JPH04106552A - Electrophotographic system lithographic printing original plate - Google Patents

Abstract

PURPOSE:To reproduce a copy picture excellent in electrostatic property with fidelity to the original picture and to prevent generation of spotted surface staining by incorporating specified nonwater solvent base dispersion resin particles having the particle size equal to or smaller than the maximum particle size of photoconductive zinc oxide particles in a photoconductive layer. CONSTITUTION:The nonwater solvent-base dispersion resin particles are copolymer resin particles obtained by dispersion polymn. reaction of an one-functional monomer (A) with another one-functional monomer (B) in the presence of the dispersion stabilizing resin in a nonwater solvent. The monomer (A) is soluble in the nonwater solvent but become insoluble after polymerized and contains polar groups such as carboxyl groups. The monomer (B) is copolymerizable with the monomer (A) and contains substd. groups containing silicon atoms and/or fluorine atoms. The resin particles may have a higher dimensional mesh structure. As for the dispersion stabilizing resin, such a resin having at least one kind of polymerizable double bond group expressed by the formula in the polymer resin is especially preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrophotographic lithographic printing original plate made by an electrophotographic method, and in particular to a photoconductive layer forming original plate of the lithographic printing original plate. This invention relates to improving compositions.

[Prior art/problems to be solved by the invention] Currently, many types of offset original plates for direct plate making have been proposed and put into practical use. A photoreceptor provided with a photoconductive layer mainly composed of adhesive particles and a binder resin is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the surface of the photoreceptor.
A widely used technique is to subsequently process the surface with a desensitizing liquid called an etchant to selectively make non-image areas hydrophilic, thereby obtaining an offset master.

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

It is already known that these performances are affected by the ratio of zinc oxide to binder resin in the photoconductive layer. For example, if the ratio of binder resin to zinc oxide particles in the photoconductive layer is reduced, Although the desensitization property of the surface of the photoconductive layer is improved and scumming is reduced, on the other hand, the internal cohesive force of the photoconductive layer itself is decreased, resulting in a decrease in printing durability due to insufficient mechanical strength. Conversely, increasing the ratio of binder resin improves stiffness resistance, but increases scumming. In particular, it goes without saying that scumming is a phenomenon related to the desensitization property of the surface of the photoconductive layer. It has become clear that it is not only influenced by the ratio of , but also largely influenced by the type of binder resin.

In particular, for offset master plates, scumming due to insufficient desensitization is a major problem as mentioned above, and in order to improve this problem, various zinc oxide binding resins that improve desensitization have been developed. It is being considered. For example, in Japanese Patent Publication No. 50-31011, a (meth)acrylate-based compound and another compound are copolymerized in the presence of fumaric acid, with a weight average molecular weight (~) of 1.8 to 10 x 104, A combination of a resin with a glass transition point (Tg) of 10 to 80°C and a copolymer consisting of a (meth)acrylate-based mercury and a mercury other than 7-malic acid; 5
3-54027 discloses a method using a terpolymer containing a (meth)acrylic acid ester having a substituent having a carboxylic acid group separated by at least 7 atoms from the ester bond, and JP-A No. 54-20735. , 57-2025
44 publications, acrylic acid and hydroxyethyl (
Those using quaternary or penta-component copolymers containing meth)acrylates, and in JP-A-58-68046, (meth)acrylic esters and carboxylic acids with alkyl groups having 6 to 12 carbon atoms as substituents. It is described that a method using a terpolymer containing a vinyl monomer is effective in improving the desensitization property of a photoconductive layer.

However, even when 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.

Further, JP-A-1-232356 and JP-A-1-261657 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. However, when evaluated in more detail as a lithographic printing original plate, it was found that the electrophotographic properties (particularly charge retention in the dark, photosensitivity, etc.) fluctuate when the environment changes (high temperature/high humidity or low temperature/low humidity), and stable In some cases, it was not possible to obtain a good copy image.

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.

In addition, when a scanning exposure method using semiconductor laser light is adopted for an electrophotographic lithographic printing original plate used as a digital direct lithography printing original plate, the time is longer than when the entire surface is simultaneously exposed using visible light, and the exposure intensity is Since there are also restrictions on electrostatic properties, higher performance is required in terms of electrostatic properties, especially 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 blurring, as well as skipping of fine lines and blurring of letters, and 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.

In other words, the first object of the present invention is to reproduce a copy image that is excellent in electrostatic properties (particularly dark charge retention and photosensitivity), faithful to the original image, and to be able to reproduce a copy image that is faithful to the original image, and to be able to prevent not only the entire surface-like background smear as an offset original plate. An object of the present invention is to provide a lithographic printing original plate which does not cause even dotted background stains and has excellent desensitization properties.

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 copy image formation 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 types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even in a scanning exposure method using semiconductor laser light.

[Means to solve the problem]

The present invention has achieved the above-mentioned object in an original plate for electrophotographic lithography comprising at least one photoconductive layer containing photoconductive zinc oxide and a binder resin on a conductive support. Electrophotographic lithographic printing characterized in that the conductive layer contains at least one type of non-aqueous solvent-based dispersed resin particles below having a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. Achieved by original version.

Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, carboxyl groups, sulfo groups, sulfino groups, phosphono groups, -P-R, [Ro represents a hydrocarbon group or -OR,0H (R, represents a hydrocarbon group)], 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 group. A monofunctional monomer (A) containing at least one polar group selected from heterocyclic groups, and the -functional monomer (A) containing a substituent containing a silicon atom and/or a fluorine atom. Copolymer resin particles obtained by carrying out a dispersion polymerization reaction of A) and a copolymerizable monofunctional monomer (B) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.

In the present invention, the non-aqueous solvent-based dispersed resin particles may form a high-order network structure.

Furthermore, as the above-mentioned dispersion stabilizing resin in the present invention, those containing at least one kind of polymerizable double bond group moiety represented by the following general formula (I) in the polymer base are particularly preferred. It will be done.

General formula (I) Vo- [In general formula (I), Vo is -D-' -COD
--OCO-+ C) I2tiOCD-, -←MoH2te "100-CONHCOD-, or -CONHCONH
-, where p represents an integer of 1 to 4, and R3 represents a hydrogen atom, carbon, or a hydrocarbon group of numbers 1 to 18)
a.

a, may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, C00-R2 or one COO-R via a hydrocarbon group, (R2 is a hydrogen atom or substituted [Represents a good hydrocarbon group] [Operation] In the present invention, non-aqueous solvent-based dispersed resin particles (hereinafter sometimes abbreviated as resin particles) are monomers containing at least one of the above-mentioned specific polar groups. and a monomer containing at least a fluorine atom and/or a silicon atom as a substituent; a polymer component that becomes insoluble in the non-aqueous solvent after polymerization;
In the case of a dispersion stabilizing resin which is formed by physicochemically adsorbing the polymer component of the dispersion stabilizing resin soluble in the non-aqueous solvent, or which contains a polymerizable double bond group moiety represented by the above formula (I), is characterized in that both types of combined components are chemically bonded.

Unlike known hydrophilic resin particles that are dispersed in the photoconductive layer, the non-aqueous solvent-based dispersed resin particles of the present invention are dispersed in the photoconductive layer, but they contain extremely lipophilic fluorine. Due to the action of polymer components containing atoms and/or silicon atoms, they become concentrated on the surface of the photoconductive layer, which is the air interface (highly lipophilic), and their average particle diameter increases It is also characterized in that it is the same as or smaller than the maximum particle diameter of the conductive zinc oxide particles, and that the particle diameter distribution is narrow and the particle diameters are uniform.

The resin particles of the present invention have the above average particle diameter, and a film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent has a contact angle (goniometer) with respect to distilled water. It is hydrophilic and exhibits a value of 50 degrees or less, preferably 30 degrees or less.

The present invention provides a printing original plate in which a non-image area of a photoconductive layer containing at least photoconductive zinc oxide and a binder resin is treated with a desensitizing liquid to make the surface hydrophilic and a lithographic printing original plate is obtained. As mentioned above, the resin particles are concentrated on the surface area, so just dispersing a small amount (50% to 10% usage amount compared to known hydrophilic resin particle technology) can reduce water retention in non-image areas. This will dramatically improve your performance.

