JP 53-5
4027, 54-20735, 57-202544
Materials disclosed in each publication are listed.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers thereof, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymers, acrylic ester polymers and copolymers, methacrylic ester polymers and copolymers, styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, itaconic diester polymers and copolymers , maleic anhydride copolymer, acrylamide copolymer,
Methacrylamide copolymer, hydroxyl-modified silicone resin,
Polycarbonate resin, ketone resin, amide resin, hydroxyl- and carboxyl-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic ester copolymer, cyclized rubber-acrylic ester copolymer, containing nitrogen atoms Copolymers containing heterocycles (heterocycles include furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy Examples include resin.

Further, as a medium to high molecular weight resin to be used in combination, it satisfies the above-mentioned physical properties and is preferably of the following general formula (II
Examples include polymers containing 30 parts by weight or more of the repeating unit polymer component represented by I).

[0095]

[C44]

[In formula (III), V is -COO-, -O
CO-, -(CH2)h -OCO-, -(CH2)
h represents -COO-, -O- or -SO2-. However, h represents an integer of 1 to 4] In general formula (III), f3 and f4 are expressed by formula (I
) represents the same content as a1 and a2 in R6 represents the same content as R3 in formula (I). General formula (I
The medium to high molecular weight binder resin containing the polymer component represented by formula (III) (hereinafter referred to as resin [B]) is, for example, a random copolymer containing the polymer component represented by formula (III). Resin (JP-A No. 63-49817, No. 63-2
20149, 63-220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-2014)
102573 etc.), graft type copolymers (JP-A No. 2-
53064, No. 2-56558, etc.), etc., of medium to high molecular weight as described in the specifications of each issue.

[0097] The non-aqueous solvent-based dispersed resin particles used in the present invention will be explained in more detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. First, to explain the monofunctional monomer (C) which is soluble in non-aqueous solvents but becomes insolubilized by polymerization, the monomer (C) has -
CO2 H, -SO2 H, -PO3 H2, -SO
2H, -OH, -CN, -CHO, -CONH2,
-SO2 NH2, -P(=O)(OH)R0, -
It contains at least one polar group selected from NR11R12, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterogroup.

Here, -P(=O)(OH)R0 and the cyclic acid anhydride-containing group are the same as explained in the section of resin [A] above. R11 and R12 may each be the same or different and represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (specifically, a hydrocarbon group having the same content as R0). However, R1
The total number of carbon atoms of 1 and R12 is 8 or less. More preferably, the total number of carbon atoms in R11 and R12 is 4 or less.

The heterocycle containing at least one nitrogen atom is preferably a 4- to 6-membered heterocycle, such as a pyridine ring, a piperidine ring,
Examples include a pyrrole ring, an imidazole ring, a pyrazine ring, a pyrrolidine ring, a pyrroline ring, an imidazoline ring, a pyrazolidine ring, a piperazine ring, a morpholine ring, and a pyrrolidone ring. These heterocycles may contain a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), an optionally substituted hydrocarbon group having 1 to 8 carbon atoms ( For example, methyl group, ethyl group, propyl group,
Butyl group, 2-chloroethyl group, 2-bromoethyl group,
2-hydroxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-carboxyethyl group, carboxymethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-
Methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-methanesulfonylethyl group, benzyl group, carboxybenzyl group, carboxymethylbenzyl group, phenyl group, carboxyphenyl group, sulfophenyl group, methanesulfonylphenyl group, ethanesulfonylphenyl group, carboxymethylphenyl group, methoxyphenyl group, chlorophenyl group, etc.), -OR13 (R13 represents the same content as the above-mentioned optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or -COOR14 group (R14 is R
(representing the same content as 13).

[0100] Moreover, the above -COOH group, -SO2 H group,
-SO3 H group, -PO3 H2 group, -P(=O)(
The OH)R0 groups each represent a metal salt of an alkali metal (e.g., lithium, sodium, potassium, etc.), an alkaline earth metal (e.g., calcium, magnesium, etc.), zinc, aluminum, or an organic base (e.g., triethylamine, pyridine, etc.). morpholine, piperazine, etc.). The monomer (C) constituting the main component of the resin particles of the present invention may contain at least one of the above polar groups and have one polymerizable double bond group in one molecule. Either is fine. More specifically, an example of the monomer (C) is shown by general formula (IV).

[0101]

[C45]

[0102] In the formula, X1 is a direct bond or -CO
O-, -OCO-, -O-, -SO2 -, -CO-,
-SO2 NR15-, -CONR15-, -CONH
COO-,-CONHCONH-,-[C(R16)(
R17)]i -, -C6 H4 - or -C6 H1
Represents 0-.

[R15 is each a hydrogen atom or a carbon number of 1 to 7]
optionally substituted hydrocarbon groups (preferably, e.g.
Methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-hydroxyethyl group, 3-bromo-2
-Hydroxypropyl group, 2-carboxyethyl group, 3
-carboxypropyl group, 4-carboxybutyl group, 3
-sulfopropyl group, benzyl group, sulfobenzyl group,
Methoxybenzyl group, carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-methanesulfonylethyl group, 2-cyanoethyl group, N,N (dichloroethyl)aminobenzyl group, N,N(dihydroxyethyl)aminobenzyl group,
chlorobenzyl group, methylbenzyl group, N,N (dihydroxyethyl)aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc.),

R16 and R17 may be the same or different and are hydrogen atoms, halogen atoms (preferably, for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) or aliphatic groups having 1 to 4 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, etc.), and i represents an integer of 1 to 6. ] W represents a polar group of the monomer (C) described above.

[0105] L3 is -[C(l1)(l2)]
-, -C6 H10-, -C6 H4 -, -[C(l
3)=C(l4)], -COO-, -OCO-, -
O-, -S-, -SO2 -, -N(l5), -CO
N(l6)-,-SO2 N(l7)-,-NHC
OO-,-Si(l8)(l9)-,-NHCON
Represents a linking group selected from H- or -CO- or a linking group formed by a combination of these linking groups. [Here, l1 to l4 may be the same or different,
Hydrogen atom, halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2 -chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group) or the formula (I
V) represents a -[L1-W] group, and l5 to l9 represent the same content as R15 above. ]

[0106] e1 and e2 may be the same or different and are hydrogen atoms, halogen atoms (preferably, for example,
fluorine atom, chlorine atom, bromine atom, etc.), -COOH group,
-COOR18 groups, -CH2 COOR18 groups (R18
represents a hydrocarbon group having 1 to 7 carbon atoms, and specifically includes the same content as the hydrocarbon group of R15 above) or an alkyl group having 1 to 4 carbon atoms (preferably, for example, a methyl group, (ethyl group, propyl group, butyl group, etc.). The above monomer (C) will be more specifically exemplified below, but the present invention is not limited thereto.

