JPH04355765A - Electrophotographic planographic printing plate material - Google Patents

Abstract

PURPOSE:To enhance water-holding capacity and printing resistance by incorporating a specified resin and specified resin particles dispersible in a nonaqueous solvent. CONSTITUTION:The photoconductive layer contains a binder resin having weight average molecular weight of 1X10<3>-2X10<4> and comprising repeating units each represented by formula I in an amount of >=30wt.%, and repeating units each having at least one of polar groups of -PO3H2, -SO3H,-COOH,-P(=O)(OH)R01, and a cyclic acid anhydride, in an amount of 0.5-15wt.%. This photoconductive layer contains other copolymer resin particles obtained by copolymerizing a monofunctional monomer C soluble in a nonaqueous solvent but to be insolubilized by polymerization and having a functional group to be allowed to produce a hydroxy group by decomposition and another monofunctional monomer D having a substituent containing an Si and/or F atom and capable of copolymerizing with the monomer C in the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent.

Description

[Detailed description of the invention]

0001

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

0002

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

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset master plate, and at the same time, the surface of the photoreceptor is easily compatible with the desensitizing treatment liquid, and the non-image areas are made sufficiently hydrophilic. It is water resistant, and the surface conductive layer with the image does not separate during printing, and it is compatible with dampening water, and the non-image area is sufficiently coated to prevent staining even when a large number of sheets are printed. It is necessary to have properties such as maintaining hydrophilicity. It has become clear that these performances are greatly influenced by the type of binder resin in the photoconductive layer.In particular, for offset master plates, various zinc oxide binder resins that improve desensitization properties are being investigated. has been done. In particular, methacrylate (or acrylate)
Examples include multi-component copolymers containing at least the component,
For example, Japanese Patent Publication No. 50-31011, Japanese Patent Publication No. 53-402
No. 7, JP-A-57-202544, JP-A-58-68
No. 046 etc. are known.

Furthermore, resins containing functional groups that generate hydrophilic groups upon decomposition are being considered as binder resins; for example, resins containing functional groups that generate hydroxyl groups upon decomposition (JP-A 1986-195684, JP-A-62-210475, JP-A-62-2104
No. 76), those containing a functional group that generates a carboxyl group upon decomposition (JP-A No. 62-21269), or those that contain a functional group that generates a hydroxyl group or a carboxyl group upon decomposition, and which also form a bridge between polymers. By preventing solubility in water and providing water swelling properties, it further prevents scumming and improves printing durability (Japanese Patent Application Laid-open No. 1-191
No. 157, JP-A-1-197765, JP-A-1-19
No. 1860, JP-A-1-185667, JP-A-1-1
No. 79052, JP-A No. 1-191158, etc.) are known.

[0005] However, even if the resin is said to be effective in improving desensitization properties as described above, when actually evaluated,
The background smearing and printing durability were still unsatisfactory.

[0006] Furthermore, JP-A-1-232356 and JP-A-1-26
1657 publications state that adding resin particles containing hydrophilic groups to the photoconductive layer is effective in improving water retention.

[0007] It has been confirmed that water retention can be significantly improved by improving these photoconductive compositions.

[0008]

[Problems to be Solved by the Invention] However, when we evaluate it in more detail as a lithographic printing original plate, we find that environmental changes (high temperature,
(high humidity or low temperature/low humidity), the electrophotographic properties (particularly charge retention in the dark, photosensitivity, etc.) fluctuate, making it impossible to obtain stable and good copied images in some cases. 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.

[0009] Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate as a digital direct lithographic printing original plate, it takes a longer time than when the entire surface is simultaneously exposed using visible light. Furthermore, since there are restrictions on the exposure intensity, higher performance is required in terms of electrostatic properties, particularly dark charge retention properties, and photosensitivity.

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

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

That is, object 1 of the present invention is to reproduce a copy image that is excellent in electrostatic properties (particularly dark charge retention and photosensitivity), is faithful to the original image, and has a uniform surface on the entire surface as an offset original plate. It is an object of the present invention to provide a lithographic printing original plate which does not cause not only stains but also dotted background stains and has excellent desensitization properties.

[0013] 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 varies from low temperature and low humidity to 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 when used in a scanning exposure method using semiconductor laser light.

[0015]

[Means for Solving the Problems] The present invention achieves the above object by forming at least one photoconductive layer on a conductive support, the photoconductive layer containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin. In the electrophotographic lithographic printing original plate having layers, the following resin [
A], and further 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 in the photoconductive layer. This is achieved by an electrophotographic lithographic printing original plate characterized by containing:

Resin [A]: 1×103 to 2×104
having a weight average molecular weight of 30% by weight or more as a polymer component of repeating units represented by the following general formula (I), -
PO3 H2 , -SO3 H, -COOH, -P(=
O) (OH) (R01) [R01 is a hydrocarbon group or -O
R02 (R02 represents a hydrocarbon group)] and a cyclic acid anhydride-containing group.

[0017]

[C4]

[However, in the above formula (I), a1,
a2 each represents a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group, and R03 represents a hydrocarbon group. ] [The above -P(=O)(OH)(R01) is

[0019]

[C5]

[0020] The non-aqueous solvent-based dispersed resin particles are soluble in the non-aqueous solvent but become insoluble by polymerization, and produce at least one hydroxyl group by decomposition. A monofunctional monomer (C) containing at least one functional group, and a monofunctional monomer containing a substituent containing a silicon atom and/or a fluorine atom and copolymerizable with the monofunctional monomer (C). It has the characteristic of being a copolymer resin particle obtained by carrying out a dispersion polymerization reaction of the monomer (D) in the presence of a dispersion stabilizing resin soluble in the solvent.

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

[0022]

[C6]

[However, in the above formulas (Ia) and (Ib), T1 and T2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR0
4 or -COOR05 (R04 and R05 each represent a hydrocarbon group having 1 to 10 carbon atoms), L1 and L2
each represents a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and a benzene ring] In the present invention, the non-aqueous solvent-based dispersed resin particles also form a higher-order mesh structure. It may be something that is currently in use.

[0024] Furthermore, as the above-mentioned dispersion stabilizing resin in the present invention, one containing at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain is particularly preferable. It is mentioned as a thing.

[0025]

[C7]

[In general formula (II), V0 is -O
-, -COO-, -OCO-, -(CH2)2OC
O-, -(CH2)2 COO-, -SO2 -, -
CONR1-, -SO2 NR1-, -C6 H4
-(-C6 H4 - is 1,2-, 1,3-, 1,4-
Represents a phenylene group. The same applies hereafter), -CONHCOO
-, or -CONHCONH- (where p is 1
represents an integer of ~4, R1 is a hydrogen atom or a carbon number of 1~4;
18), b1 and b2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom,
The lithographic printing original plate of the present invention represents a cyano group, a hydrocarbon group, -COO-R2, or -COO-R2 via a hydrocarbon group (R2 represents a hydrogen atom or a hydrocarbon group which may be substituted)] The surface of the photoconductive layer, which is the uppermost layer, is made hydrophilic by treating the non-image area of the photoconductive layer containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin with a desensitizing liquid. This is a printing original plate that is used as a lithographic printing original plate.