Furthermore, since only a small amount is present in the photoconductive layer, it does not impede electrophotographic properties at all, and can stably maintain good performance even under harsh conditions of high temperature and high humidity, or low temperature and low humidity. It became like that.

On the other hand, in the resin particles of the present invention, if the resin particles have a particle size larger than the zinc oxide particle size, the electrophotographic properties will deteriorate (particularly, uniform charging properties will not be obtained), and as a result, in the copied image. Uneven density in the image area, text/
Breakage or skipping of thin lines, or blurring of the non-image area may occur.

Specifically, the resin particles of the present invention have a maximum particle diameter of 5.
It is not more than μω, preferably not more than 1 μm. The average particle diameter of the particles is 1.0 μm or less, preferably 0.5 μm or less.

Note that 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 is preferable to use particles with a diameter of 0.001 .mu.m or more, since the particle size is similar to that of dispersion, and the effect of particles on improving water retention capacity is diminished.

In addition, in the present invention, the resin particles include a hydrophobic polymer component,
In other words, the dispersion stabilizing resin is made by bonding the corresponding polymer component, and since this hydrophobic part interacts with the binder resin of the photoconductive layer, the anchoring effect of this part prevents moisture during printing. It does not dissolve with water and can maintain good printing characteristics even when printing a large number of sheets.

Furthermore, in the present invention, 1. If the resin particles form a high-order network structure, the dissolution in water is further suppressed, and on the other hand, water swelling properties are exhibited, and water retention properties are further improved.

In the present invention, the resin particles that do not form a higher-order network structure as described above or the resin particles that do form a higher-order network structure (hereinafter simply referred to as network resin particles) contain 100% by weight of photoconductive zinc oxide. It is preferable to use the amount of 0.01 to 10% by weight based on the weight of each part. 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.

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, we will explain the monofunctional monomer (A) which is soluble in non-aqueous solvents but becomes insolubilized by polymerization.
The monomer (A) has -CO2)1 in its molecular structure.
, -SO,)I, -PD,H,,5O2)1. -0
1(, -CN, -CHD -CONI(.

H Contains at least one polar group selected from a hydrate-containing group and a nitrogen atom-containing heterocyclic group.

In the above polar group, -R, is an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group,
Propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group,
benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, etc.) or -R3° group (R, . represents the same content as the hydrocarbon group of Ro).

Ro 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 R). . However, the total number of carbon atoms in R11 and R12 is 8 or less.

More preferably, the total number of carbon atoms in R11 and R1+ is 4 or less.

In addition, 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 acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic anhydride, and cyclohexane-1,2-dicarboxylic anhydride. Monozoo, cyclohexene-1゜2-dicarboxylic acid anhydride ring, 2,3-bicyclo[2,2,2]octane dicarboxylic acid anhydride ring, etc. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hexyl group.

Further, examples of aromatic dicarboxylic anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic anhydride ring, pyridine-dicarboxylic anhydride ring, thiophene-dicarboxylic anhydride ring, etc. is, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (the alkoxy group includes, for example, (methoxy group, nidoxy group, etc.) may be substituted.

Further, the above-mentioned heterocycle containing at least one nitrogen atom preferably includes a 4- to 6-membered heterocycle, such as a pyridine ring, a piperidine ring, a virol ring,
imidazole ring, pyrazine ring, pyrrolidine ring, viroline ring, imidacilline ring, pyrazolidine ring, piperazine ring,
Examples include morpholine ring and pyrrolidone ring.

These heterocycles may contain substituents, such as halogen atoms (fluorine atoms, chlorine atoms,
bromine atom, etc.), an optionally substituted hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 24
Droxyethyl 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.) -OR+s (Rls
represents the same content as the optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or -COOR,, group (R14
represents the same content as Rts).

In addition, the above -COOR group, -3O,H group, 503H group, 1
5RISH (e.g. lithium, sodium, potassium etc.) alkaline earth metals (e.g. calcium, magnesium etc.),
Metal salts such as zinc, aluminum or organic bases (e.g.
triethylamine, pyridine, morpholine, piperazine, etc.).

The monomer (A) 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 (A) is shown by general formula (II).

General formula (n)
O-I6 R+s is each a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, 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
IN (dichloroethyl)aminobenzyl group, N, N(
RIl, Lt may be the same or different, and is a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an aliphatic group having 1 to 4 carbon atoms (preferably, for example, a methyl group, an ethyl group, (propyl group, butyl group, etc.), and i represents an integer of 1 to 6. ] W represents the polar group of the monomer (A) described above.

-c-c=c+, -coo-, -oco-, -o-
, -5S02=CON SO, N 1° represents a linking group formed by a combination of these linking groups.

[Here, 1 and 14 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, etc.) or formula (n
) represents a -[L, -111:] group, 1, to 1. represents the same content as the above RIS. ] b+ and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom,
chlorine atom, bromine atom, etc.) -CDOR group, -CDOR
, a group, -CI(, COOR,, group (R18 represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, the above RIS
) or carbon number 1
-4 alkyl group (preferably, for example, methyl group, ethyl group, propyl group, butyl group, etc.).

The above monomer (A) will be more specifically exemplified below, but the present invention is not limited thereto.

(Margin below) (a-1) C) I2=CH 0OH CONH2, -[1’0NHC2H6゜DOCH3 (a-3) C11,=C 0OHH(CHfYlOH C.I. n: integer from 1 to 12 C00 (CHf?iC mouth OH vertical line (a a: ■ CH3 H 0NH2 -3O2NH2 D.H. (a-8) (a-9> C0D(CH2t, 5O3H integer (a-15) C112=C a: -H, -C) 13 N (a-22) H-N(C2H,>3 a ni -H.

”CH3 (a-23) CH,=C Hot COO(CH2) 20CO(CH,), CD01l
(a-18) a: Hl-CH.

CL=C a ni -■ -CH.

C0NH.

CI(,=C COD ([:Hl), DCDCII=CH-CDD
Ha knee h.

CH.

-CH, CD0CR.

(a (a CH2=C CD(CH2)2NHCO(C)12),, CDONC
H2 ■ CH3 a: -H, -CH5 COD(CH2)2N(CH3)2 n: An integer from 1 to 10 (a (a-29) CH.

COD(CH2) ,,OCO(CL)-CDONC
H,=C a: ■ C1l.

a: ■.

CH3゜ CH2CD0CH3 COD(CH,)2N(CH,CH2DH).

n: an integer of 2 to 10 (a m: an integer of 1 to 10 (however, n+m) is 10 or less) (a CH2=C (a COO(CH2Cl(2[1-hOcO(CH,), C
OO1la knee H.

-CHs.

CI n: an integer from 1 to 4 UUUthL: HUthUH m= an integer from 1 to 4 (a-32) (a-37) ['1(2=C COD(CH2)2NHCO(C)+2)zcOONa
a knee h.

CH.

CH,,C00CH.

(a-33) (a-38) (a (a-34) (a CL=CH a: H Cl1゜ (a-41) a: CH.

CH.

(a-42) (a-46) (a-43) (a-44) CI(.

CI (2=C CDDC)1. -CI(CH2DC[1(CH2)2C
OOHH (a-45) (a-47) CH2=C1l-Ct120CD (CHiCOOHn:
An integer of 1 to 3 (a-48) A monofunctional compound containing a substituent containing at least one fluorine atom and/or silicon atom, which can be copolymerized with the polar group-containing monomer (A) as described above. Regarding the monofunctional monomer (B), the monofunctional monomer (B) of the present invention may be any compound as long as it satisfies the above requirements. Further, although the specific contents of the substituents will be explained below, they are not limited to these chemical structures.

Examples of substituents containing a fluorine atom include -ChF
zh++ (h represents an integer from 1 to 12) iCh)
1cFaH (J represents an integer of 1 to 11).

Examples of silicon atom-containing substituents include numbers) It will be done.