Here, a is -H, -CH3, -Cl,
-CH2COOH or -CH2COOCH3, b is -CH3, -COOH, -CONH2, -
CONHC2 H5 or -COOCH3, C
represents -CH3 or -H, d represents -CH3, -H or -Cl, e represents -H, -CH3, -CH2C
OOH or -CH2COOCH3, f is -H
, -CH3 or -CH2COOCH3, R
19 represents -H, -CH3 or -C2H5, Y
1 is -SO3H, -COOH, -CH2OH, -
O-P(=O)(OH)2,-SO2H,-CON
H2 , -SO2 NH2 or -OH, Y2
represents -OH or -NH2, n1 represents an integer of 1 to 12, n2 represents an integer of 1 to 4, and n3 represents an integer of 2 to 4.
represents an integer of 12, n4 represents an integer of 1 to 11, n
5 represents an integer of 1 to 10, n6 represents an integer of 2 to 10, n7 represents an integer of 1 to 3, m1 represents an integer of 1 to 1
represents an integer of 0, and m2 represents an integer of 1 to 4.

[0108]

[C46]

[0109]

[C47]

[0110]

[C48]

[0111]

[C49]

[0112]

[C50]

[0113]

[C51]

[0114]

[C52]

[0115]

[C53]

[0116]

[C54]

[0117]

[C55]

[0118]

[C56]

[0119]

[C57]

[0120]

[C58]

[0121]

[C59]

[0122]

[C60]

[0123]

[C61]

[0124]

[C62]

[0125]

[C63]

[0126]

[C64]

[0127]

[C65]

[0128]

[C66]

[0129]

[C67]

[0130]

[C68]

[0131]

[C69]

[0132] Along with the polar group-containing monomer (C) as described above, other copolymerizable monomers other than these may be contained as a polymer component. Examples of other monomers include monomers that are copolymerized with monomers corresponding to repeating units of the general formula (V) described later or monomers corresponding to components represented by the formula (V). As a polymerization component in the resin, the proportion of monomer (C) present is 30% by weight or more, preferably 50% by weight or more.
% by weight or more, and if other copolymerizable monomers are contained, the amount is at most 20% by weight or less.

[0133] What is important about the polymerization component which is insoluble in this non-aqueous solvent is that it satisfies the above-mentioned hydrophilicity expressed by the contact angle with respect to distilled water of 50 degrees or less. Next, the dispersion stabilizing resin of the present invention will be explained. It is important that the dispersion stabilizing resin is solvated and soluble in the nonaqueous solvent, and plays a dispersion stabilizing effect in so-called nonaqueous dispersion polymerization. Specifically, for 100 parts by weight of the solvent, Any material may be used as long as it dissolves at least 5% by weight at a temperature of 25°C.

[0134] The weight average molecular weight of the dispersion stabilizing resin is 1×
103 to 5×105, preferably 2×103
~1x105, particularly preferably 3x103 ~5
×104. The weight average molecular weight of the resin is 1×10
If it is less than 3, agglomeration of the produced dispersed resin particles will occur, making it impossible to obtain fine particles with a uniform average particle size. On the other hand, if it exceeds 5×10 5 , the effect of the present invention of improving water retention while satisfying electrophotographic properties when added to a photoconductive layer will be diminished.

The dispersion stabilizing resin of the present invention may be any polymer as long as it is soluble in the non-aqueous solvent, but specifically, K. B. J. Barrett “Dispersion”
Polymerization in Org
anic Media” John Wiley an
d Sons (published in 1975), R. Dowpenc
o,D. P. Hart, Ind. Eng. Chem. P
rod. Res. Develop. 12, (No.1)
, 14 (1973), Toyokichi Tange, Japan Adhesive Association Journal 2
3(1), 26 (1987), D. J. Walbrid
ge, NATO. Adv. Study Inst. S
er. E. No. 67, 40 (1983), Y. Sas
aki and M. Yabuta,Proc,1
0th, Int. Conf. Org. Coat. Sci
．． Technol, 10, 263 (1984) and other reviews include cited polymers.

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. acrylate homopolymers, methacrylate copolymers, acrylate copolymers, alkyd resins, etc.

More specifically, examples of the polymer component serving as a repeating unit of the dispersion stabilizing resin of the present invention include a component represented by the following general formula (VI).

[0138]

[C70]

In formula (V), X2 is V0 of formula (II)
The details are described in the explanation of V0 in formula (II).

R12 is an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
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,
2,3-epoxypropyl group, 2,3-diacetoxypropyl group, 3-chloropropyl group, 4-ethoxycarbonylbutyl group, etc.), optionally substituted alkenyl groups having 3 to 22 carbon atoms (e.g. allyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group,
octadecenyl group, oleyl group, linoleyl group), optionally substituted aralkyl group having 7 to 22 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group,
2-naphthylmethyl group, 2-(2'-naphthyl)ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
methoxybenzyl group, dimethoxybenzyl group, butylbenzyl group, methoxycarbonylbenzyl group, etc.), optionally substituted alicyclic groups having 4 to 12 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chloro cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), carbon number 6 or more
22 optionally substituted aromatic groups (e.g. phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, anthranyl group, chlorophenyl group, bromophenyl group, butylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Octyloxyphenyl group, ethoxycarbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N,N-dibutylaminophenyl group, N
-methyl-N-dodecylphenyl group, thienyl group, hyranyl group, etc.).

[0141] f1 and f2 are b1 and f2 in formula (II),
b2 represents the same content as b1 in formula (II) for details.
, b2. As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained together with the above-mentioned components and other polymer components.

[0142] Any other polymer component may be used as long as it copolymerizes with the monomer corresponding to the component represented by the general formula (V). Examples of the corresponding monomer include:
α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (heterocycles include pyran ring, pyrrolidone ring, imidazole ring, pyridine ring, etc.)
, vinyl group-containing carboxylic acids (e.g. acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc.), vinyl group-containing carboxyamides (e.g. acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid, etc.) acid hemiamide, itaconic acid diamide, etc.).

[0143] In the dispersion stabilizing resin of the present invention, the polymer component represented by the general formula (V) is 10% of the total polymer of the resin.
It is 30 parts by weight or more, preferably 50 parts by weight or more in 0 parts by weight. Furthermore, it is preferable that the dispersion stabilizing resin of the present invention contains at least one kind of polymerizable double bond group moiety represented by the above-mentioned general formula (II) in the polymer chain. The polymerizable double bond group portion will be explained below.

[0144]

[C71]

In general formula (II), V0 is -O-
, -COO-, -OCO-, -(CH2)p -OC
O-, -(CH2)p-COO-, -SO2-,
-CONR01, -SO2 NR01, -C6 H4
-, -CONHCOO-, or -CONHCONH- (p represents an integer of 1 to 4).

[0146] In addition to a hydrogen atom, R01 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (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-
methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g. 2-bromopropyl group, etc.),
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, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
Or, an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group) , ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
acetamidophenyl group, propioamidophenyl group,
dodecoylamidophenyl group, etc.).

[0147] When V0 represents -C6 H4 -,
The benzene ring may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxymethyl group, etc.). group, ethoxy group, propioxy group, butoxy group, etc.).

b1 and b2 may be the same or different, preferably a hydrogen atom, a halogen atom (
For example, chlorine atom, bromine atom, etc.), cyano group, carbon number 1~
4 alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R02 or COOR02 via a hydrocarbon (R02 is a hydrogen atom or a carbon atom with 1 to 1 carbon atoms)
18 alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically, the same content as explained for R01 above) .