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

The resin particles [L] used in the present invention have an average particle size that is the same as or smaller than the maximum particle size of the photoconductive zinc oxide particles, and have a narrow particle size distribution and uniform particle size. It is something that In addition, the resin particles [L] undergo hydrolysis and redox reactions during desensitization treatment.
The above-mentioned hydrophilic group [monofunctional monomer (C)] that was protected by a chemical reaction such as a photolysis reaction generates a hydroxyl group and is converted from hydrophobic to hydrophilic property, and a fluorine atom. and/or a fluorine atom and/or a silicon atom by bonding a polymer component [monofunctional monomer (D)] containing at least a repeating unit containing a substituent containing at least one silicon atom. This indicates that migration and concentration phenomena occur on the surface of the photoconductive layer due to the large lipophilicity of the substituent contained therein. Furthermore, a dispersion stabilizing resin that stabilizes the dispersion of non-aqueous dispersed resin particles is adsorbed to a copolymer portion to be insolubilized in the reaction process of polymerization granulation, and/or a polymerizable resin represented by the above formula (II) is used. In the case of a dispersion stabilizing resin containing a double bond group moiety, both polymer components are chemically bonded.

The binder resin [A], which is another important feature of the present invention, contains a specific polymer component represented by formula (I) and has the above-mentioned specific polar group at least in the side chain of the polymer. It is characterized by being a low molecular weight polymer formed by bonding.

In the photoconductive layer of the present invention, photoconductive zinc oxide particles, a spectral sensitizing dye, and the resin particles [L] are dispersed by the resin [A] containing at least the binder resin, and further After the formation of the photoconductive layer, the resin particles [L] immediately migrate to the surface portion of the surface layer and are present in a concentrated manner in the vicinity of the surface.

That is, when the photoconductive zinc oxide particles, the spectral sensitizing dye, the resin particles [L] and the resin [A] are dispersed,
A low molecular weight resin [A] consisting of a specific polar group bonded to a specific position adsorbs to the stoichiometric defects of the photoconductive zinc oxide and causes the zinc oxide and the dye to interact with each other. Appropriate coverage and adsorption conditions compensate for trapping of photoconductive zinc oxide and dramatically improve concentration characteristics, while ensuring sufficient dispersion of photoconductive zinc oxide and suppressing agglomeration. This is thought to be due to this.

In particular, with conventional binder resins, when the type of spectral sensitizing dye changes, interactions such as adsorption are adversely affected, making it impossible to obtain satisfactory electrophotographic properties. However, when the resin [A] of the present invention is used, extremely excellent performance can be achieved even with dyes used particularly for spectral sensitization for semiconductor laser light.

[0033] Another important aspect of the original plate for an electrophotographic lithographic printing system is that the non-image area is made sufficiently hydrophilic through desensitization treatment, and has high water retention properties that prevent ink from adhering during printing. In the lithographic printing original plate of the present invention, the resin particles [L] concentrated on the surface portion of the photoconductive layer are desensitized to remove the specific hydrophilic groups (hydroxyl groups). By forming and exhibiting hydrophilicity, non-image areas are sufficiently modified to be hydrophilic and exhibit sufficient water retention without causing scumming. Furthermore, resin [
It is also possible to make the non-image area hydrophilic by desensitizing the zinc oxide particles uniformly dispersed in A] by a known method.

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

Furthermore, the resin particles contain a polymer component containing fluorine atoms and/or silicon atoms, and as a result, the particles migrate and concentrate on the surface of the photoconductive layer, resulting in an insensitive resin. It can be mentioned that the amount of addition is required to be extremely small in order to produce the same effect (water retention) as the effect of the known technology by exhibiting hydrophilicity through the chemical treatment.

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 deteriorate (particularly, uniform charging properties cannot be obtained), and as a result, In the copied image, density unevenness in the image area, broken or skipped characters and thin lines, and background fog in the non-image area occur.

Specifically, the resin particles of the present invention have a maximum particle size of 2 μm or less, preferably 0.5 μm or less. The average particle diameter of the particles is 0.8 μm or less, preferably 0.5 μm or less.

[0038] The smaller the particle diameter of the resin particles, the larger the specific surface area, which brings about good effects on the above-mentioned electrophotographic properties, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, If it is too large, it will resemble the case of molecular dispersion, and the effect of particles on improving water retention capacity will be diminished, so it is preferable to use the particle size at 0.001 μm or more.

Furthermore, in the present invention, the resin particles are made of a hydrophobic polymer component, that is, a dispersion stabilizing resin is bound to a corresponding polymer component, and this hydrophobic portion is bonded to the binder resin of the photoconductive layer. Because of the interaction, the anchor effect of this part prevents it from being eluted by dampening water during printing, and good printing characteristics can be maintained even when printing a large number of sheets.

Further, in the present invention, if the resin particles form a higher-order mesh 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 wire structure as described above or the resin particles that do form a higher-order wire structure (hereinafter simply referred to as "wire resin particles") contain 100% by weight of photoconductive zinc oxide. It is preferably used in an amount of 0.05 to 30% by weight. If the resin particles or mesh resin particles are less than 0.05% by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 30% 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.

Binder resin (A) used in the present invention is described below.
will be explained in detail. In weight [A], the weight average molecular weight is 1 x 103 to 2 x 104, preferably 3
x103 to 1 x104, and the glass transition point of the resin [A] is preferably -30°C to 110°C, more preferably -20°C to 90°C.

If the molecular weight of the resin [A] is less than 103, the film forming ability will decrease and sufficient film strength cannot be maintained, while if the molecular weight is more than 2 x 104, even if the resin of the present invention is used, In photoreceptors using infrared to infrared spectral sensitizing dyes, fluctuations in dark decay retention and photosensitivity become somewhat large under harsh conditions of high temperature and high humidity, and low temperature and low humidity.
The effect of the present invention in obtaining stable copied images is diminished.

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

[0044] The polar group content in resin [A] is 0.5
If it is less than % by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the polar group content is more than 15% by weight, the dispersibility decreases no matter how low the molecular weight is, and furthermore, background smudge increases when used as an offset master.

Further, as the low molecular weight resin [A], those represented by the general formula (Ia) and general formula (Ib) described above,
Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring at the 2-position and/or the 2-position and the 6-position
(Hereinafter, this low molecular weight material will be referred to as resin [A']).

Formula (Ia) and/or in resin [A']
Or, the proportion of the copolymerized component of the methacrylate corresponding to the repeating unit of formula (Ib) is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the specific polar group-containing polymer component is the proportion of the resin [A' ]0.5 per 100 parts by weight
-15% by weight, preferably 1-10% by weight.

Next, the repeating unit represented by the general formula (I), which is contained in the resin [A] in an amount of 30% by weight or more, will be further explained. In general formula (I), a1 and a2 are preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -COO-R06, or a hydrocarbon group. - through the group
COO-R06 (R06 is a hydrogen atom or a carbon number of 1 to 1
8 represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as described for R03 below) .

Hydrocarbons in the -COO-R06 group via the hydrocarbon include methylene group, ethylene group,
Examples include propylene group.

R03 is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group) group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc.), optionally substituted alkenyl groups having 2 to 18 carbon atoms (e.g. vinyl group, allyl group) , isopropenyl group, butenyl group, hexenyl group, heptenyl group,
octenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (benzyl group, phenethyl group,
naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.)
, an optionally substituted cycloalkyl group having 5 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), an optionally substituted aryl group (
For example, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group. group, ethoxycarbonylphenyl group, cyanophenyl group, etc.).