Examples include polysiloxane structures, etc. However, R3, R, and R5 may be the same or different,
An optionally substituted hydrocarbon group or -OR, group (R,
represents the same content as the hydrocarbon group of R3).

R3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group,
Hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2.2゜2-trifluoroethyl group, 2-cyanoethyl group, 3.3.3-)lifluoropropylene Biru group, 2-methoxyethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 2.2.2.2'2', 2'-hexafluoroisopropyl group, etc.) having 4 to 18 carbon atoms. Alkenyl groups that may be substituted (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2 -hexenyl group, 4-methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, - naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group,
(dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.) or 6 to 12 carbon atoms optionally substituted aromatic groups (e.g. phenyl group, naphthyl group,
tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, tesyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.)
It can be mentioned.

In the OR9 group, Rs represents the same content as the hydrocarbon group of R3 above.

Rs, R,, Ra may be the same or different and represent the same symbol content as R3, R,, R6.

Next, specific examples of the monofunctional monomer (B) having a substituent containing a fluorine atom and/or a silicon atom as described above are shown below. However, the scope of the present invention is not limited thereto.

(b-1) CH2=C C00CH, CH2ChP2h,.

(b-3) CH2=C C00CH, CH, (CF,)YCF, Hj: 1 to 11
(b-4) i: An integer of 1 to 3 (b-5) (b-7) Cl(,=C C0D(CH2)2NH3O,Rf Rf: -CLChF2h++ (b-6) 1:1 to 6 Integer SO,Rf (b-10) CH2=C C[]NHCOORf (b (b CH,=C CD0CR2CF2CF211 (b COO3i-C-Hs 6H5 CH2=C (b Coo(CH2)O-Rf (b CH2= C R,/CD port (CH2) 20si-L' CH,=C CH3 R3/ C00(CL)Si OCH3 R,/, R2'R3':[][')13 Alkyl group having 1 to 12 carbon atoms ( b-14) (b CH,=C CH5 Coo (CH2)20Si CH3 CH3 CH.

(b (b CH,=C CH3 Hs C')1.=c R,/CD[](CH2) 20si-tO3i(b)-,[
1:H3CH.

CH3 q: integer from 1 to 20 R3/ (b (b [:H,=[: CH.

CH,=CR,/C0D(CH2)-0Si-tCH,→-,CDOR,
'CD0CH,5i-R2' CH.

R, / (b (b-23) ' 5t-CH3 CH3 (b-28) CH,=C CDDC) 12cF, cF2HcF3 (b-29) to C1,82n+1 CH3CH3CH3 r: Monomer containing a polar group such as 0 or an integer from 1 to 20 or more (A) and phew! Along with the elementary atom and/or silicon atom-containing monomer (B), 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 (I) described later or monomers corresponding to the components represented by the formula (II[).

As a polymerization component in the resin, the proportion of monomer (A) present is 30% by weight or more, preferably 50% by weight or more, and the proportion of monomer (B) is 0.5% to 30% by weight. %, preferably 1% to 20% by weight. When other copolymerizable monomers are contained, the amount is at most 20% by weight or less.

It is important that the polymerization component is insoluble in the non-aqueous solvent as long as it can satisfy 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.

The weight average molecular weight of the dispersion stabilizing resin is 1×103 to 5×
105, preferably 2x103 to 1x105, particularly preferably 3x10' to 5x10'. When the weight average molecular weight of the resin is less than 1X10', agglomeration of the produced dispersed resin particles occurs, making it impossible to obtain fine particles with a uniform average particle size. On the other hand, if it exceeds 5X105,
When added to the photoconductive layer, the effect of the present invention of improving water retention while satisfying electrophotographic properties is diminished.

The dispersion stabilizing resin of the present invention may be any polymer as long as it is soluble in the non-aqueous solvent.
, Barrett r Dispersion Po
Lym-erization in Organic
MediaJJohn Wiley and5ons
(Published in 1975) R, Dowpenco, [], P
.

Hart, Ind, Eng, Chem, Pro
d, Res, Develop, 1 2° (Nα1)
14 (1973), Toyokichi Tange, Japan Adhesive Association Ruins 2
3 (1), 26 (1987) D, J, Wa
lbridge S NAT port, Adv, 5tudy
In5t, Ser.

B, N (167, 40 (1983) Y, 5asa
ki and M, Yabuta, Proc.
, 10th, Int, Conf, Org.

Coat, Sci, Technol, 10. 2 6
3 (1984) etc., the cited polymers are listed.

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, acrylates These include homopolymers, methacrylate copolymers, acrylate copolymers, alkyd resins, and the like.

More specifically, the polymer component serving as a repeating unit of the dispersion stabilizing resin of the present invention has the following general formula (I
Examples include the component represented by [I].

General formula (II[) c, c2 -fCH-C+- X, -R2, In formula (I), x2 is V of formula (I). represents the same content as V in formula (I) for details. described in the description.

R21 is an optionally substituted alkyl group having 1 to 22 carbon atoms (e.g., 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, dodecenyl 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),
An optionally substituted alkenyl group having 3 to 22 carbon atoms (e.g. allyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group, octadecenyl group,
oleyl group, lylyl group, etc.), optionally substituted aralkyl groups 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.), substituted with 4 to 12 carbon atoms alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chlorocyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), optionally substituted aromatic groups having 6 to 22 carbon atoms ( For example, 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, phthoxylponylphenyl group, butylmethylphenyl group, N
, N-dibutylaminophenyl group, N-methyl-N-dodecylphenyl group, thienyl group, hyranyl group, etc.).

CI+ C2 represents the same content as al+ 12 in formula (I), and details are described in the explanation of al+ alil in formula (I).

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

Any other polymer component may be used as long as it copolymerizes with the monomer corresponding to the component represented by the general formula (I[r), and examples of the corresponding monomer include, for example, α-olefin , acrylonitrile, methachloronitrile, vinyl-containing heterocycles (heterocycles include, for example, pyran ring, pyrodrine ring, imidazole ring, pyridine ring, etc.) vinyl group-containing carboxylic acids (for example, acrylic acid, methacrylic acid, crotonic acid, itacon) acids, maleic acid, etc.) Vinyl group-containing carboxamides (e.g. acrylamide,
(methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.).

In the dispersion stabilizing resin of the present invention, the polymer component represented by general formula (III) is at least 30 parts by weight, preferably at least 50 parts by weight, based on 100 parts by weight of the total polymer of the resin.

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 (I) in the polymer base.

The polymerizable double bond group portion will be explained below.

General formula (1) %Formula% In general formula (1), vo is -0--COO--OC
O-fC)1. i0C'0- (-f"H,)
p-e-fin-CONHCOO- or -CONHC
represents ONH- (p represents an integer from 1 to 4).

In addition to a hydrogen atom, R1 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group,
2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.) optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g. 2-methyl-1-propenyl group, 2-butenyl group, 2-methoxyethyl group, 2-bromopropyl group, etc.) -pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), substituted groups having 7 to 12 carbon atoms. optional aralkyl group (e.g., benzyl group, phenethyl group,
-7enylfuropyl 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-cyclohexyl group,
-cyclopentylethyl group, etc.), or carbon number 6-1
2 optionally substituted aromatic groups (for example) engineerinyl 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, en)-1-dicarbonylphenyl group, acetamidophenyl group, pioamidophenyl group, dobcyroylamidophenyl group, etc.).

It 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.).

al and C2 may be the same or different from each other,
Preferably hydrogen atoms, halogen atoms (e.g. chlorine atoms,
bromine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group) -COO-R2 or C00R2 via hydrocarbon (
R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, specifically,
(Represents the same content as explained for R1 above)
represents.

Examples of the hydrocarbon in the =C[l[l-R, group] via a hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in general formula (I), V.

is -COO--0CO--CH20CD-1-CH2
C[]00- -C[1NH--3O7Nl(--C
ONHCOD- or may be different and represents a hydrogen atom, a methyl group, [:0OR2 or -CH2COOR2, (
R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Even more preferably al
+ Either one of C2 always represents a hydrogen atom.