[0149] Hydrocarbons in the -COO-R02 group via the hydrocarbon include methylene group, ethylene group,
Examples include propylene group.

More preferably, in general formula (II), V0 is -COO-, -OCO-, -CH2OC
O-, -CH2 COO-, -O-, -CONH-, -
SO2 NH-, -CONHCOO- or -C6 H4
-, b1 and b2 may be the same or different, and hydrogen atom, methyl group, -COOR02 or -
CH2 COOR02, (R02 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.); still more preferably b1, b2 One of them always represents a hydrogen atom.

Specifically, as the polymerizable double bond group-containing moiety represented by the general formula (II), CH2 = CH
-CO-O-, CH2=C(CH3)-CO-O-
, CH(CH3)=CH-CO-O-, CH2=C
(CH2COOCH3)-CO-O-, CH2=
C(CH2COOH)-CO-O-, CH2=CH
-CONH-, CH2=C(CH3)-CONH-
, CH(CH3)=CH-CONH-, CH2=C
(CH3)-CONHCOO-, CH2=CH-O
-CO-, CH2 = CH-CH2 -O-CO-, C
H2 = CH-O-, CH2 = C(COOH)-CH
2-CO-O-, CH2=C(COOCH3)-C
H2 -CO-O-, CH2 = CH-C6 H4 -
etc.

[0152] These polymerizable double bond group-containing moieties are bonded directly to the main chain of the polymer chain or via an arbitrary linking group. Specifically, the connecting group is a divalent organic residue, such as -O-, -S-, -N(d1)-
, -SO-, -SO2-, -COO-, -OCO-,
-CONHCO-, -NHCONH-, -CON(d2
)-SO2 (d3)- and -Si (d4)(
d5) represents an organic residue composed of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from d5). Here, d1 to d5 represent the same content as R01 in formula (II).

As a divalent aliphatic group, for example, -(C(k
1 )(k2 ))-,-(C(k1)=C(k2
))-, -(C≡C)-, -C6 H10-,

[0154]

[C72]

[0155] {k1 and k2 may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q represents -O-, -S- or -NR20-, R20 is an alkyl group having 1 to 4 carbon atoms, -CH2
Cl or -CH2Br}.

[0156] Examples of divalent aromatic groups include benzene ring groups, naphthalene ring groups, and 5- or 6-membered heterocyclic groups (the hetero atoms constituting the heterocycle are selected from oxygen atoms, sulfur atoms, and nitrogen atoms). containing at least one type of heteroatom). These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, etc.), and alkoxy groups having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

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.

[0158] Specifically, the polymerizable double bond group-containing moiety described above is bonded randomly within the polymer chain, or bonded only to one end of the main chain of the polymer chain. Preferably, a polymer (hereinafter referred to as a monofunctional polymer) in which a polymerizable double bond group-containing moiety is bonded only to one end of the main chain of the polymer chain is preferable.
(abbreviated as M)).

General formula (II) of the above monofunctional polymer [M]
) The following are specific examples of the polymerizable double bond group-containing moiety and the moiety composed of an organic residue linked to the moiety, but the present invention is not limited thereto. However, in each of the following examples, P1 is -H, -CH3
-, -CH2COOCH3, -Cl, -Br or -
CN, P2 represents -H or -CH3, X represents -Cl or -Br, n represents an integer from 2 to 12,
m represents an integer of 1 to 4.

[0160]

[C73]

[0161]

[C74]

[0162]

[C75]

[0163]

[C76]

[0164]

[C77]

[0165]

[C78]

[0166]

[C79]

[0167]

[C80]

[0168]

[Chemical formula 81]

[0169]

[C82]

[0170]

[Chemical formula 83]

[0171]

[Chemical formula 84]

[0172]

[Chemical formula 85]

[0173]

[C86]

[0174]

[Chemical formula 87]

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

For example, (1) a method of copolymerizing monomers containing two polymerizable double bond groups with different polymerization reactivity in the molecule, (2) a method of copolymerizing monomers containing two polymerizable double bond groups with different polymerization reactivity; After obtaining a polymer by copolymerizing a monofunctional monomer containing a reactive group such as Reacts with organic low-molecular compounds containing double bond groups,
Commonly known methods include a method of introducing by so-called polymer reaction.

[0177] As the above method (1), for example, Japanese Patent Application Laid-open No. 1986-
Examples include the method described in Japanese Patent No. 185962. As for the above method (■), specifically, Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (published in 1976), JP-A-6
It is described in detail in Japanese Patent Application No. 1-43757 and the specification filed as Japanese Patent Application No. 1-149305.

[0178] For example, a polymer reaction using a combination of a functional group of group A and a functional group of group B shown in Table 1 below is a commonly known method. In addition, R22, R in Table-1
23 is a hydrocarbon group and has the same content as l8 and l9 in L1 of the above formula (IV).

[0179]

[Table 1]

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

Specifically, P. Dreyfuss &
R. P. Quirk, Bncycle. Polym.
Sci. Eng. , 7, 551 (1987), P. F.
Rempp, E. Franta, Adv. Polym.
Sci. , 58, 1 (1984), V. Percec,
Appl. Poly. Sci. , 285, 95 (198
4), R. Asami, M. Takari, Macro
mol. Chem. Suppl. ,12,163(19
85), P. Rempp. ,et al,Macro
mol. Chem. Suppl. , 8, 3 (1984)
, Yuji Kawakami, Chemical Industry, 38, 56 (1987), Yuya Yamashita, Polymer, 31, 988 (1982), Shiro Kobayashi,
Polymer, 30, 625 (1981), Toshinobu Higashimura, Japan Adhesive Association Journal, 18, 536 (1982), Koichi Ito, Polymer Processing, 35, 262 (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987, No. It can be synthesized according to the methods described in reviews such as 10, 5 and the literature/patents cited therein.

[0182] More specifically, as a method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing repeating units corresponding to a radically polymerizable monomer can be synthesized by
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application No. 1-206989, No. 1-69011, etc., and contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] is disclosed in Japanese Patent Application No. 1-56379, No. 1-58989,
It can be obtained in the same manner as the methods described in the specifications of the applications as No. 1-56380.

As explained above, the dispersed resin particles of the present invention are copolymer resins obtained by dispersing and polymerizing the polar group-containing monofunctional monomer (C) in the presence of the above dispersion stabilizing resin. It is a particle. Furthermore, when the dispersed resin particles of the present invention have a network structure, the above polar group-containing monofunctional monomer (C
) [abbreviated as polymer component (C)] The polymers are bridged to form a high-order network structure.