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

In formula (Ia), T1 and T2 are preferably hydrogen atoms, chlorine atoms and bromine atoms, respectively, as well as hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), carbon number 7
~9 aralkyl groups (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group,
methoxybenzyl group, chloro-methyl-benzyl group) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR0
4 and -COOR05 (preferred examples of R04 and R05 include those described above as preferred hydrocarbon groups having 1 to 10 carbon atoms).

In formulas (Ia) and (Ib), L
1 and L2 are each a direct bond connecting -COO- and a benzene ring or -(CH2)n1- (n1 is 1 to 3
), -CH2 OCO-, -CH2 CH
2 A linking group having 1 to 4 linking atoms such as OCO-, -(CH2O)m1- (m1 represents an integer of 1 or 2), -CH2CH2O-, and more preferably a direct bond or A linking group having 1 to 2 bonded atoms can be mentioned.

Formula (Ia) used in the resin [A] of the present invention
) or (Ib) Specific examples of copolymer components corresponding to the repeating units represented by (Ib) are listed below. However, the scope of the present invention is not limited thereto. The following (a-1
) to (a-20), n is an integer of 1 to 4, m is 0
or an integer of 1 to 3, p is an integer of 1 to 3, R10 to R13
are either -Cn H2n+1 or -(CH2)m
-C6 H5 (however, n and m are the same as above), X1
and X2 may be the same or different, and are a hydrogen atom, -
Represents either Cl, -Br, or -I.

[0054]

[Chemical formula 8]

[0055]

[Chemical formula 9]

[0056]

[Chemical formula 10]

[0057]

[Chemical formula 11]

[0058]

[Chemical formula 12]

[0059]

[Chemical formula 13]

[0060]

[Chemical formula 14]

[0061]

[Chemical formula 15]

[0062]

[Chemical formula 16]

[0063]

[Chemical formula 17]

Next, the polar groups in the polar group-containing component characteristic of the low molecular weight resin [A] will be explained. The polar group is -PO3 H2, -SO3 H, -COOH, -P
It is preferable that at least one type is selected from (=O)(OH)R01 and a cyclic acid anhydride-containing group.

-P(=O)(OH)R01 group means that R01 above represents a hydrocarbon group or -OR02 group (R02 represents a hydrocarbon group), specifically, R01 has 1 to 2 carbon atoms.
2 aliphatic groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group) , allyl group,
crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.), or an optionally substituted aryl group (e.g. Phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group , butoxyphenyl group, etc.), and R02 is R
The content is the same as 01.

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

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

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

The polar group-containing copolymerization component of the resin [A] is, for example, one represented by general formula (I) [general formula (Ia), (Ib)
Any vinyl compound containing a polar group that can be copolymerized with a monomer corresponding to a repeating unit shown in ]” Baifukan (published in 1986)
It is described in etc. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α
-acetoxymethyl form, α-(2-amino)methyl form,
α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α,β-dichloro form methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid) , 4-methyl-
2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid Half ester derivatives of vinyl or allyl groups of acids,
and ester dielectrics of these carboxyl or sulfonic acids, compounds containing the polar group in the substituent of amide derivatives, and the like.

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

[0071]

[Chemical formula 18]

[0072]

[Chemical formula 19]

[0073]

[C20]

[0074]

[C21]

[0075]

[C22]

[0076]

[C23]

[0077]

[C24]

[0078]

[C25]

[0079]

[C26]

[0080]

[C27]

[0081]

[C28]

[0082]

[C29]

[0083]

[C30]

[0084]

[Chemical formula 31]

[0085]

[C32]

[0086]

[Chemical formula 33]

[0087]

[C34]

[0088]

[C35]

[0089]

[C36]

[0090]

[C37]

[0091]

[C38]

[0092]

[C39]

[0093]

[C40]

[0094]

[C41]

[0095]

[C42]

[0096]

[C43]

Furthermore, the low molecular weight resin [A] of the present invention ([A
']) refers to the monomers of general formula (I), (Ia) and/or (Ib) described above and the monomer containing the polar group, as well as other monomers other than these. It may be contained as a polymerization component.

Examples of such other copolymerization components include, for example, methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those described in general formula (I), as well as α-olefins. vinyl carboxylates or acrylic esters (e.g. carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid,
naphthalene carboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (e.g. dimethyl ester, diethyl ester, etc.)
, acrylamides, methacrylamides, styrenes (e.g. styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds , vinyl ketone-containing compounds, heterocyclic vinyls (eg, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.). It is desirable that these other monomers do not exceed 30% by weight in the resin [A].

Resin [A] has a weight average molecular weight of 1×10
It is a random copolymer with a low molecular weight of 3 to 2 x 104, but the polymerization method for these is a conventionally known method.
By selecting polymerization conditions, it can be easily synthesized by methods such as radical polymerization and ionic polymerization. Radical polymerization reaction is advantageous and preferable from the viewpoint of purification, apparatus reaction method, etc., considering the monomer to be polymerized, the reaction temperature of the polymerization solvent, etc.

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

Furthermore, a method of using a chain transfer agent in combination is also known. For example, a desired weight average molecular weight can be adjusted by using a mercapto compound, a halogenated compound, etc. in an amount of 0.01 to 10 parts by weight based on the total monomer amount.

[0102] Low molecular weight resin [A] ([A'
) is preferably used in combination with the above-mentioned known resin for photoconductive zinc oxide. The ratio of low molecular weight resin to other resins is preferably 5-50/95-50 (weight ratio).

In the present invention, the ratio of photoconductive zinc oxide, resin (total binder resin) and resin particles [L] is 1
00/10 to 100/0.01 to 10 (weight ratio) is preferable. Further, the resin [A] preferably accounts for 5 to 50% by weight of the total binder resin of 10 to 100%.

[0104] Other resins used in combination have a weight average molecular weight of 3 x 104 to 1 x 106, preferably 5 x 104.
It is a medium to high molecular weight substance of ~5x105. Further, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C.

For example, typical examples include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl These include butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin, etc.

Specifically, Ryuji Shibata and Jiro Ishiwata, "Polymer" Vol. 17, p. 278 (1968), Harumi Miyamoto and Hidehiko Takei, "Imaging", 1973 (No. 8), No. 9
Page, Koichi Nakamura (ed.) "Practical technology of binders for insulating materials" Chapter 10, C. H. C. Publishing (1985), D. D.
Tatt, S. C. Heidecker, Tappi,
49 (No. 10), 439 (1966), E. S. B
altazzi, R. G. Blanclotte e
tal, Photo. Sci. Eng. 16 (No.5
), 354 (1972), Nguyen Tranh Khe, Isamu Shimizu, Eiichi Inoue, Electrophotography Society Journal 18 (No. 2),
28 (1980), Japanese Patent Publication No. 50-31011, Japanese Patent Publication No. 5
3-54027, 54-20735, 57-202
544, 58-68046, and the like.

[0107] Further, as a medium to high molecular weight resin which is a preferable resin to be used in combination, it satisfies the above-mentioned physical properties and preferably contains 30% by weight or more of a polymer component having a repeating unit represented by the following general formula (III). Examples include polymers.