That is, the polymerizable double bond group-containing moiety represented by the general formula (I) is specifically CH2C00CH3 CH2COOH CH2=C O=C-0-'['11. =CH-C0NHCH-CH
s CH,=C-C0NH-, CH=CH-C0NH-C)
+3 0CH2=C
-[:0NHCOD-CI(2=CH-0-CCH,=
Examples include CH-CH, -0-C-CH, =C11-0, and the like.

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, -D--3-d+ -N--3O--3O2--COD--'0COd2
da = C[INHCO-1-NH['0NH-1-['[)
s divalent aliphatic group or divalent aromatic group, or a combination of these divalent residues, optionally with intervening bonding groups selected from N--3[], N- and Si- represents an organic residue composed of Here, d1 to d represent the same content as R1 in formula (I).

Examples of divalent aliphatic groups include e, e, e2fc+C=
(e+ and C2 may be the same or different, and each represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 12 carbon atoms. Represents a group (for example, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromomethyl group, a butyl group, a hesyl group, an octyl group, a nonyl group, a decyl group, etc.).Q is -8- or -NR20- represents an alkyl group having 1 to 4 carbon atoms, -CH2Cl or -CH2Br
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 an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran Ei, 1.3
-oxazoline ring and the like.

Specifically, the polymerizable double bond group-containing moiety described above is randomly bonded into the polymer chain, or is bonded only to one end of the main chain of the polymer chain. Preferably, a polymer (hereinafter abbreviated as -functional polymer [M]) in which a polymerizable double bond group-containing portion is bonded only to one end of a polymeric main button is used.

The following are specific examples of the polymerizable double bond group-containing moiety represented by the general formula (I) of the functional polymer CM) above and the moiety composed of an organic residue linked to the moiety: However, it is not limited to these. However, on each side below, Pl is -H, -CH3, -C11, C0
0C113, -CI, -Br or -CN, R2 represents 1 or -CH3, X represents -01 or =Br, n represents an integer of 2 to 12, m is an integer of 1 to 4 shows.

(C-1) C'H, = C-C0D (CH2h 0 (C-2) CH.

CI(=CH-0(CH,h 0 (C-3) CH, =CH- (C-8) CH2”C)I CHCH20- 1l (C-9) CH2=　C-[”0OC11,C)lcl120H (C-4) CH, = CH-CM.

(C-5) C)l 2= C-Con (CH=)τNH-(C-
6) CH,=C-CD0CH,CHCH20-Kano (C-7) P.

CH2=C-C0NII(CH2+- (C-13) CH, = C-C0D (CH, +; 1-(C-14) CH2=C-CON■(CH2-)? (C-22) P2 CH2=C COO (CH2CH2 Kano? CD (CH effect H3 CH=CH CH.

COD Exit H2CHCH200 Exit (C) 12s 10 Kano N (C-17) CH2=CH CH2 coo-qcH=shicho ([knee 23) CH2CH2X (C-25) CH,=CH-CH20CO(CH,).

(C-26> (C-30) CH3 C)1. = [')I CH2C[][l(b)I2).

N C[][1CH2CH2 (C-27) CH.

(C-28) (C-29> [:D[l[Hschz) Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group moiety in the side chain of the polymer. Synthesis can be carried out by conventionally known methods.

For example, ■ a method of copolymerizing monomers containing two polymerizable double bond groups with different polymerization reactivity in the molecule; ■ a method of copolymerizing monomers containing two polymerizable double bond groups with different polymerization reactivity; ■ a method of copolymerizing a monomer containing two polymerizable double bond groups with different polymerization reactivity; After copolymerizing a functional monomer containing a functional group to obtain a polymer, a polymerizable double bond containing another reactive group is chemically bonded to a reactive group in the side chain of the polymer. Commonly known methods include a method of introducing a polymer through a reaction with an organic low-molecular compound containing a group, ie, a so-called polymer reaction.

As the method (①) above, for example, Japanese Patent Application Laid-Open No. 60-185962
Examples include the method described in Japanese Patent Publication No.

Specifically, Giyu Iwakura uses the method described in ■ above.

Keisuke Kurita "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (published in 1976), JP-A-61-43757, Patent Application Hei 1-14
It is described in detail in the specification filed as No. 9305.

For example, a polymer reaction using a combination of a group A functional group and a group B functional group shown in Table 1 below is a commonly known method. Note that R2□ and R23 in Table 1 are hydrocarbon groups, and represent the same contents as Is and Is in Ll of the above formula (n).

Table 1 The monofunctional polymer [M] containing a polymerizable double bond group at one end of the main chain, which is more preferable as the dispersion stabilizing resin of the present invention, can be produced by a conventionally known synthesis method. can. For example, a) a monofunctional polymer [M] is produced by reacting various reagents at the ends of a living polymer obtained by anionic or cationic polymerization.
Terminal obtained by radical polymerization using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, hydroxyl group, or amino group in the molecule. A method using a radical polymerization method to obtain a monofunctional polymer [M] by reacting a polymer with a reactive group bond with various reagents, c) A method using the above radical polymerization method on a polymer obtained by a polyaddition or polycondensation reaction. Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced in the same manner as described above.

Specifically, P, Dreyfuss & RoP, Qu
irk.

Bncycle, Polym, Sci, Bng, 7.
551 (1987) P, P, ReLIlpp, B
, Franta, Adv, Polym, Sci, .
58゜1 (1984), V. Percec, A.
ppl, Poly, Sci.

285.95 (1984), R0^sami, M.
Taka-ri, Macroo+o1. Chem,
5upp1. , 1 2. 1 6 3 (1985
), P,Rempp,, et al, Mac
romol, Chem.

5upp1. , 8. 3 (1984), Yuji Yogami, Kagaku Kogyo, 38.56 (1987), Yuya Yamashita, Kobunshi, 31.988 (1982), Shibe Kobayashi.

Kobunshi, 30, 625 (1981), Toshinobu Higashimura.

Japan Adhesive Association Journal, 18.536 (1982) Hiroshi Ito -
1 Polymer Processing, 35.262 (1986), Takashi Higashi, Takashi Tsuda 1 Functional Materials, 1987゜klo, 5, and other reviews, and the literature and patents cited therein.

More specifically, as a method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radically polymerizable monomer is synthesized according to Japanese Patent Application Laid-Open No. 2-67563.
Publication No. 63-64970, Japanese Patent Application No. 1-2069
89, No. 1-69011 in the application specifications, etc., and is a polymer containing a polyester structure or a polyether structure as a repeating unit [Ml is described in Japanese Patent Application No. 1-56379, No. 1-69011. 58989, 1-563
It can be obtained in the same manner as the methods described in the detailed description of the application as each item No. 80.

As explained above, the dispersed resin particles of the present invention contain a monofunctional monomer containing a polar group (A) and a monofunctional monomer containing a silicon atom and/or a fluorine atom (B) for stabilizing the dispersion. These are copolymer resin particles obtained by dispersion polymerization in the presence of a resin.

Furthermore, when the dispersed resin particles of the present invention have a network structure, the above-mentioned polar group-containing functional monomer (A) and the monofunctional monomer containing a fluorine atom and/or a silicon atom (B
) as a polymer component [abbreviated as polymer component (A)], the polymers are bridged to form a high-order network structure.

That is, the dispersed resin particles of the present invention contain polymer component (A)
It is a non-aqueous latex consisting of a part insoluble in a non-aqueous dispersion solvent and a polymer that is soluble in the solvent, and if it has a network structure, the part insoluble in the solvent is The molecules of the formed polymer component (A) 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.

The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (a) a method of crosslinking a polymer containing the polymer component (A) with various crosslinking agents or curing agents; (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 when carrying out a polymerization reaction; This can be carried out by a method such as a method in which the combined component (A) and a polymer containing a component containing a reactive group are crosslinked by a polymerization reaction or a polymer reaction.

Examples of the crosslinking agent used in the method (a) above include compounds commonly used as crosslinking agents.

Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" published by the Society of Polymer Science, Baifukan (1986), etc. Can be used.

For example, silane coupling of organic silane compounds (e.g., vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, T-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane, etc.) (e.g., toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) isocyanate, polymeric polyisocyanate, etc.), polyol-based compounds (e.g., 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1.1.1-trimethylolpropane, etc.), polyamine-based compounds (e.g., , ethylenediamine, r-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.) Polyepoxy group-containing compounds and epoxy resins (for example, "New Epoxy Resins" edited by Hiroshi Kakiuchi, Sho. Compounds described in Kodo (published in 1985), “Epoxy Resin” edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (published in 1969), etc. Melamine resins (for example, Miwa-be,
Compounds described in "Uria Melamine Resin" edited by Hideo Matsunaga, Nikkan Kogyo Shimbunsha (published in 1969), poly(
meth)acrylate compounds' (for example, compounds described in Makoto Okawara, Takeo Saegusa, and Toshinobu Higashimura, "Oligomer", Kodansha (published in 1976), Eizo Omori, "Functional Acrylic Resin", Technosystem (published in 1985), etc. Specific examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, Examples include oligoester acrylates and methacrylates thereof.

In addition, as a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polymerizable functional group of a polyfunctional oligomer, which are caused to coexist by the above method, Specifically, CH2=CH-CH2-, CH,=
CH-C-0-, CH,=CH-CL=C-C-0-C
H=CH-C-0-, CH2=CHC0NHI CH, =C-C0NH-CH=CH-C0NH-CH,
=C1l-CH,-0-C-CH,=[”H-NHCO
CH,=CH-CH2-NHCO-CH2=CH-8 ports.

Examples include CH2=CH-COCH2=CHOCH2=CHS. 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 styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. , ethylene glycol, vegetal ethylene glycol, triethylene glycol, polyethylene glycol #200, #40
0, #600.1.3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), or polyhydroxyphenol (such as hydroquinone, resorcinol, catechol, etc.) (derivative of) methacrylic acid,
Acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers, vinyl esters of dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) , allyl esters, vinylamides or allylamides: polyamines (e.g. ethylenediamine, 1°3-
Examples include condensates of propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, 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, methacryloyl propionic acid,
Reactants of alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonyl acetic acid, 2-
ester derivatives containing vinyl groups such as allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) 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, allyl methacryloyl propionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl methyl acrylate oxycarbonyl ethylene ester, N-allylacrylamide, N-allyl methacrylamide, N-allyl itaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohol @ (e.g. aminoethanol, ■-aminopropanol, 1-aminobutanol, 1 -aminohexanol,
2 to aminobutanol, etc.) and a carboxylic acid containing a vinyl group.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10 mol% based on the total amount of monomer (A) and other monomers coexisting with (A). below,
Preferably, it is used in an amount of 5 mol % or less to polymerize and 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 can be 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.

As a method for forming a network structure, polyfunctional monomers can be used as a method for forming a network structure, because monodisperse particles with a uniform particle size can be obtained through dispersion polymerization, and microparticles of 0.5 μm or less can be easily obtained. The method in which a polymer is used is preferred.

As described above, the network-dispersed resin particles of the present invention consist of a polymer component containing a repeating unit containing a polar group, a repeating unit having a fluorine atom and/or a silicon atom-containing substituent, and a polymer component that is soluble in the non-aqueous solvent. These are polymer particles containing a polymer component and having a structure in which molecular chains are highly cross-linked.

The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles may be any organic solvent as long as it has a boiling point of 200° C. or lower, and it may be used alone or in combination of two or more.

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

By synthesizing dispersed resin particles using a dispersion polymerization method in these non-aqueous solvent systems, the average particle diameter of the resin particles can easily be 1 μm.
In addition, the particle size distribution is very narrow and monodisperse particles can be obtained.

Specifically, K, Bj, Barrett Dis
persionPolymerization in
Organic Media J John
Wiley (1975), Part of Murata Kasuri, Polymer processing, 23.20 (1974), Tsunetaka Matsumoto and Toyokichi Tange, Japan Adhesive Association trace 9.183 (1973>, Tange Toyokichi, Japan Adhesive Association trace 23.26 ( (1987), D.J., W.
albridge 5NATO, ^dv, 5tudy
, In5t, Ser.

B, Nα67.40 (1983), British Patent No. 89
3429, 934038, U.S. Patent No. 11
22397, 3900412, 4606989 specifications, JP 60-179751, JP 60-1859
The method is disclosed in 63 publications and the like.

The dispersion resin of the present invention is composed of at least one of monomers (A), monomers (B), and a dispersion stabilizing resin, and when forming a network structure, polyfunctional monomers are optionally added. In any case, the important thing is that
If the resin synthesized from these monomers is insoluble in the nonaqueous solvent, a desired dispersed resin can be obtained.

More specifically, the monomer (A) and the monomer (
Based on B), 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. Further, the molecular weight of the decomposed resin particles of the present invention is 104 to 10.
6, preferably 104 to 5X105.

In order to produce the dispersed resin particles used in the present invention as described above, monomer (A), monomer (B) 9, a dispersion stabilizing resin, and a polyfunctional monomer (D) are generally used. may be polymerized by heating in a nonaqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, butyllithium. Specifically, (i) monomer (A), monomer (B)
9. A method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin and a polyfunctional monomer (D), (ii) dropping a mixture of the above polymerizable compound and a polymerization initiator into a nonaqueous solvent, or There are methods of adding it arbitrarily, and the method is not limited to these, and any method can be used for production.

The total amount of polymerizable compounds is 5 parts by weight per 100 parts by weight of the nonaqueous solvent.
The amount is about 80 parts by weight, preferably 10 to 50 parts by weight.

The amount of polymerization initiator is 0.1 to 5% by weight of the total amount of polymerizable compounds. Further, the polymerization temperature is about 30 to 180°C, preferably 40 to 120°C. Reaction time is 1-1
5 hours is preferred.

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 conventionally known resin can be used. For example, alkyd resins, vinyl acetate resins, polyester resins, styrene-butadiene resins, acrylic resins, etc., as cited in the explanation of the prior art, are mentioned, and specifically, Ryuji Kurita and Tsugube Ishiwata, Kobunshi, Vol. No. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (N118
), page 9, and other known materials cited in the review.

Preferably, one of them is a random copolymer group containing methacrylate as a polymer component, which is known as a binder resin for electrophotographic photoreceptors that use photoconductive zinc oxide as an inorganic photoconductor. For example, special public service
42, 50-31011, JP-A-50-98324,
No. 50-98325, Special Publication No. 54-13977, No. 59
-35013, JP-A-54-20735, JP-A-57-20
Examples include those described in 2544 publications.

Further, a random copolymer of methacrylate and a copolymer containing an acidic component such as a carboxyl group, a sulfo group, or a phosphono group with a weight average molecular weight of 20,000 or less, and another resin or heat and/or a weight average molecular weight of 30,000 or more. Binder resin composed of a combination with a compound that hardens with light: For example, JP-A-63-2
20148, JP 63-220149, JP 2-3
4860, 2-40660, 253064, 1-
Examples include those described in each No. 102573 publication.

Alternatively, a polymer having a weight average molecular weight of 20,000 or less, containing a methacrylate component, and containing an acidic group at one end of the polymer main chain, and another resin having a weight average molecular weight of 30,000 or more, or Binder resin composed of a combination with a compound that cures with heat and/or light: For example, JP-A-1-16
9455, 1-280761, 1-214865,
Also included are polymer groups such as those described in Japanese Patent Application No. 2-874, Japanese Patent Application No. 63-221485, Japanese Patent Application No. 63-220442, and Japanese Patent Application No. 63-220441.

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 account for no more than 40% by weight of the photoconductive zinc oxide, preferably no more than 20% by weight of the photoconductive zinc oxide.

If the content of other photoconductive materials exceeds 40% by weight, the effect of improving the hydrophilicity of non-image areas as a lithographic printing original plate will be weakened.

The total amount of binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, per 100 parts by weight of the photoconductor.