[0184] That is, the dispersed resin particles of the present invention are non-aqueous latex consisting of a portion insoluble in a non-aqueous dispersion solvent consisting of the polymer component (C) and a polymer soluble in the solvent. When the polymer component has a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged. As a result, the network resin particles become poorly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

[0185] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (a) the polymer component (C
) A method of crosslinking a polymer containing the following with various crosslinking agents or curing agents, (b) when carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (C),
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, and (c) the polymer component (C
) and a polymer containing a component containing a reactive group by a polymerization reaction or a polymer reaction.

[0186] As the crosslinking agent in the above method (a), compounds that are commonly used as crosslinking agents can be mentioned. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. Can be used.

For example, organic silane compounds (such as vinyltrimethoxysilane, vinyltributoxysilane,
Silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc.)
, polyisocyanate compounds (e.g. toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate) , polymeric polyisocyanate, etc.),
Polyol compounds (e.g. 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (e.g. ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylene diamine, hexamethylene diamine, N-aminoethyl piperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Shokodo (published in 1985), Kuniyuki Hashimoto Compounds described in "Epoxy Resin" edited by Nikkan Kogyo Shinbunsha (1969), etc.), melamine resin (for example, described in "Uria Melamine Resin" edited by Ichiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shinbunsha (1969), etc.) poly(meth)acrylate compounds (e.g., “Oligomers” edited by Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, Kodansha (1)
(published in 1976), Eizo Omori "Functional Acrylic Resin" Technosystem (published in 1985), etc., specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1
, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate, and methacrylates thereof.

[0188] Furthermore, in the method (b) above, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polyfunctional oligomer can be polymerized. Specific examples of functional groups include CH2 = CH-CH2 -, CH2 = CH-CO-
O-, CH2=CH-, CH2=C(CH3)-
CO-O-, CH(CH3)=CH-CO-O-, C
H2=CH-CONH-, CH2=C(CH3)
-CONH-, CH(CH3)=CH-CONH-,
CH2 = CH-O-CO-, CH2 = C(CH3
)-O-CO-, CH2 = CH-CH2 -O-CO
-, CH2 = CH-NHCO-, CH2 = CH-C
H2-NHCO-, CH2=CH-SO2-, C
H2 = CH-CO-, CH2 = CH-O-, CH2
=CH-S-, etc. can be mentioned. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of monomers having two or more polymerizable functional groups include, for example, monomers or oligomers having the same polymerizable functional groups, such as styrene derivatives such as divinylbenzene and trivinylbenzene: polyvalent Alcohol (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200,
#400, #600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), or polyhydroxyphenols (such as hydriquinone, resorcinol, catechol, etc.) esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid (derivatives of methacrylic acid, acrylic acid or crotonic acid); dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itacon) vinyl esters, allyl esters, vinyl amides or allylamides of polyamines (e.g. ethylene diamine,
, 3-propylene diamine, 1,4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

Monomers or oligomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups (such as methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, aryloyl Reactants of alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) and alcohols or amines ester derivatives or amide derivatives containing vinyl groups such as vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, etc. Allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl methyloxycarbonyl ethylene acrylate, N-allylacrylamide, N-
allyl methacrylamide, N-allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.) or amino alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and a vinyl group. Examples include condensates with carboxylic acids containing .

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is monomer (C)
and 10 relative to the total amount of other monomers coexisting with (C)
Polymerization is performed using mol % or less, preferably 5 mol % or less, to form a resin. Furthermore, in the case of forming a chemical bond and bridging the polymers by the reaction of the reactive groups between the polymers in the method (c) above, it is carried out in the same manner as the reaction of ordinary organic low-molecular compounds. be able to. Specifically, it can be synthesized according to the same method as described in the method for synthesizing the dispersion stabilizing resin.

[0192] In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can be easily obtained, so polyfunctional polymerization is recommended as a method for forming a network structure. Method (b) using monomers is preferred. As described above, the network-dispersed resin particles of the present invention contain a repeating unit containing a polar group and a polymer component soluble in the non-aqueous solvent, and have a structure in which the molecular chains are highly cross-linked. It is a particle of a polymer having

[0193] As the non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles, any organic solvent with a boiling point of 200°C or less may be used, and it may be used alone or in a mixture of two or more. good.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, diethyl ketone, ethers such as diethyl ether, tetrahydrofuran, dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, hexane, octane, decane, dodecane, tridecane , C6-14 aliphatic hydrocarbons such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples include halogenated hydrocarbons such as trichloroethane. However, it is not limited to the compound examples described above.

[0195] By synthesizing dispersed resin particles in these non-aqueous solvent systems by dispersion polymerization, the average particle size of the resin particles can easily be 0.8 μm or less, and the particle size distribution is extremely narrow and monodisperse. particles.

Specifically, K. B. J. Barrett
“Dispersion Polymerization
in Organic Media"John
Wiley (1975), Koichiro Murata, Polymer Processing,
23, 20 (1974), Tsunetaka Matsumoto and Toyokichi Tange, Journal of Japan Adhesive Association 9, 183 (1973), Toyokichi Tange, Journal of Japan Adhesive Association 23, 26 (1987), D. J. Walbri
dge, NATO. Adv. study. Inst. S
er. B. No. 67, 40 (1983), British Patent Nos. 893429 and 934038, U.S. Patent Nos. 1122397, 3900412, and 4606989
Specifications of each issue, JP-A-60-179751, JP-A-60-18
The method is disclosed in 5963 publications and the like.

The dispersion resin of the present invention is composed of at least one kind each of monomer (C) and dispersion stabilizing resin, and when forming a network structure, a polyfunctional monomer (D
), and in any case, what is important is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, the desired dispersed resin can be obtained. More specifically, it is preferable to use the dispersion stabilizing resin in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, based on the monomer (C) to be insolubilized. Further, the molecular weight of the dispersed resin particles of the present invention is 104 to 106, preferably 10
4 to 5×105.

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

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the nonaqueous solvent.
~50 parts by weight. The amount of polymerization initiator is 0.1 to 5% by weight of the total amount of polymerizable compounds. Also, the polymerization temperature is 30
The temperature is about 180°C, preferably 40 to 120°C. The reaction time is preferably 1 to 15 hours. The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

As the binder resin for the photoconductive layer of the present invention, any of the conventionally known resins can be used in addition to the resin [A]. Examples include alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc., as cited in the description of the prior art. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8), page 9, and other known materials cited in the review.

Preferably, a group of random copolymers containing methacrylate as a polymer component, which is known as a binder resin for electrophotographic photoreceptors using photoconductive zinc oxide as an inorganic photoconductor, is one example. For example, JP 50-2242, JP 50-31011, JP 50-
98324, 50-98325, Special Publication No. 54-139
77, 59-35013, JP-A-54-20735,
Examples include those described in Publications No. 57-202544.

[0202] Furthermore, a random copolymer of methacrylate and a monomer containing an acidic component such as a carboxyl group, a sulfo group, or a phosphono group and another resin or a heat and/or Or a binder resin composed of a combination with a compound that hardens with light: for example, JP-A-63-220148, JP-A-63-220149,
JP 2-34860, JP 2-40660, JP 2-53
064, 1-102573, and the like.