[0108]

[C44]

[In formula (III), III is -COO-
, -OCO-, -(CH2)q -OCO-, -(C
H2 )q represents -COO-, -O- or -SO2 -. However, q represents an integer of 1 to 4.] In the general formula (III), f3 and f4 are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms), cyano groups, or alkyl groups having 1 to 4 carbon atoms (e.g. , methyl group, ethyl group, propyl group, butyl group, etc.). R1
3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group) group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group,
2-hydroxyethyl group, 2-methoxyethyl group, 2-
ethoxyethyl group, 3-hydroxypropyl group, etc.), optionally substituted alkenyl groups having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.) ),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (
For example, benzyl group, phenethyl group, naphthylmethyl group,
2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.),
Aryl groups that may be substituted (e.g. phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group) , iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, nitrophenyl group, etc.).

[0110] As the medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (III), for example, a random copolymer resin containing the polymer component represented by the formula (III) (Unexamined Japanese Patent Publication No. 63-49817, No. 63-22
0149, JP 63-220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-2
11766, 1-102573), formula (II
A copolymer containing a polymer component represented by I) and partially crosslinked in advance (JP-A-2-34860, JP-A-2-4066)
No. 0 publications), graft-type block copolymers produced by polymerizing a monofunctional macromonomer consisting of a polymer component of a specific repeating unit and a monomer corresponding to the component represented by formula (III) (Patent Application No. 0) 63-203933, 63-207
317, Patent Application Hei 1-163796, 1-212994,
1-229379 and 1-189245 (which the present inventors have already applied for).

Next, the non-aqueous solvent-based dispersed resin particles used in the present invention will be explained in detail. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization.

The non-aqueous solvent-based dispersed resin particles of the present invention contain at least one functional group that becomes insoluble in the non-aqueous solvent after polymerization and that decomposes to produce at least one hydroxyl group.
Polymer component consisting of monofunctional monomer (C) containing species [
A polymer component (C)] and a monofunctional monomer (D) containing at least a fluorine atom and/or a silicon atom as a substituent are combined into a dispersion stabilizing resin that is soluble in the non-aqueous solvent. It is characterized by being obtained by polymerization in the presence of

[0113] The resin particles used in the present invention have an average particle size that is the same as or smaller than the maximum particle size of the photoconductive zinc oxide particles, and have a narrow particle size distribution and uniform particle size. It is.

Specifically, the resin particles of the present invention have a maximum particle diameter of 2 μm or less, preferably 0.5 μm or less. The average particle diameter of the particles is 0.8 μm or less, preferably 0.5 μm or less.

[0115] The smaller the particle diameter of the dispersed 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, If the particle size is too large, it will resemble the case of molecular dispersion, and the effect of particles on improving water retention capacity will be diminished, so it is preferable to use the particle size at 0.001 μm or more.

[0116] The molecular weight of the dispersed resin particles is 104~
106, preferably 104 to 5×105.

[0117] In the present invention, resin particles that do not form a higher-order wire structure as described above or resin particles that do have a higher-order wire structure (hereinafter simply referred to as "wire resin particles") are photoconductive oxidized resin particles. It is preferably used in an amount of 0.01 to 10% by weight based on 100 parts by weight of zinc. If the resin particles or mesh resin particles are 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.

Monomer (C) as a polymerization component in the resin
The abundance ratio of monomer (D) is 30% by weight or more, preferably 50% by weight or more, and the abundance ratio of monomer (D) is 0.5% by weight to 3% by weight.
0% by weight, preferably 1% to 20% by weight. When other copolymerizable monomers are contained, the amount is at most 20% by weight or less.

[0119] Specifically, the solubility of the dispersion stabilizing resin of the present invention in the nonaqueous solvent is such that it dissolves at least 5% by weight in 100 parts by weight of the solvent at a temperature of 25°C.

[0120] The weight average molecular weight of the dispersion stabilizing resin is 1 x 103 to 5 x 105, preferably 2 x 1
03 to 1×104, particularly preferably 3×103 to
It is 5×104.

[0121] The weight average molecular weight of the dispersion stabilizing resin is 1×1
If it is less than 0.03, the produced dispersed resin particles will aggregate, making it impossible to obtain fine particles with a uniform average particle size. On the other hand, if it exceeds 5 x 105, the effect of the present invention of improving water retention while satisfying electrophotographic properties when added to the surface layer will be diminished.

[0122] In the total number of repeating units in the dispersion stabilizing resin of the present invention, repeating units having a substituent containing a fluorine atom and/or a silicon atom account for 40% by weight of the total.
It is preferable that the content is 6 or more, more preferably 6
It is 0 to 100% by weight.

[0123] When the above-mentioned components of the present invention are less than 40% by weight of the total, the effect of concentrating the resin particles on the surface layer when dispersed in the surface layer decreases, and as a result, the effect of improving water retention as a printing original plate decreases. fades away.

Preferably, 1 part of the dispersion stabilizing resin is added to the monomer (C) and monomer (D) to be insolubilized as described above.
~50% by weight, more preferably 2-30% by weight.

The resin particles [L] of the present invention dispersed in the photoconductive layer will be explained in more detail below.

Monomer (C) containing at least one functional group that can be decomposed to generate at least one hydroxyl group (hereinafter simply referred to as hydroxyl group-forming functional group-containing monomer (C)) used in the present invention ) will be explained in detail.

The functional groups contained in the hydroxyl group-forming functional group-containing resin of the present invention generate hydroxyl groups by decomposition, and the number of hydroxyl groups generated from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the hydroxyl group-forming functional group-containing resin has the general formula (IV):
-O-L] is a resin containing at least one kind of functional group.

In general formula (IV) [-O-L], L
is -Si(R1')(R2')(R3'), -C
O-Y1, -CO-Z-Y2, -CH=CH-CH
3 or

[0130]

[C45]

Represents [0131]. However, R1 ′, R2 ′, R
3', R4', R5', and R6' may be the same or different and each represents a hydrogen atom, a hydrocarbon group, or -O
-R'(R' represents a hydrocarbon group), Y1,
Y2 represents a hydrocarbon group, Z represents an oxygen atom, a sulfur atom or an -NH- group, and X represents a sulfur atom or an oxygen atom.

The functional group represented by the above general formula [--O--L] generates a hydroxyl group upon decomposition, and will be explained in more detail below. L is −Si (R1 ′)(R2 ′
)(R3 ′), R1 ′, R2
', R3' may be the same or different, preferably a hydrogen atom, an optionally substituted carbon number of 1 to 1
8 linear or branched alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.) ),
Optionally substituted alicyclic groups (e.g. cyclopentyl group,
cyclohexyl group, etc.), 7 to 1 carbon atoms that may be substituted
2 aralkyl groups (e.g. benzyl group, phenethyl group,
fluorobenzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, 3-phenylpropyl group, etc.)
or an aromatic group that may be substituted (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or -O-R'(R' is It represents a hydrocarbon group, and specifically represents the same substituents as the hydrocarbon groups of R1', R2' and R3' above.

[0133] When L represents -CO-Y1, Y1 is preferably an optionally substituted straight or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group, a trichloromethyl group, a trifluoromethyl group). , methoxymethyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-i-propyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.), optionally substituted with 6 to 1 carbon atoms
2 aryl group (eg, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

When L represents -CO-Z-Y2, Z represents an oxygen atom, a sulfur atom or an -NH- bonding group, and Y2 has the same meaning as Y1 described above. Further L
but,

[0135]

[C46]

In the case where X represents an oxygen atom or a sulfur atom. R4', R5', and R6' may be the same or different, and specifically represent the same contents as R1 to R3 described above.