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) Page 12, C. J. Young et al.: RCA Re
view 15.

469 pages (1954), Wataru Kiyota: Transactions of the Institute of Electrical Communication Engineers J 63-C (No, 2) 97 pages (1980), Yuji Harasaki et al., Industrial Chemistry Journal pages 66, 78 and 18B (19
63), Tadaaki Tani, Journal of the Photographic Society of Japan 35.208 pages (19
72), etc. Review references such as nocarbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthine dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, logcyanine dyes, styryl dyes, etc.) Phthalocyanine dyes (
may contain metal), etc.

More specifically, examples of those mainly using carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include JP-B No. 51-452, JP-A No. 50-90334, JP-A No. 50-114227, 53-3
No. 9130, No. 53-82353, U.S. Patent No. 3
Examples include those described in the specifications of No. 052540 and No. 4054450, and Japanese Patent Application Laid-open No. 16456/1983.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as rhodacyanine dyes include F, M
, Hammer rThe Cyanine Dy
esand Re1ated Compounds J
It is possible to use the pigments described in et al., and more specifically,
U.S. Patent No. 3047384, U.S. Patent No. 3110591, U.S. Patent No. 31
21008, 3125447, 3128179, 3132942, 3622317, British Patent Nos. 1226892, 1309274, 14058
98 specifications, Japanese Patent Publication No. 48-7814, No. 55-18
Examples include dyes described in 892 publications and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
, 47-44180, JP 51-41061, JP 49-5034, 49-45122, 57-46
245, 56-35141, 57-157254,
61-26044, 61-27551, U.S. Pat. No. 361954, U.S. Pat. No. 4175956,
rResearch Disclosure J 19
Examples include those described in 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 above-mentioned review: Imaging 1973 (No.
, 8) Electron-accepting compounds cited in reviews such as page 12 (e.g., halogens, benzoquinones, 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, Nihon Kagaku Information Publishing Department (1986) Examples include alkane compounds, hindered phenol compounds, p-phenyl diamine compounds, and the like.

The amount of these various additives added is not particularly limited, but
Usually 0, OO1 to 2.0 per 100 parts by weight of photoconductor.
It is 0 parts by weight.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

In addition, when a photoconductive layer is used as a charge generation layer in a laminated photoreceptor consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.5μ. 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.

Typical resins used to form the charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl oxide copolymer resin, and polyacrylic resin. , polyolefin resin, urethane resin, polyester resin,
Thermoplastic resins and curable resins such as epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the 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 impregnated with a low-resistance substance is used in the same manner as in the past. those that have been subjected to conductive treatment, such as those that have been 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 also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. A water-resistant adhesive layer is provided on the surface of the support, at least one pre-coat layer is provided as necessary on the surface layer of the support, and a conductive plastic base coated with A1 or the like is laminated onto paper. Things can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, electronic photography, 14, (NOll) p2-11
(1975), Hiroyuki Moriga.

"Introductory Special Paper Chemistry" Kobunshi Publishing Association (1975) M, F
, Hoover, J1Macroo+o1. Sci,
Chern, ^-4(6).

Those described on pages 1327 to 1417 (1970) and the like are used.

In order to actually produce the lithographic printing original plate of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives are placed on a conductive support in a volatile hydrocarbon solvent with a boiling point of 200°C or less. An electrophotographic photosensitive layer (photoconductive layer) can be formed and manufactured by dissolving or dispersing it, coating it, and drying it. Specifically, preferred organic solvents are halogenated hydrocarbons having 1 to 3 carbon atoms, such as di-T:10 methane, chloroform, 1°2-dichloroethane, tetrachloroethane, dichloropropane, and trichloroethane. 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.

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-described structure by a conventional method, and then subjecting the non-image area to a desensitization treatment. 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-62-2003, which uses ferrocyanic compounds as the main desensitizing agent,
239158, 62-292492, 63-999
93, 63-9994, Special Publication No. 40-7334, 4
5-33683, Japanese Patent Publication No. 57-107889, Special Publication No. 4
6-21244, 44-9045, 47-3268
1, 55-9315, and JP-A-52-101102.

In addition, Japanese Patent Publications No. 43-28408, No. 45-24609, and No. 51-Sho.
103501, No. 54-10003, No. 53-838
05, 53-83806, 53-127002, 54-44901, 56-218.9, 57-27
96, No. 57-20394, No. 59-207290, Japanese Patent Publications No. 38-9665, No. 3, using a water-soluble polymer capable of forming metal chelates as the main ingredient.
9-22263, 40-763, 43-28404
, No. 47-29642, No. 52-126302, No. 52-134501, No. 53-49506, No. 53-5
9502, 53-104302, etc., and those described in JP-A-53-1989 using a metal complex compound as the main ingredient.
-104301, Tokuko Shou 55-15313, Shou 54-4
1924 publications, etc., or Japanese Patent Publication No. 39-137 using inorganic and organic acid compounds as main ingredients.
Examples include those described in JP-A No. 02, JP-A No. 40-10308, JP-A No. 46-26124, JP-A-51-118501, and JP-A No. 56-111695.

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.

〔Example〕

Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Production example 1 of resin for dispersion stabilization: [P-1:1 dodecyl methacrylate 97 g 1 glycidyl methacrylate 3 g
A mixed solution of 200 g of toluene and 200 g of toluene was heated to 75° C. while stirring under a nitrogen stream. 2.2'-azobisisobutyronitrile (abbreviation A, 1.B, N,) 1.0
g was added and stirred for 4 hours, and further ^, 1. B, N, 0.5g
was added and stirred for 4 hours. Next, 5 g of methacrylic acid and 1.0 g of N,N-dimethyldodecylamine were added to the reaction mixture.
g.

Add 0.5 g of t-butylhydroquinone and raise the temperature to 11
The mixture was stirred at 0°C for 8 hours. After cooling, it was re-precipitated in methanol 21 to collect a slightly brownish oil, and then dried.

The yield was 73 g, and the weight average molecular weight (-) was 3.6 x 10'.

[P-13 H3CH3 f C'H, -C+T-fCH, -C-+r- Production example 2 of resin for dispersion stabilization: [P-212-Ethylhexyl methacrylate 100 g.

A mixed solution of 150 g of toluene and 50 g of U isopropanol was heated to 75° C. with stirring under a nitrogen stream.

2.2'-azobis(4-cyanovaleric acid) (abbreviation A,
Add 2g of C, V, ) and react for 4 hours, and then add A, C4,
0.8 g was added and reacted for 4 hours. After cooling, it was reprecipitated into methanol 21, and the oil was collected and dried.

A mixture of 50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate, and 150 g of tetrahydrofuran was dissolved, and dicyclohexylcarboniimide (D,
A mixed solution of 8 g of C,C,), 0.2 g of 4-(N,N-dimethylamino)pyridine, and 20 g of methylene chloride was added dropwise at a temperature of 25 to 30°C, 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 off the precipitated insoluble matter, the filtrate was reprecipitated into methanol 11 and the oily matter was filtered. 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. The yield was 32g and -4,2X10'.

CP-21 CH.

A mixed solution of 4 g of toluene and 200 g of toluene was heated to 70° C. while stirring under a nitrogen stream. A.1. B
, N, as 1. Og was added and reacted for 8 hours.

Next, 8 g of glycidyl methacrylate and N
, 1.0 g of N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added, and at a temperature of 100°C, 1.
Stirred for 2 hours. After cooling, the reaction solution was mixed with methanol 2I
! 82 g of an oily substance was obtained. The number average molecular weight of the polymer was 5.600.

CP-3: ] Hs sH- Production example 3 of dispersion stabilizing resin: [P-3) butyl methacrylate] 96 g, Production example 1 of thioglyco resin particles: CL-1] acrylic acid 47.5 g, 2,
2.2.2', 2', 2' Hexafluoroisopropyl methacrylate [monomer (B-1)] 2.5 g, resin of Production Example 1 of dispersion stabilizing resin [P-117.5 g and methyl ethyl ketone 275 .8 g of the mixed solution was heated to 65° C. with stirring under a nitrogen stream. 2.2'-Azobis(isovaleroni)IJru) (abbreviation A, I, V, N
, ) was added and reacted for 2 hours. V,
N.