[0203] Alternatively, a polymer having a weight average molecular weight of 20,000 or less and containing a methacrylate component and containing an acidic group at one end of the polymer main chain, and other polymers having a weight average molecular weight of 30,000 or more. A binder resin composed of a resin or a combination of a compound that cures with heat and/or light: For example, JP-A-1-169455, JP-A-1-280761, JP-A-1-2
14865, Publications No. 2-874, Patent Application No. 1983-22
1485, 63-220442, 63-22044
Also included are polymer groups such as those described in each specification of No. 1.

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Furthermore, other inorganic photoconductors such as titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, etc. may be used in combination. However, these other photoconductive materials contain less than 40% by weight of the photoconductive zinc oxide;
Preferably it is 20% by weight or less. Other photoconductive materials are 4
If it exceeds 0% by weight, the effect of improving the hydrophilicity of non-image areas as a lithographic printing original plate will be weakened.

[0205] The total amount of binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight of the total binder resin to 100 parts by weight of the photoconductor (of which resin [A] is 5 to 100 parts by weight).
70 parts by weight), preferably 15 to 70 parts by weight)
A proportion of 50 parts by weight is used. In addition, total binder resin 10
The amount of the resin particles is 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8) No. 1
2 pages, C. J. Young et al.: RCA Review
15, 469 pages (1954), Wataru Kiyota: Journal of the Institute of Electrical Communication, J63-C (No. 2), 97 pages (19
80), Yuji Harasaki et al., Industrial Chemistry Journal 66, 78 and 18
8 pages (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35, 20
Carbonium-based dyes cited in reviews such as page 8 (1972),
Diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, cytylyl dyes, etc.), phthalocyanine dyes (which may contain metals), etc. can be mentioned.

More specifically, as for those mainly using carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, Japanese Patent Publication No. 51-4
52, JP-A No. 50-90334, No. 50-114227
, 53-39130, 53-82353 publications,
Examples include those described in U.S. Pat. No. 3,052,540, U.S. Pat. Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include F. M. Hammer “The Cya”
nine Dyes and Related C
It is possible to use pigments described in US Pat. No. 3,047,384 and US Pat.
10591, 3121008, 3125447, 3128179, 3132942, 3622317
Specifications of each issue, British Patent No. 1226892, British Patent No. 13092
74, 1405898 specifications, Japanese Patent Publication No. 1978-1978
14, No. 55-18892, and the like.

[0208] Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region, JP-A-47-840, JP-A-47-44180, and JP-A-51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 361954, U.S. Patent No. 4175956
Specifications of each issue, “Research Disclosure
re'', 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers can be used in combination. For example, the review mentioned above: Imaging 19
73 (No. 8), page 12, etc., electron-accepting compounds (e.g., halogens, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., “Recent development and practical application of photoconductive materials and photoreceptors” Chapters 4 to 6: Japan Scientific Information Co., Ltd. Publishing Department (1986) Examples include polyarylalkane compounds, hindered phenol compounds, and p-phenylenediamine compounds cited in the review.

[0210] The amount of these various additives added is not particularly limited, but is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0μ, especially 10-50μ is suitable. In addition, when a photoconductive layer is used as the charge generation layer of a photoconductor with a stacked structure of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01~
1μ, particularly 0.05 to 0.5μ is suitable. Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes, and the like. The thickness of the charge transport layer is preferably 5 to 40 microns, particularly 10 to 30 microns.

[0211] As the resin used for forming the charge transport layer,
Typical examples are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride acid copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, and epoxy. Thermoplastic resins and curable resins such as resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet is impregnated with a low-resistance substance, just as in the conventional case. those that have been subjected to conductive treatment, such as those that are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and to prevent curling, and those that are coated with at least one layer for the purpose of preventing curling, etc. Those with a water-resistant adhesive layer on the surface of the body, those with at least one pre-coat layer provided as necessary on the surface layer of the support, and those with a conductive plastic substrate on which Al or the like is vapor-deposited and laminated with paper. Things can be used.

[0213] Specifically, as an example of a conductive substrate or a conductive material, see Yukio Sakamoto, Electrophotography, 14, (No. 1
), p2-11 (1975), Hiroyuki Moriga, "Introduction to the Science of Special Paper", Kobunshi Publishing Association (1975), M. F. Hoov
er, J. Macromol. Sci. Chem. A-
4(6), pp. 1327-1417 (1970), etc. are used.

[0214] In order to actually produce the original plate for lithographic printing of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives, etc. are placed on a conductive support by volatile carbonization with a boiling point of 200°C or less. An electrophotographic photosensitive layer (photoconductive layer) can be produced by dissolving or dispersing it in a hydrogen solvent, coating it, and drying it. The organic solvent used is
Specifically, dichloromethane, chloroform, 1,2
- 1 to 3 carbon atoms, such as dichloroethane, tetrachloroethane, dichloropropane or trichloroethane;
Preferred are halogenated hydrocarbons. Other various solvents used in coating compositions, 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, and the above-mentioned solvents. Mixtures of can also be used.

[0215] A printing plate using the lithographic printing original plate of the present invention is produced by forming a copy image on the electrophotographic original plate having the above-mentioned structure by a conventional method, and then desensitizing the non-image area. be done. The desensitizing treatment used in the present invention may be carried out by desensitizing zinc oxide according to a conventionally known method. As a method for desensitizing zinc oxide, any conventionally known treatment liquid can be used. For example, JP-A-62-239158, JP-A-62-292492, and JP-A-63-1 using ferrocyanic compounds as the main agent for desensitization.
99993, 63-9994, Special Publication No. 40-7334
, 45-33683, JP 57-107889, JP 46-21244, JP 44-9045, JP 47-3
2681, 55-9315, JP-A-52-10110
2 publications, etc.

[0216] In addition, Japanese Patent Publications No. 43-28408, No. 45-24609,
JP 51-103501, JP 54-10003, JP 53-83805, JP 53-83806, JP 53-12
7002, 54-44901, 56-2189, 57-2796, 57-20394, 59-207
A water-soluble polymer capable of forming a metal chelate as described in each publication of No. 290 was used as the main ingredient. Special Public Service 1977-1996
65, 39-22263, 40-763, 43-
28404, 47-29642, JP-A-52-126
302, 52-134501, 53-49506,
Those described in Publications No. 53-59502 and No. 53-104302, etc., using metal complex compounds as the main ingredient,
JP-A-53-104301, JP-A-55-15313,
54-41924, etc., or those using inorganic and organic acid compounds as the main ingredient,
9-13702, 40-10308, 46-261
24, JP-A-51-118501, JP-A No. 56-11169
Examples include those described in each No. 5 publication. The conditions for the treatment are preferably a temperature of 15°C to 60°C and an immersion time of 10 seconds to 5 minutes.

[0217]

[Examples] Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. Synthesis Example 1 of Resin [A]: [A-1] A mixed solution of 96 g of benzyl methacrylate, 4 g of thiosalicylic acid, and 200 g of toluene was heated to a temperature of 75% under a nitrogen stream.
Warmed to ℃. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviated as A.I.B.N.) was added and reacted for 4 hours. Furthermore, A. I. B. N. Add 0.4g of A. for 2 hours, then add A. I. B. N. 0.2g of was added and stirred for 3 hours. The obtained copolymer [A-1] has the following structure,
Its weight average molecular weight was 6.8 x 103.