Monomer [C] containing at least one functional group selected from the group of general formula [-O-L] used in the present invention can be easily synthesized by conventionally known organic synthesis reactions. can do.

For example, "New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [V]" edited by the Chemical Society of Japan, page 2497 (published by Maruzen Co., Ltd.), J. F. W. McOmie “Pr.
otective groups in Org
anic Chemistry” (Plenum
Press. (published in 1973), T. W. Greene
Protective groups in O
rganic Synthesis” (John
Wiley & Sons-Interscience
It can be produced by a synthetic reaction similar to the method for introducing a protecting group into a hydroxyl group as described in J. CE, 1981).

More specifically, the monomer (C) containing a functional group represented by the general formula [--O--L] as described above may include, for example, a compound represented by the following general formula (V).

[0140]

[C47]

In formula (V), X' is -O-, -CO-, -
COO-, -OCO-, -N(Q1)CO-, -CO
N(Q2)-,-SO2-,-SO2 N(Q3)
-, -N(Q4)SO2 -, -CH2 COO-,
-CH2 OCO-, -[C(g1)(g2)]n
-, aromatic group, or heterocyclic group [However, Q1
, Q2, Q3, and Q4 each represent a hydrogen atom, a hydrocarbon group, or -[Y'-O-L] in formula (V), and g1
, g2 may be the same or different, and hydrogen atoms,
represents a hydrocarbon group or (Y'-O-L) in formula (V), and n represents an integer of 0 to 18].

[0142] Y' represents a carbon-carbon bond which may be via a hetero atom that connects the bonding group ), for example -[C(g3)(g4
)]-,-C6 H10-,-C6 H4-,-(
CH=CH)-, -O-, -S-, -N(g5)-,
-COO-, -CONH-, -SO2 -, -SO2
It consists of bonding units such as NH-, -NHCOO-, -NHCONH-, etc., singly or in combination (however, g
3, g4, and g5 have the same meanings as g1 and g2, respectively).

L has the same meaning as in formula (IV). d1 and d2 may be the same or different and are a hydrogen atom, a hydrocarbon group (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted with -COOH etc.), -COOH or -
COO-W [W represents a C1-C18 alkyl group, alkenyl group, aralkyl group, alicyclic group, aromatic group which may be substituted with a substituent containing the general formula (-OL) group ] represents.

More specifically, the following compounds may be mentioned as monomers containing a functional group of the general formula [--O--L]. However, Me represents a methyl group.

[0145]

[C48]

[0146]

[C49]

[0147]

[C50]

[0148]

[C51]

[0149]

[C52]

According to another preferred embodiment of the present invention, the hydroxyl group-generating functional group-containing resin has a functional group having at least two hydroxyl groups located sterically close to each other and simultaneously protected with one protecting group. It is a resin containing at least one kind of.

Examples of functional groups having at least two hydroxyl groups in a protected form that are sterically close to each other include the following general formulas (VI) and (VII).
, (VIII), and (IX).

[0152]

[C53]

In formula (VI), J1 and J2 may be the same or different and represent a hydrogen atom, a hydrocarbon group or -O
-O-R''(R'' represents a hydrocarbon group), and U represents a carbon-carbon bond which may be via a heteroatom (however, the number of atoms between oxygen atoms is 5 or less).

[0154]

[C54]

In formula (VII), U is as defined above.

[0156]

[C55]

In formula (VIII), R7, R8 and U
is as defined above.

[0158]

[C56]

In formula (IX), J1 and J2 are as defined above. J3 is a hydrogen atom, or an aliphatic group having 1 to 8 carbon atoms (for example, an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, or a benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, or chlorobenzyl group) (represents an aralkyl group such as a group).

A more detailed explanation of the functional group is as follows. In formula (VI), J1 and J2 may be the same or different, preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, hexyl group,
2-methoxyethyl group, octyl group, etc.), carbon number 7-9
an optionally substituted aralkyl group (e.g. benzyl group,
phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic groups having 5 to 7 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, chlorophenyl group) group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.) or -O-R'''(R''' is J1
, J2).

[0161] U represents a carbon-carbon bond which may be via a heteroatom, and the number of atoms between oxygen atoms is 5 or less. At least two hydroxyl groups as described above
Monomer (C) protected with two protecting groups can be synthesized by the method described in the same known technical documents cited in the synthesis method of [-O-L].

More specifically, examples of monomers containing the functional group include the following. However, a is -
Indicates H or -CH3.

[0163]

[C57]

[0164]

[C58]

[0165]

[C59]

A monofunctional monofunctional compound containing a substituent containing at least two fluorine atoms and/or silicon atoms, which can be copolymerized with the monomer (C) containing a functional group that can be decomposed to form a hydroxyl group as described above. Regarding the monofunctional monomer (D), the monofunctional monomer (D) of the present invention may be any compound that 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 the fluorine atom-containing substituent include -C h F2h+1 (h represents an integer from 1 to 12)
, -(CF 2 ) j CF2 H (j is 1 to 11
), -C 6 H l F l' [(l
, l' are each an integer of 1 to 5, provided that l+l'=5) or (l=5-l', l' is an integer of 1 to 5).

Examples of silicon atom-containing substituents include:
-Si(R3)(R4)(R5), -S
Examples include i(R 6 )(R 7 )O k -R8 (k represents an integer of 1 to 20), a polysiloxane structure, and the like.

[0169] However, R 3 , R 4 , and R 5 may be the same or different, and may be a substituted hydrocarbon group or an -OR9 group (R 9 has the same content as the hydrocarbon group of R 3 ).

R 3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group,
Dodecyl group, hexadecyl group, 2-chloroethyl group, 2
-bromoethyl group, 2,2,2-trifluoroethyl group,
2-cyanoethyl group, 3,3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2
-methoxycarbonylethyl group, 2,2,2,2',2
',2'-hexafluoroisopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
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 carbon Number 6
~12 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, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxy (carbonylphenyl group, acetamidophenyl group, propylamidophenyl group, dodecoylamidophenyl group, etc.).

In the -OR9 group, R 9 represents the same content as the hydrocarbon group of R 3 above.

R 6 , R 7 , R 8 may be the same or different, and R 3 , R 4 , R 5
represents the same symbol content as .

Next, specific examples of repeating units having a substituent containing a fluorine atom and/or a silicon atom as described above are shown below. Here, b represents H or CH3,
Rf is -CH2ChC2h+1-(CH
2) 2-(CF2)j CF2H, R1', R2', R3' have 1 carbon number
~12 alkyl group, R'' is -Si(CH3
) 3, h is an integer from 1 to 12, and j is from 1 to
represents an integer of 11, i represents an integer of 1 to 3, and l represents an integer of 1 to 3.
q represents an integer of 1 to 20, r represents 0 or an integer of 1 to 20, and t represents an integer of 2 to 12. However, the scope of the present invention is not limited thereto.

[0174]

[C60]

[0175]

[C61]

[0176]

[C62]

[0177]

[C63]

[0178]

[C64]

[0179]

[C65]

[0180]

[C66]

[0181]

[C67]

[0182] Together with the polar group-containing monomer (C) and the fluorine atom- and/or silicon atom-containing monomer (D) as described above, other copolymerizable monomers other than these are polymerized. It may be contained as a combined component.