0.25 g was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth [L-
No. 11 was a latex with a polymerization rate of 100% and an average particle size of 0.38 μm.

Production Example 2 of Resin Particles: CL-21 Dispersion Stabilizing Resin AA-2 [: Manufactured by Toagosei Macromonomer: Macromonomer IW 3X10317.5g having methyl methacrylate as a repeating unit and 133g of methyl ethyl ketone were stirred under a nitrogen stream. The mixture was heated to 65°C.

To this, 41.5 g of acrylic acid, 2,2.2-)lifluoroethyl methacrylate [monomer (B-2): 12
, 5 g, A, 1. A mixed solution of 0.5 g of V, N, and 150 g of U methyl x thyl ketone was added dropwise over 1 hour, and the mixture was further stirred for 1 hour. Furthermore, A, I, V, N,
0.25 g was added and stirred for 2 hours. After cooling, the obtained white dispersion [L-21
The latex had a polymerization rate of 100% and an average particle size of 0.19 μm.

Production examples 3 to 16 of resin particles: [L-31 to [L-
16] In Production Example 2 of Resin Particles, each monomer in Table 2 below [(B-3) to (B16):12. 5g
A white dispersion was obtained in the same manner as in Production Example 2, except that . The polymerization rate of each latex [: (L-3) to (L-16)] was 100%, and the average particle size was 0.15 to 0.23μ.
It was in the range of m.

Production examples 17 to 24 of surface resin particles: CL-17] to [
L-24: ] Dispersion stabilizing resin AB-6C Macromonomer manufactured by Toagosei Aji: A mixed solution of 7.5 g of macromonomer HMw lX10' with n-butyl acrylate as a repeating unit and 133 g of methyl ethyl ketone was stirred under a nitrogen stream. It was heated to 65°C.

To this, 48.5 g of monomer (A) shown in Table 3 below was added.

Said monomer (B-6) 1.5 g%A, 1. V,N
, and 150 g of methyl ethyl ketone was added dropwise over 1 hour. Continue stirring for another 1 hour.
,A,1. 0.25 g of V and N were added and stirred for 2 hours. After cooling, each of the white dispersions (L-17] to CL-241 obtained by filtering through a 200 mesh nylon cloth was a latex with a polymerization rate of 100% and an average particle size in the range of 0.13 to 0.25 μl. there were.

Production Example 25 of Resin Particles: 47.5 g of CL-25:1 acrylic acid, 2.5 g of monomer (B-4), 1 g of ethylene glycol dimethacrylate, 1 g of resin for dispersion stabilization [P-317 g and diethyl ketone 27.5
g as a mixed solution, and the subsequent operations are as in Production Example 1 of Resin Particles.
It was synthesized in a similar manner. The obtained white dispersion [L-2
5] had a polymerization rate of 100% and an average particle size of 0.18 μm.

Production examples 26 to 36 of resin particles: [L-26E~]
L-36:] In Production Example 25 of Resin Particles, resin particles CL were produced in the same manner as in Production Example 25, except that the polyfunctional compound shown in Table 4 below was used instead of 1 g of ethylene glycol dimethacrylate.
-263 to [L36] were produced. The polymerization rate of each particle was 100%, and the average particle size was 0.18 to 0.23 μm.

Example 1 and Comparative Examples A-B Example 1 Binder resin CB-1 having the following structure] 40 g, photoconductive zinc oxide 200 g, uranine 0.03 g, rose bengal 0
．． 06g, tetrabromophenol blue 0.02g,
A mixture of 0.20 g of maleic anhydride and 300 g of toluene was dispersed in a ball mill for 4 hours. To this was added 0.8 g (as solid content) of dispersed resin particles [L-2], and the mixture was further dispersed for 10 minutes. This dispersion for forming a photosensitive layer was applied to electrically conductive treated paper using a wire spar so that the dry adhesion amount was 20 g/m'' and dried at 100°C for 3 minutes. An electrophotographic light-sensitive material was produced by leaving it for 24 hours under these conditions.

-5,3X10' (weight ratio) Comparative Example A In Example 1, dispersed resin particles [:L-212, Og
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that .

Comparative Example B Production of comparative resin particles: [LR-1] Acrylic acid 50
After preparing a mixed solution of 7.5 g of g1 dispersion stabilizing resin [AA2] and 275 g of methyl ethyl ketone, the following operations were performed in the same manner as in Resin Particle Production Example 1 to produce resin particles [LR-1]. The polymerization rate was 100% and the average particle size was 0.20μ. ] A photoreceptor was prepared in the same manner as in Example 1, except that 0.8 g (in terms of solid content) was used.

The film properties (surface smoothness) and electrostatic properties of these photosensitive materials,
The desensitization property (represented by the contact angle of the photoconductive layer with water after desensitization treatment) and printability of the photoconductive layer were investigated. Printability is
Fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film)
An image was formed by exposure and development using developer ELF-T, and a lithographic printing plate obtained by desensitization was used for investigation. (The printing machine used was Hamadastar 800SX model made by Hamadastar ■.) Summarizing the above results,
It is shown in Table-5.

The implementation aspects of the evaluation items listed in Table-5 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested using a Beck smoothness tester (Kumagai Riko □
The smoothness (sec/cc) was measured under the condition of an air volume of 1 cc.

Note 2) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer-3P-428 model manufactured by Kawaguchi Electric). After that, leave it for 10 seconds, and the surface potential at this time is V
+o was measured. Then, the potential V70 was measured after standing in the dark for 6D seconds, and the potential retention after dark decaying for 60 seconds, that is, the dark decay retention rate [D, R, R (%)
)] to (: (V?O/V,D) x 100 (%)
]. In addition, the surface of the photoconductive layer is heated by corona discharge.
After charging to 0V, the surface of the photoconductive layer was then illuminated with an illumination intensity of 2.0.
Irradiated with visible light of Lux, surface potential V +.

The time required for the light to attenuate to 1/10 is determined, and the exposure amount El,, O (lux seconds) is calculated from this. Similarly, V
The time required for +o to attenuate to 1/100 is determined, and the exposure amount E 1/100 (1ux-sec) is calculated from this.

Note 3) Imaging performance: Each photosensitive material and fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film ■) were used for one day and night at room temperature and humidity (20℃, 65%).
After being left to stand, a copy image is formed by making a plate, and the image (fogging, image quality) of the obtained copy original plate is visually observed (this is referred to as I). The image quality (2) of the copied image is tested in the same manner as in (I) above, except that plate making is performed at high temperature and high humidity (30° C., 80%).

Note 4) Raw plate water retention: Each photosensitive material itself (original plate without plate making, abbreviated as raw plate) is treated with desensitizing treatment liquid ELF-E manufactured by Fuji Photo Film ■.
An aqueous solution prepared by diluting X 5 times with distilled water was used and passed through an etching machine once. Next, these plates were printed using a Hamada Star 8005X model manufactured by Hamada Star ■, 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 making each photosensitive material in the same manner as in 3) above,
Using an aqueous solution of LP-EX diluted twice with distilled water,
After passing through an etching machine once, 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 Examples A to B were good, and the actual imaging performance and the copied images were all clear.

When each of these photoreceptors was desensitized and the degree of hydrophilization of the non-image area was evaluated, both Comparative Examples A and B showed significant background smudge due to adhesion of printing ink, and the hydrophilization of the non-image area was not sufficient. was not carried out.

Furthermore, when the lithographic plate of the present invention was actually printed after making a plate and subjected to a desensitization process, 6,000 prints with clear images and print quality were obtained without any occurrence of scumming.

On the other hand, in Comparative Examples and B, the background smudge in the non-image area became significant from the beginning of printing.

As described above, the electrophotographic lithographic printing original plate of the present invention is the only one in which the hydrophilicity of the non-image area has sufficiently progressed and free from blurring.