[0218]

[Chemical formula 88]

Synthesis Examples 2 to 13 of Resin [A]: [A-2]
~ [A-13] In Synthesis Example 1 of Resin [A], each resin [A] was prepared in the same manner as in Synthesis Example 1, except that the monomers shown in Table 2 below were used in place of 96 g of benzyl methacrylate. -2] ~ [A
-13] was synthesized. The weight average molecular weight of each resin is 6.0
×103 to 8×103.

[0220]

[Table 2]

[0221]

[Table 3]

[0222]

[Table 4]

Synthesis Examples 14 to 24 of Resin [A]: [A-1
4] to [A-24] In Synthesis Example 1 of resin [A], 96 g of benzyl methacrylate and 4 g of thiosalicylic acid were replaced with methacrylates and mercapto compounds shown in Table 3 below, and 200 g of toluene was replaced with 150 g of toluene. Resins [A-14] to [A-24] were synthesized in the same manner as in Synthesis Example 1, except that 50 g of isopropanol was used. The weight average molecular weight of each copolymer obtained was 6.8 x 103.

[0224]

[Table 5]

[0225]

[Table 6]

[0226]

[Table 7]

Synthesis example 25 of resin [A]: [A-25] 1
-100g naphthyl methacrylate, 150g toluene
A mixed solution of 50 g of isopropanol was heated to 80° C. under a nitrogen stream. 5.0 g of 4,4'-azobis(4-cyano)valeric acid (abbreviated as A.C.V.) was added and stirred for 5 hours. Furthermore, A. C. V. Add 1g of A. for 2 hours, then add A. C. V. 1 g of was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5 x 103.

[0228]

[Chemical formula 89]

Synthesis Example 26 of Resin [A]: [A-26] A mixed solution of 50 g of methyl methacrylate and 150 g of methylene chloride was cooled to -20° C. under a nitrogen stream. 1.0 g of the 10% 1,1-diphenylhexyllithium hexane solution prepared just before was added and stirred for 5 hours. After stirring carbon dioxide at a flow rate of 10 ml/cc for 10 minutes, cooling was stopped and the reaction mixture was left stirring until it reached room temperature. Next, this reaction mixture was reprecipitated into a solution of 50 cc of 1N hydrochloric acid dissolved in 1 liter of methanol, and a white powder was collected by filtration. After washing this powder with water until it becomes neutral,
Dry under reduced pressure. Yield 18g, weight average molecular weight 6.5x
It was 103.

[0230]

[C90]

Synthesis Example 27 of Resin [A]: [A-27] A mixed solution of 95 g of benzyl methacrylate, 4 g of thioglycolic acid, and 200 g of toluene was heated at a temperature of 75 g under a nitrogen stream.
Warmed to ℃. A. C. V. After adding 1.0 g of A. and reacting for 6 hours, further A. C. V. 0.4g of was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 7.8×1
It was 03.

[0232]

[Chemical formula 91]

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 75° C. with stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviated as A.I.B.N.)1.
0g was added and stirred for 4 hours, and further A. I. B. N. 0
．． 5 g was added and stirred for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction mixture.
The mixture was stirred at a temperature of 110°C for 8 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, a slightly brownish oil was collected, and then dried. Yield: 73g, weight average molecular weight: 3.6×1
It was 04.

[0234]

[C92]

[0235] Production example 2 of resin for dispersion stabilization: [P-2] 2
- 100 g of ethylhexyl methacrylate, 1 part of toluene
A mixed solution of 50 g and isopropanol was heated to 75° C. with stirring under a nitrogen stream. 2,2'-
2g of azobis(4-cyanovaleric acid) (abbreviated as A.C.V.) was added and reacted for 4 hours, and further A.C.V. C. V. 0.8g
was added and reacted for 4 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, and the oil was collected and dried. 50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate,
Dissolve a mixture of 150 g of tetrahydrofuran, and add 8 g of dicyclohexylcarboniimide (D.C.C.) to it.
g, 0.2 g of 4-(N,N-dimethylamino)pyridine
and 20g of methylene chloride at a temperature of 25-30℃.
The mixture was added dropwise, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added to this reaction mixture and stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol, and the oily matter was collected by filtration. Furthermore, this oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 1 liter of methanol, and the oily substance was collected and dried. Yield 32g and weight

[0236] The weight average molecular weight was 4.2 x 104.

[0237]

[C93]

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

[0239]

[C94]

Production Example 1 of Resin Particles: [L-1] 50 g of acrylic acid, resin of Production Example 1 of Dispersion Stabilizing Resin [P-1]
A mixed solution of 7.5 g and 275.8 g of methyl ethyl ketone was heated to 65° C. with stirring under a nitrogen stream. 2,2
'-azobis(isovaleronitrile) (abbreviation A.I.V.
．． N. ) was added and reacted for 2 hours, and further A. I
．． V. N. 0.25g was added and reacted for 2 hours. After cooling, the white dispersion [L-1] obtained by passing through a 200 mesh nylon cloth had a polymerization rate of 96% and an average particle size of 0.30μ.
It was M's latexte. Production example 2 of resin particles: [L-2] Dispersion stabilizing resin AA-2 [manufactured by Toagosei Co., Ltd. Macromonomer: Macromonomer having methyl methacrylate as a repeating unit: Weight average molecular weight 3 x 103] 7.5 g and A mixed solution of 133 g of methyl ethyl ketone was heated to 65° C. with stirring under a nitrogen stream.

[0241] To this, 50 g of acrylic acid, A. I. V.
N. A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour, and the mixture was further stirred for 1 hour. Furthermore, A. I. V. N. Add 0.25g and stir for 2 hours. After cooling, the white dispersion [L-2] obtained by passing through a 200 mesh nylon cloth had a polymerization rate of 96% and an average particle size of 0.19.
It was micrometer latex. Production examples 3 to 16 of resin particles: [L-3] to [L-16]
In Production Example 2 of resin particles, each monomer in Table 4 below [
A white dispersion was obtained in the same manner as in Production Example 2, except that 2.5 g of (A-2) to (A-16) were used. Each latex [
(L-3) to (L-16)] had a polymerization rate of 95 to 98%, and an average particle size in the range of 0.15 to 0.23 μm.

[0242]

[Table 8]

Production Example 23 of Resin Particles: [L-23] 46.5 g of acrylic acid, 3.5 g of ethylene glycol dimethacrylate, resin of Production Example 3 of Dispersion Stabilizing Resin [P-3
] 7 g and diethyl ketone 27.5 g,
The subsequent operations were performed in the same manner as in Production Example 1 of resin particles. The obtained white dispersion [L-25] had a polymerization rate of 98% and an average particle size of 0.20 μm. Production examples 24 to 36 of resin particles: [L-24] to [L-3
6] In Production Example 23 of Resin Particles, resin particles [L- 26] to [L-36] were produced. The polymerization rate of each particle is 95-98% and the average particle size is 0.15-0.
．． It was 25 μm.