Other monomers include the general formula (X) shown below.
A monomer corresponding to the repeating unit of formula (X)
Examples include those copolymerized with monomers corresponding to the components shown in .

[0184] It is important that the polymeric component insoluble in this non-aqueous solution has a hydrophilicity of 50 degrees or less as expressed by the above-mentioned contact angle with distilled water.

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

For example, olefin polymers, modified olefin polymers, styrene-olefin copolymers, aliphatic carboxylic acid vinyl ester copolymers, modified maleic anhydride copolymers, polyester polymers, polyether polymers, methacrylate homopolymers. acrylate homopolymers, methacrylate copolymers, acrylate copolymers, alkyd resins, etc.

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

[0188]

[C68]

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

R21 is an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, dosaconyl group, 2-(N,N-dimethylamino)ethyl group, 2
-(N-morpholino)ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-(α-thienyl)ethyl group, 2-carboxyethyl group, 2-methoxycarbonylethyl group,
2,3-epoxypropyl group, 2,3-diacetoxypropyl group, 3-chloropropyl group, 4-ethoxycarbonylbutyl group, etc.), optionally substituted alkenyl groups having 3 to 22 carbon atoms (e.g. allyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group,
octadecenyl group, oleyl group, linoleyl group), optionally substituted aralkyl group having 7 to 22 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group,
2-naphthylmethyl group, 2-(2'-naphthyl)ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
methoxybenzyl group, dimethoxybenzyl group, butylbenzyl group, methoxycarbonylbenzyl group, etc.), optionally substituted alicyclic groups having 4 to 12 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chloro cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), carbon number 6 or more
22 optionally substituted aromatic groups (e.g. phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, anthranyl group, chlorophenyl group, bromophenyl group, butylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Octyloxyphenyl group, ethoxycarbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N,N-dibutylaminophenyl group, N
-methyl-N-dodecylphenyl group, thienyl group, hyranyl group, etc.).

c1 and c2 are b1 and c2 in formula (II),
b2 represents the same content as b1 in formula (II) for details.
, b2.

[0192] As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the above-mentioned components.

[0193] Any other polymer component may be used as long as it copolymerizes with the monomer corresponding to the component represented by the general formula (X). Examples of the corresponding monomer include:
α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (heterocycles include pyran ring, pyrrolidone ring, imidazole ring, pyridine ring, etc.)
, vinyl group-containing carboxylic acids (e.g. acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc.), vinyl group-containing carboxamides (e.g. acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid, etc.) acid hemiamide, itaconic acid diamide, etc.).

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

Further, the dispersion stabilizing resin of the present invention contains a photo- and/or thermosetting functional group in an amount of 30 parts by weight or more, preferably 20 parts by weight or less based on 100 parts by weight of the total polymer of the resin. You may. Examples of the photo- and/or thermosetting functional groups contained include those other than polymerizable functional groups, and specific examples include functional groups for forming crosslinked structures of particles, which will be described later.

1 of the polymer components as the dispersion stabilizing resin
For example, when a heat-curable and/or photo-curable group is contained, elution can be further suppressed by further chemically bonding with the binder resin.

Furthermore, it is preferable that the dispersion stabilizing resin of the present invention contains at least one polymerizable double bond group moiety represented by the above-mentioned general formula (II) in the polymer chain.

The polymerizable double bond group portion will be explained below.

[0199]

[C69]

In general formula (II), V0 is -O-
, -COO-, -OCO-, -(CH2)p -OC
O-, -(CH2)p-COO-, -SO2-,
-CONR1, -SO2NR1, -C6H4
-, -CONHCOO-, or -CONHCONH- (p represents an integer of 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, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (such as 2-bromopropyl group),
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
Or, an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group) , ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
acetamidophenyl group, propioamidophenyl group,
dodecoylamidophenyl group, etc.).

[0202] When V0 represents -C6 H4 -,
The benzene ring may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxymethyl group, etc.). group, ethoxy group, propioxy group, butoxy group, etc.).

b1 and b2 may be the same or different, preferably a hydrogen atom, a halogen atom (
For example, chlorine atom, bromine atom, etc.), cyano group, carbon number 1~
4 alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R2 or COOR2 via a hydrocarbon (R2 is a hydrogen atom or a carbon atom with 1 to 1 carbon atoms)
represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group of 18, which may be substituted, and specifically represents the same content as explained for R1 above) .

[0204] Hydrocarbons in the -COO-R2 group via the hydrocarbon include methylene group, ethylene group,
Examples include propylene group.

More preferably, in general formula (II), V0 is -COO-, -OCO-, -CH2OC
O-, -CH2 COO-, -O-, -CONH-, -
SO2 NH-, -CONHCOO- or -C6 H4
-, b1 and b2 may be the same or different, and represent a hydrogen atom, a methyl group, -COOR2 or -
CH2 COOR2 (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Still more preferably b1, b2 One of these always represents a hydrogen atom.

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

[0207] These polymerizable double bond group-containing moieties are bonded directly to the main chain of the polymer chain or via an arbitrary linking group. Specifically, the connecting group is a divalent organic residue, such as -O-, -S-, -N(d1)-
, -SO-, -SO2-, -COO-, -OCO-,
-CONHCO-, -NHCONH-, -CON(d2
)-SO2 (d3)- and -Si (d4)(
d5) represents an organic residue composed of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from d5). Here, d1 to d5 represent the same content as R1 in formula (II).

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

020
9]

[C70]

[0210] {k1 and k2 may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q represents -O-, -S- or -NR20-, R20 is an alkyl group having 1 to 4 carbon atoms, -CH2
Cl or -CH2Br}.

[0211] 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 a furan ring, a thiophene ring, a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring.

[0213] Specifically, the polymerizable double bond group-containing moiety as described above is bonded randomly within the polymer chain, or bonded only to one end of the main chain of the polymer chain. Preferably, a polymer (hereinafter referred to as a monofunctional polymer) in which a polymerizable double bond group-containing moiety is bonded only to one end of the main chain of the polymer chain is preferable.
(abbreviated as M)).

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

[0215]

[C71]

[0216]

[C72]

[0217]

[C73]

[0218]

[C74]

[0219]

[C75]

[0220]

[C76]

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

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

[0223] As the method (①) above, for example,
Examples include the method described in Japanese Patent No. 185962. As for the above method (■), specifically, Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (published in 1976), JP-A-6
It is described in detail in Japanese Patent Application No. 1-43757 and the specification filed as Japanese Patent Application No. 1-149305.

[0224] 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. In addition, R22, R in Table-1
23 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, carboxy benzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group,
2-methoxyethyl group, 3-methoxypropyl group, 2-
methanesulfonylethyl group, 2-cyanoethyl group, N,
N(dichloroethyl)aminobenzyl group, N,N(dihydroxyethyl)aminobenzyl group, chlorobenzyl group, methylbenzyl group, N,N(dihydroxyethyl)aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group group, acetylphenyl group, etc.).