Example 2 In Example 1, 5.7 g of binder resin [B-2] having the following structure and 132.3 g of binder resin 1"B-3 were used instead of 38 g of binder resin CB-1. An electrophotographic material was prepared in the same manner as in Example 1.

CD[1CH2C’gH5CDDH ~ 6. OX 1 0’ [3-33 PS%Il　6.5X10' Each characteristic was measured in the same manner as in Example 1.

The following are particularly harsh environmental conditions (30°C.

80% RH).

Electrostatic characteristics V,, : -560VD, R,R:
90% E l/la: 11.31ux-sec E l/
loo: 32 1ux0sec Imaging performance: Very good (◎) Fresh plate water retention: 〃 (◎) Background smudge on printed matter: No background smudge up to 6000 sheets Each of the photosensitive materials of the present invention has chargeability and dark charge retention rate. , has excellent photosensitivity, and actual copied images and printed matter can be used at high temperatures and high humidity (30℃,
Even under the harsh conditions of 80% RH), clear images with no soil burr were obtained.

Examples 3 to 12 Instead of 0.8 g of dispersed resin particles in Example 2,
Each photosensitive material was produced in the same manner as in Example 2, except that 1.0 g (in terms of solid content) of each resin particle [L] of the present invention shown in Table 6 below was used.

The electrostatic properties and printing properties were evaluated in the same manner as in Example 2.

Table 6 Each photosensitive material exhibited almost the same characteristics as Example 2 in terms of electrostatic properties and imaging performance.

Furthermore, when the performance of the offset lithographic original plates was evaluated after being desensitized, the water retention properties of the green plates were good, and 6,000 sheets could be printed after actual plate making.

Example 13 and Comparative Examples CD Resin CB-516, Og with the following structure, resin with the following structure [
B-6] 34 g 1 200 g of zinc oxide, 18 g of cyanine dye [A] Oyo with the following structure and 300 g of toluene
After the mixture was dispersed in a ball mill for 4 hours, resin particles [L-1711°Og (as solid content) were added thereto and further dispersed for 5 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20 g/m', dried at 100°C for 3 minutes, and then heated at 20°C in the dark for 6 minutes.
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under the condition of 5% RH.

Resin CB-5] 〜6.5 An electrophotographic material was prepared in the same manner as in Example 1.

Comparative Example An electrophotographic light-sensitive material was prepared in the same manner as in Example 13, except that 3 g of resin particles [LR-1] were added instead of resin particles CL-1711 and Og.

The film properties (surface smoothness), film strength, electrostatic properties, imaging performance, and electrostatic properties of these photosensitive materials under environmental conditions of 30° C. and 80% RH were investigated. 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 7.

Among the evaluation items shown in Table 7, 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, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric). After that, leave it for 10 seconds, and at this time the surface potential V
1G was measured.

Then, the potential V after being allowed to stand still for 180 seconds in the dark
+110 and the retention of the potential after dark decaying for 180 seconds, that is, the dark decay retention rate [DRR (%)] is (
Visa/Via) x 100 (%) was calculated.

In addition, after the surface of the photoconductive layer is charged to -400V by corona discharge, it is irradiated with monochromatic light with a wavelength of 780n+n, the time required for the surface potential (V,.) to decay to 171O is determined, and from this the exposure amount E is determined. 1/10 (erg/co+')
Calculate.

Also, find the time until the surface potential (Vto) attenuates to 17100, and calculate the exposure amount E l/+011 (er
g/cm2).

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 a 2.0mW output gallium-aluminum-arsenide semiconductor laser (oscillation wavelength 780).
45 erg/nm) on the surface of the photosensitive material.
After exposure at a irradiation dose of cm2, a pitch of 25 μm, and a scanning speed of 330 m/sec, the reproduced image (fogging, Image quality) was visually evaluated.

The photoreceptors of Example 12 of the present invention and Comparative Example C had good electrostatic properties and good imaging properties.

On the other hand, the comparative example had deteriorated electrostatic properties and was significantly affected by it, especially when the environmental conditions changed, and even in actual copied images, ground force blur and breaks in letters and thin lines occurred.

On the other hand, among the desensitized original plates, only those of the present invention;
The non-image area was sufficiently hydrophilized and no adhesion of printing ink was observed, and up to 6,000 sheets could be printed.

In Comparative Example C, the hydrophilicity was insufficient, and in Comparative Example, the raw plate water retention was sufficient, but the copied image actually deteriorated in the original plate after plate making, so the printed matter was also affected by this. An unsatisfactory print was obtained from the press run.

Examples 14 to 19 In Example 13, binder resin particles CL-17 of the present invention
Each photosensitive material was prepared in the same manner as in Example 13, except that 1 g of each of the resin particles CL) shown in Table 8 below was used in place of Ig.

As shown in Table 8, excellent electrostatic properties were obtained in the present invention not only at room temperature (20° C., 65% RH) but also at high temperature and high humidity (30° C., 80% RH).

In addition, both the imaging properties and the water retention properties were good, and when printing was performed using it as an offset master original plate, more than 6,000 prints with clear image quality and no background smudge were obtained.

Examples 20 to 31 Resin CB-7 with the following structure] 6.0 g, Resin C with the following structure
B-8334g, photoconductive zinc oxide 200g, phthalic anhydride 0.20g, cyanine dye with the following structure [B)O,
After dispersing a mixture of 18 g of fi and 300 g of toluene in a ball mill for 4 hours, 0.9 g of resin particles shown in Table 9 below were obtained.
(as solid content) and dispersed for 5 minutes. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 20 g/m'', dried at 100°C for 3 minutes,
Then, an electrophotographic light-sensitive material was prepared by leaving it in a dark place for 24 hours at 20° C. and 65% RH.

Resin [B-'71 Resin CB-8) Hs Cyanine Dye [B] Table According to the present invention, it is possible to obtain an electrophotographic photoreceptor having excellent electrostatic properties and mechanical properties even under severe conditions. Also, as a planographic printing original plate, it is possible to print a large number of prints with clear image quality and no background smear.

Furthermore, the original plate of the present invention is effective in a scanning exposure method using semiconductor laser light.

The electrostatic properties and printing properties of each of the photosensitive materials produced in Examples 20 to 31 were measured in the same manner as in Example 13. All of them had excellent chargeability, dark charge retention, and photosensitivity, and were superior to actual Even under severe conditions of high temperature and high humidity (30° C., 80% RH), the copied images provided clear images with no occurrence of soil blurring or skipping of thin lines. Furthermore, when printed as an offset master original plate, more than 6,000 to 8,000 prints with clear images without blurring in the non-image areas could be printed.

〔Effect of the invention〕

Claims (3)

[Claims] (1) In an electrophotographic lithographic printing original plate comprising at least one photoconductive layer containing photoconductive zinc oxide and a binder resin on a conductive support, the photoconductive layer contains An original plate for electrophotographic lithographic printing, characterized in that it contains at least one type of non-aqueous solvent-based dispersed resin particles below having a particle diameter that is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles. Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, carboxyl groups, sulfo groups, sulfino groups, phosphono groups, ▲ mathematical formulas, chemical formulas, tables, etc. that are soluble in the non-aqueous solvent but become insolubilized by polymerization. There is ▼ [R_0 is a hydrocarbon group or -OR_1_0(
R_1_0 represents a hydrocarbon group], 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 and a monofunctional monomer containing a substituent containing a silicon atom and/or a fluorine atom and copolymerizable with the monofunctional monomer (A). copolymer resin particles obtained by carrying out a dispersion polymerization reaction with the compound (B) in the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent. (2) The original plate for electrophotographic lithographic printing according to claim (1), wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. (3) Claim (1) characterized in that the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (I) in the polymer chain. The original plate for electrophotographic lithographic printing described above. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the general formula (I), V_0 is -O-, -COO
-, -OCO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ -CONHCOO-, or -CONHCONH- (however, p represents an integer of 1 to 4, R_1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a_1
, a_2 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R
_2 or -COO-R_2 (R_2
represents a hydrogen atom or a hydrocarbon group that may be substituted]