[0244]

[Table 9]

Example 1 and Comparative Examples A to B Example 1 6 g of resin [A-4] (33.2 g of binder resin [B-1] having the following structure as solid content, 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was heated in a homogenizer at 6×10 3 r.p. p. m. 10 at the rotation speed of
Dispersed for minutes. 0.8g of dispersed resin particles [L-2]
(as solid content) and further, the rotation speed 1 x 103
r. p. m. Dispersion was performed for 1 minute. This dispersion for forming a photosensitive layer was applied to electrically conductively treated paper using a wire bar so that the dry adhesion amount was 25 g/m 2 , and dried at 100° C. for 3 minutes. Then, in a dark place at 20°C and 65% RH,
By leaving it for 4 hours, an electrophotographic light-sensitive material was produced.

[0246]

[C95]

Comparative Example A An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 0.8 g of dispersed resin particles [L-2] was not added. Comparative Example B In Example 1, 6 g of resin [A-4] and resin [B-
1] Instead of 33.2g, resin with the following structure [R-1]
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 39.2 g was used.

[0248]

[C96]

Film properties (surface smoothness), electrostatic properties, desensitization of the photoconductive layer (represented by contact angle with water of the photoconductive layer after desensitization treatment), and printing of these photosensitive materials I looked into gender. Printability was determined using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using developer ELP-T to form an image through exposure and development, followed by desensitization. It was investigated using a printing board. (The printing machine used was Hamadastar 800SX manufactured by Hamadastar Co., Ltd.)
The above results are summarized in Table 6.

0250]

[Table 10]

[0251] The implementation of the evaluation items listed in Table 6 is as follows. Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air volume of 1
The smoothness (sec/cc) was measured under cc conditions. Note 2) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH.
-6 using a paper analyzer (Paper Analyzer-SP-428 model manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material.
After corona discharge for 20 seconds at kV, leave it for 10 seconds,
The surface potential at this time was measured as V10. Then, the potential V70 was measured after leaving it for 60 seconds in the dark.
The retention of the potential after dark decay for seconds, that is, the dark decay retention rate (D.R.R. (%)) is determined by [(V70/V10) x 10
0 (%)]. After the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was then irradiated with visible light at an illuminance of 2.0 lux, and the time required for the surface potential V10 to attenuate to 1/10 was determined. , from which the exposure amount E1/10 (lux/second) is calculated. Similarly V10
The time required for the light to attenuate to 1/100 is determined, and the exposure amount E1/100 (lux·sec) is calculated from this time.

Note 3) Imaging properties: After leaving each photosensitive material and a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) at room temperature and humidity (20°C, 65%) for one day and night, plate making and copying are performed. An image is formed, and the image (fog, image quality) of the obtained original copy plate is visually observed (this is designated as I). Image quality II of the copied image is determined by plate making at high temperature and high humidity (30℃, 8℃).
The test is conducted in the same manner as in I above, except that the test is carried out at 0%). Note 4) Raw plate water retention: Each photosensitive material itself (original plate without plate making: i.e., abbreviated as raw plate) is an aqueous solution prepared by diluting the desensitizing treatment liquid ELP-EX manufactured by Fuji Photo Film Co., Ltd. five times with distilled water. The film was passed through an etching machine once. Next, these plates were processed using Hamada Star 80 manufactured by Hamada Star Co., Ltd.
Printing was carried out using Model 05X, and the presence or absence of scumming on the 50th printed matter after printing was visually evaluated.

Note 5) Background stains on printed matter: After each photosensitive material was plate-made in the same manner as in Note 3) above, it was passed through an etching machine once using ELP-EX as dampening water.
These original plates for offset masters were printed, and the number of prints until background stains on the printed matter could be visually determined was determined. The electrostatic properties of the present invention and Comparative Example A are good, and the actual imaging performance is also good.
All of the copied images had clear image quality. However, in Comparative Example B, the photosensitivity was lowered, and the imaging performance also showed that thin lines, letters, and thin line parts with low density were missing and unclear. When each of these photoconductors was desensitized and the degree of hydrophilization (raw plate water retention) of the non-image area was evaluated, Comparative Examples A and B both showed significant background smearing due to printing ink adhesion. The area was not sufficiently hydrophilized.

[0254] Furthermore, when the lithographic plate of the present invention was subjected to desensitization treatment and printed after plate making, 10,000 prints with clear images and print quality were obtained without any occurrence of scumming. On the other hand, Comparative Example A using resin [A] but not using resin particles
After printing about 5,000 sheets, scumming occurred on the prints. In Comparative Example B, which uses a known resin and resin particles, but uses a reduced amount of resin particles similar to that of the photoreceptor of the present invention, scumming occurred after about 3,000 sheets. As described above, the electrophotographic lithographic printing original plate of the present invention is the only original plate for electrophotographic lithography in which the hydrophilicity of the non-image area is sufficiently developed and the background fog does not occur.

Example 2 In Example 1, 6 g of resin [A-4], 6 g of resin [B-1]
] 33.2 g and resin particles [L-2] 0.8 g, resin [A-25] 4 g, resin with the following structure [B-2]
An electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that 35.0 g and 1.0 g of resin particles [L-23] were used.

0256]

[C97]

[0257] Each characteristic was measured in the same manner as in Example 1. The following are particularly harsh environmental conditions (30℃, 80%RH).
) shows the measurement results below. Electrostatic characteristics V10: -600VD. R.
R: 88% E1/10: 10.0 lux・secE1
/100:16 lux・sec imaging performance
: Very good (◎) Fresh version water retention :
'' (◎) Background smudge on printed matter: No background smear up to 10,000 sheets.Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention, and photosensitivity, and actual copied images and printed matter also survive high temperatures and high humidity ( Clear images without background fog were obtained even under harsh conditions (30° C., 80% RH).

Examples 3 to 14 Resin particles [L] and resin [A] used in Example 1
, instead of resin [B], 0.9 g (as solid content) of the resin particles [L] of the present invention shown in Table 7 below and resin [A] 5
Each photosensitive material was produced in the same manner as in Example 1, except that 34 g of resin [B-3] having the following structure was used. The electrostatic properties and printing properties were evaluated in the same manner as in Example 2.

0259]

[C98]

0260]

[Table 11]

[0261] When the electrostatic properties and printing properties of each photosensitive material were measured in the same manner as in Example 1, all of them had excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images were also stable at high temperatures. Even under harsh conditions of humidity (30° C., 80% RH), clear images were produced without background fog or skipped fine lines. Furthermore, when the performance of the offset lithographic original plates was evaluated after being desensitized, the water retention properties of the raw plates were good, and 10,000 sheets could be printed even after actual plate making. Example 15 and Comparative Examples C to D Resin [A-6] 6.0 g: Resin [B-4] 3 with the following structure
4g, zinc oxide 200g, cyanine dye with the following structure [I
] A mixture of 0.018 g and 300 g of toluene was heated to 6×10 3 r.p. in a homogenizer. p. m. 10 at the rotation speed of
After dispersing for a minute, 1.0 g (as solid content) of resin [L-23] was added thereto, and the rotation speed was increased to 1×103 r.p.m.
p. m. Dispersion was performed for 1 minute. . This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/m2, dried at 100°C for 3 minutes, and then left in the dark for 2 hours.
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of 0° C. and 65% RH.