[0225]

[Table 1]

[0226] More preferred as the dispersion stabilizing resin of the present invention is a -containing polymerizable double bond group moiety at one end of the main chain.
The functional polymer [M] can be produced by a conventionally known synthesis method. For example, a) a method using an ionic polymerization method in which a monofunctional polymer [M] is obtained by reacting various reagents with the ends of a living polymer obtained by anionic polymerization or cationic polymerization, and b) a method using carboxyl groups and hydroxyl groups in the molecule. Using a polymerization initiator and/or chain transfer agent containing a reactive group such as a group or an amino group, a polymer with terminal reactive groups bonded by radical polymerization is reacted with various reagents to form a monofunctional polymer. A method using a radical polymerization method to obtain the polymer [M]; c) a polyaddition condensation method in which a polymerizable double bond group is introduced into a polymer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. For example, the method by

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

[0228] More specifically, as a method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing repeating units corresponding to a radically polymerizable monomer can be synthesized by
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application No. 1-206989, No. 1-69011, etc., and contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] is disclosed in Japanese Patent Application No. 1-56379, No. 1-58989,
It can be obtained in the same manner as the methods described in the specifications of the applications as No. 1-56380.

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

Furthermore, when the dispersed resin particles of the present invention have a network structure, the above polar group-containing monofunctional monomer (C
) and a silicon atom and/or fluorine atom-containing monofunctional monomer (D) as a polymerizable component [abbreviated as polymer component (C)], the polymers are bridged,
It forms a high-order network structure.

[0231] That is, the dispersed resin particles of the present invention are non-aqueous latex consisting of a portion insoluble in a non-aqueous dispersion solvent consisting of the polymer component (C) and a polymer soluble in the solvent. When the polymer component has a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged.

[0232] As a result, the network resin particles become poorly soluble or insoluble in water. in particular,
The solubility of the resin in water is 80% by weight or less, preferably 5% by weight or less.
It is 0% by weight or less.

[0233] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (a) the polymer component (C
) A method of crosslinking a polymer containing (b) with various crosslinking agents or curing agents, (b) carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (C),
A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and (c) the polymer component (C
) and a polymer containing a component containing a reactive group through a polymerization reaction or a polymer reaction.

[0234] As the crosslinking agent in the above method (a), compounds commonly used as crosslinking agents can be mentioned. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. Can be used.

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

[0236] Furthermore, in the method (b) above, polymerization of a polyfunctional monomer (also referred to as polyfunctional monomer (E)) or polyfunctional oligomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (E)) Specifically, the sexual functional group is CH2=CH-C
H2-, CH2=CH-CO-O-, CH2=C
H-, CH2=C(CH3)-CO-O-, CH(
CH3)=CH-CO-O-, CH2=CH-CO
NH-, CH2=C(CH3)-CONH-, CH
(CH3)=CH-CONH-, CH2=CH-O
-CO-, CH2=C(CH3)-O-CO-, C
H2=CH-CH2-O-CO-, CH2=CH
-NHCO-, CH2 = CH-CH2 -NHCO-
, CH2=CH-SO2-, CH2=CH-CO
-, CH2 = CH-O-, CH2 = CH-S-, and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

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

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

Furthermore, in the case of forming a chemical bond and bridging between polymers by the reaction of the reactive groups between the polymers in the method (c) above, it is possible to use a method similar to the reaction of ordinary organic low-molecular compounds. The same can be done. Specifically, it can be synthesized according to the same method as described in the method for synthesizing the dispersion stabilizing resin.

[0241] In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can be easily obtained, so polyfunctional polymerization is recommended as a method for forming a network structure. Method (b) using monomers is preferred.

As described above, the network-dispersed resin particles of the present invention contain a repeating unit containing a polar group and a polymer component soluble in the non-aqueous solvent, and the molecular chains are highly cross-linked. It is a particle of a polymer having a similar structure.

[0243] As the non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles, any organic solvent with a boiling point of 200°C or less may be used, and it may be used alone or in a mixture of two or more. good.

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

[0245] By synthesizing dispersed resin particles in these non-aqueous solvent systems by dispersion polymerization, the average particle size of the resin particles can easily be 0.8 μm or less, and the particle size distribution is extremely narrow and monodisperse. particles.

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

The dispersed resin particles of the present invention contain at least 1 portion each of monomer (C), monomer (D), and dispersion stabilizing resin.
When a network structure is formed, a polyfunctional monomer (E) is coexisting as necessary.In any case, the important thing is that the resin synthesized from these monomers If the particles are insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, 1 part of the dispersion stabilizing resin is added to the monomer (C) and monomer (D) to be insolubilized.
It is preferable to use 50% by weight, more preferably 2 to 30% by weight. Further, the molecular weight of the dispersed resin particles of the present invention is 104 to 106, preferably 104
~5×105.

[0248] In order to produce the dispersed resin particles used in the present invention as described above, monomers (C) and monomers (D
), a dispersion stabilizing resin, and a polyfunctional monomer (E) are further heated and polymerized in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, butyllithium in a nonaqueous solvent. That's fine. Specifically, (i) monomer (C),
Monomer (D), dispersion stabilizing resin and polyfunctional monomer (E
) A method of adding a polymerization initiator to the mixed solution of (ii)
There is a method in which a mixture of the polymerizable compound and a polymerization initiator is added dropwise or optionally to a non-aqueous solvent, and the method is not limited to these, and any method can be used for production.

[0249] The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the nonaqueous solvent.
~50 parts by weight.

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

[0251] The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

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 less than 40% by weight of the photoconductive zinc oxide, preferably less than 20% by weight.

[0254] When the amount of other photoconductive materials exceeds 40% by weight,
The effect of improving the hydrophilicity of the non-image area as a lithographic printing original plate is weakened.

[0255] The photoconductive zinc oxide according to the present invention includes:
It is sufficient to use what is conventionally known in this type of technical field.
Not only so-called zinc oxide, but also zinc oxide treated with acid, zinc oxide pretreated with pigment, and kneaded and re-pulverized (
It may be a so-called press treatment) or the like, and is not particularly limited.

[0256] The total amount of binder resin used for the inorganic photoconductive material is 1 part by weight of the binder resin per 100 parts by weight of the photoconductor.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 50 parts by weight.

The spectral sensitizing dye used in the photoconductive layer of the present invention may be any conventionally known dye and these may be used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (N
o. 8) Page 12, C. J. Young et al.: RCA
Review 15, 469 pages (1954), Wataru Kiyota: Journal of the Institute of Electrical Communication J63-C (No. 2)
97 pages (1980), Yuji Harasaki et al., Industrial Chemistry Magazine 66,
78 and 188 pages (1963), carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes ( Examples include oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, cytylyl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like.

More specifically, as carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes, there are
52, JP-A No. 50-90334, No. 50-114227
, 53-39130, 53-82353 publications,
Examples include those described in U.S. Pat. No. 3,052,540, U.S. Pat.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F. M. Hammer “The Cya”
nine Dyes and Related C
It is possible to use pigments described in US Pat. No. 3,047,384 and US Pat.
10591, 3121008, 3125447, 3128179, 3132942, 3622317
Specifications of each issue, British Patent No. 1226892, British Patent No. 13092
74, 1405898 specifications, Japanese Patent Publication No. 1978-1978
14, No. 55-18892, and the like.

[0260] Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region, JP-A-47-840, JP-A-47-44180, and JP-A-51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 361954, U.S. Patent No. 4175956
Specifications of each issue, “Research Disclosure
re'', 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

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

[0262] The amount of these various additives added is not particularly limited, but is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0μ, especially 10-50μ is suitable.

[0263] When a photoconductive layer is used as the charge generation layer of a photoconductor with a stacked charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 1μ. 0
．． 5μ is suitable.

Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes, and the like. The thickness of the charge transport layer is preferably 5 to 40 microns, particularly 10 to 30 microns.