0262]

[C99]

Comparative Example C An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 1.0 g of resin particles [L-23] in Example 15 was not added. Comparative Example D In Example 15, 6.0 g of resin [A-6] and resin [
B-4] Instead of 34 g, the resin used in Comparative Example A [R
-1] An electrophotographic light-sensitive material was produced in the same manner as in Example 15, except that 39 g was used. The film properties (surface smoothness), film strength, electrostatic properties, imaging properties, and electrostatic properties of these photosensitive materials were investigated under environmental conditions of 30° C. and 80% RH. Furthermore, when these photosensitive materials were used as original plates for offset masters, the photoconductive desensitization properties (water retention properties) and printability (scumming, printing durability, etc.) were investigated. The above results are summarized in Table 8.

0264

[Table 12]

[0265] Among the evaluation items shown in Table 8, the smoothness of the photoconductive layer and the scumming of printed matter were evaluated in the same manner as in Example 1. Electrostatic properties and imaging properties were tested in the following manner. Note 6) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH.
-6k using a paper analyzer (Paper Analyzer SP-428 model manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material.
After corona discharge for 20 seconds at V, leave it for 10 seconds,
At this time, the surface potential V10 was measured. Next, the potential V190 was measured after leaving it in the dark for 18 seconds,
The ability to retain the potential after dark decaying for 180 seconds, that is, the dark decay retention rate [D. R. R. (%)], (V190 /V
10)×100(%).

[0266] Furthermore, corona discharge can cause the surface of the photoconductive layer to -
After charging to 400V, irradiate with monochromatic light with a wavelength of 780nm, calculate the time until the surface potential (V10) attenuates to 1/10, and calculate the exposure amount E1/10 (erg/cm).
2) Calculate. Also, the surface potential (V10) is 1/100
Find the time it takes for the light to attenuate, and then calculate the exposure amount E1/1.
00 (erg/cm2) is calculated. Note 7) Imaging properties: Each photosensitive material was left for one day and night under the following environmental conditions. Next, it is charged with -5kV and used as a light source with 2.0mW.
Output gallium-aluminum-arsenic semiconductor laser (
4 on the surface of the photosensitive material using an oscillation wavelength of 780 nm).
After exposure under an irradiation dose of 5erg/cm2), a pitch of 25 μm, and a scanning speed of 330 m/sec,
The image was developed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer, and the resulting copy image (fogging, image quality) was visually evaluated. The photoreceptors of Example 15 of the present invention and Comparative Example C had good electrostatic properties and good imaging properties.

On the other hand, in Comparative Example D, the electrostatic properties were deteriorated and were significantly affected by this, especially when the environmental conditions changed, and even in actual copied images, background fog and breaks in characters and thin lines occurred. On the other hand, among the desensitized original plates, only the one of the present invention had sufficient hydrophilicity in the non-image areas and could print up to 10,000 sheets without any adhesion of printing ink or the like. In Comparative Example C, the hydrophilization was insufficient, and in Comparative Example D, the copied image was actually deteriorated in the original plate after plate making, and due to this influence, only unsatisfactory printed matter was obtained from the beginning of printing. There wasn't. Examples 16 to 29 In Example 15, 5 g (as solid content) of each resin [A] and 1.5 g (solid amount) of resin particles [L] in Table 9 below were used instead of resin [A] and resin particles [L]. Quantity) or as resin [B], resin [B-5] with the following structure
An electrophotographic light-sensitive material was produced in the same manner as in Example 15, except that 33.5 g was used.

0268

[Chemical formula 100]

0269]

[Table 13]

[0270] Each photosensitive material is exposed to high temperature and high humidity (30°C,
Even under conditions of 80% RH), excellent electrostatic properties were obtained in the present invention. In addition, both the imaging properties and the water retention properties were good, and when printed using it as an offset master original plate, more than 10,000 prints with clear image quality and no background smudge were obtained.

0271]

Effects of the Invention According to the present invention, it is possible to obtain an electrophotographic photoreceptor having excellent electrostatic properties and mechanical properties even under severe conditions, and it can also be used as an original plate for lithographic printing without background smearing. It is possible to print a large number of prints with clear image quality. Furthermore, the original plate of the present invention is effective in a scanning exposure method using semiconductor laser light.

Claims (4)

[Claims] 1. An original plate for electrophotographic lithography comprising at least one photoconductive layer containing photoconductive zinc oxide and a binder resin provided on a conductive support, wherein the photoconductive layer The binder resin contains at least one resin [A] shown below, and the photoconductive layer has a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. At least 1 non-aqueous solvent-based dispersed resin particle of
An original plate for electrophotographic planographic printing characterized by containing seeds. Resin [A]: has a weight average molecular weight of 1 x 103 to 2 x 104, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and -PO3H
2, -SO3H, -COOH, -P(=O)(O
H) R1 [R1 is a hydrocarbon group or -OR2 (R2
represents a hydrocarbon group] and a cyclic acid anhydride group. [Formula (I) above, a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R3 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, they are soluble in the non-aqueous solvent but become insolubilized by polymerization.
Carboxyl group, sulfo group, sulfino group, phosphono group, -P(=O)(OH)R0 [R0 represents a hydrocarbon group or -OR10 (R10 represents a hydrocarbon group)]
, hydroxyl group, formyl group, amide group, cyano group,
A monofunctional monomer (C) containing at least one polar group selected from an amino group, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterocyclic group is soluble in the non-aqueous solvent and has a stable dispersion. Copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a resin. 2. The electrophotographic lithographic printing original plate according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 3. Claim 1, wherein the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. and 2. The original plate for electrophotographic planographic printing according to 2. [In general formula (I), V0 is -O-, -COO,
-OCO-, -(CH2)p -OCO-, -(CH
2) p-COO-, -SO2-, -CONR01-
, -SO2 NR01-, -C6 H4 -, -CON
HCOO- or -CONHCONH- (where p represents an integer of 1 to 4, R1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b1, b2
may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R02, or -COO-R02 via a hydrocarbon group (R02 is a hydrogen atom or an optionally substituted hydrocarbon group). (represents a hydrogen group) 4. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as a copolymer component represented by the general formula (I). The original plate for electrophotographic lithographic printing according to any one of claims 1 to 3, characterized in that it contains at least one. embedded image [However, in the above formulas (Ia) and (Ib), T1
and T2 are each independently a hydrogen atom and a carbon number of 1 to 1
0 hydrocarbon group, chlorine atom, -COR4 or -COO
R5 (R4 and R5 each represent a hydrocarbon group having 1 to 10 carbon atoms), L1 and L2 each represent -COO
- and the number of single bonds or connected atoms connecting the benzene ring: 1 to 4
]