[0265] As the resin used for forming the charge transport layer,
Typical examples are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride acid copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, and epoxy. Thermoplastic resins and curable resins such as resins, melamine resins, and silicone resins are used as appropriate.

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

[0267] Specifically, as an example of a conductive substrate or a conductive material, see Yukio Sakamoto, Electrophotography, 14, (No. 1
), p2-11 (1975), Hiroyuki Moriga, "Introduction to the Science of Special Paper", Kobunshi Publishing Association (1975), M. F. Hoov
er, J. Macromol. Sci. Chem. A-
4(6), pp. 1327-1417 (1970), etc. are used.

[0268] In order to actually produce the original plate for lithographic printing of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives, etc. are placed on a conductive support by volatile carbonization with a boiling point of 200°C or less. An electrophotographic photosensitive layer (photoconductive layer) can be produced by dissolving or dispersing it in a hydrogen solvent, coating it, and drying it. The organic solvent used is
Specifically, dichloromethane, chloroform, 1,2
- 1 to 3 carbon atoms, such as dichloroethane, tetrachloroethane, dichloropropane or trichloroethane;
Preferred are halogenated hydrocarbons. Other various solvents used in coating compositions, such as aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride, and the above-mentioned solvents. Mixtures of can also be used.

[0269] A printing plate using the lithographic printing original plate of the present invention is prepared by forming a copy image on the electrophotographic original plate having the above-mentioned structure by a conventional method, and then subjecting the non-image area to a desensitization treatment. be done. The desensitization treatment used in the present invention involves hydrolyzing the resin particles of the present invention by passing them through a treatment solution, decomposing them by redox reaction, decomposing them by light irradiation, etc. to remove hydroxyl groups. Examples include a method in which resin particles are hydrophilized and zinc oxide is desensitized with a desensitization treatment liquid. In the latter case, (1) desensitizing zinc oxide particles and resin particles is carried out simultaneously. ■ After making the zinc oxide particles desensitized, the resin particles are decomposed. (2) Any procedure can be used, such as decomposing the resin particles and then subjecting the zinc oxide particles to a desensitizing reaction.

[0270] As a method for desensitizing zinc oxide, any conventionally known treatment liquid can be used. for example,
Using a ferrocyanic compound as the main desensitizing agent,
JP 62-239158, JP 62-292492, JP 63-99993, JP 63-9994, JP 40-7
334, 45-33683, JP-A-57-10788
9, Special Publication No. 46-21244, No. 44-9045, No. 4
7-32681, 55-9315, Japanese Patent Application Publication No. 52-10
1102 publications, etc. However, from the viewpoint of the safety of the treatment liquid, the following treatment liquids are preferred.

For example, Japanese Patent Publications No. 43-28408 and No. 45-24609 using a phytic acid compound as the main ingredient
, JP-A-51-103501, JP-A No. 54-10003,
53-83805, 53-83806, 53-1
27002, 54-44901, 56-2189,
57-2796, 57-20394, 59-20
7290, which uses a water-soluble polymer capable of forming a metal chelate as the main ingredient,
665, 39-22263, 40-763, 43
-28404, 47-29642, JP-A-52-12
6302, 52-134501, 53-49506
, No. 53-59502, No. 53-104302, etc., JP-A No. 53-104301, No. 55-15313 using a metal complex compound as the main ingredient.
, No. 54-41924, etc., or Japanese Patent Publications No. 39-13702, No. 40-10308, No. 46-26 using inorganic and organic acid compounds as main ingredients.
124, JP-A-51-118501, JP-A No. 56-1116
Examples include those described in each No. 95 publication.

[0272] The method for desensitizing the resin particles, ie, the method for decomposing the protected hydroxyl groups, is arbitrarily selected depending on the decomposition reactivity of the protected hydroxyl groups. One such method is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 or alkaline conditions of pH 8 to 12. These pH values can be easily adjusted using known compounds. Alternatively, a method using a redox reaction using a reducing or oxidizing water-soluble compound is possible, and known compounds can be used as these compounds, such as anhydrous hydrazine, sulfite, lipoic acid,
Examples include hydroquinones, formic acid, thiosulfates, hydrogen peroxide, persulfates, quinones, and the like.

[0273] The processing solution may contain other compounds in order to promote the reaction or improve the storage stability of the processing solution. For example, add 1 part by weight of a water-soluble organic solvent to 100 parts by weight of water.
It may contain up to 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol,
ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate,
ethyl formate, etc.), and these may be used alone or in combination of two or more.

[0274] In addition, 0 parts of surfactant was added to 100 parts by weight of water.
．． It may be contained in an amount of 1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants. For example, Hiroshi Horiguchi, “New Surfactants,” Sankyo Publishing Co., Ltd. (published in 1975), Ryohei Oda, Kazuhiro Teramura, “Synthesis of Surfactants and Their Applications,” Maki Shoten (
(1980), etc. can be used.

[0275] The scope of the present invention is not limited to the above-mentioned specific compound examples. The processing conditions are a temperature of 15°C.
The immersion time is preferably 10 seconds to 5 minutes at ~60°C. Furthermore, as a method for decomposing a specific functional group by light irradiation, a step of irradiating it with "chemically active light" may be included sometime after the toner image is obtained during plate making. That is, after electrophotographic development, light irradiation may be performed during fixing of the toner image, or after fixing by other conventionally known fixing methods, such as heat fixing, pressure fixing, solvent fixing, etc., light irradiation may be performed. It performs irradiation.

[0276] Examples of the "chemically active light" used in the present invention include visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays,
Any radiation such as γ rays or α rays may be used, but ultraviolet rays are preferred. More preferably wavelength 310 nm to wavelength 5
It is preferable to use one that can emit light in the 00 nm range, and generally a high-pressure or ultra-high pressure mercury lamp or the like is used. Light irradiation treatment is usually performed from a distance of 5cm to 50cm.
Irradiation for seconds to 10 minutes is sufficient.

0277]

[Examples] Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. Binder resin [
A] Synthesis Example 1: [A-1] Benzyl methacrylate 9
After heating a mixed solution of 5 g of acrylic acid, 5 g of acrylic acid, and 200 g of toluene to a temperature of 90°C under a nitrogen stream, 2,2'-azobisisobutyronitrile (abbreviated as A.I.B.N.) 6
．． 0g was added and reacted for 4 hours. Furthermore, A. I. B. N.
2 g was added and reacted for 2 hours. The obtained copolymer [
A-1] had a weight average molecular weight of 8,500. Synthesis example 2/28 of binder resin [A]: [A-2] to [A-28]
Resins [A-2] to [A-28] in Table 2 below were synthesized under the same polymerization conditions as in Synthesis Example 1 for Resin [A].

[0278]

[Table 2]

0279]

[Table 3]

0280]

[Table 4]

0281]

[Table 5]

0282]

[Table 6]

0283

[Table 7]

0284

[Table 8]

Synthesis Example 29 of Binder Resin [A]: [A-29
] After heating a mixed solution of 95 g of 2,6-dichlorophenyl methacrylate, 5 g of acrylic acid, 2 g of n-dodecyl mercaptan, and 200 g of toluene to a temperature of 80° C. under a nitrogen stream, A. I. B. N. 2g was added and reacted for 4 hours, then A. I. B. N. Add 0.5g and continue for 2 hours. I. B. N. 0.5 g was added and reacted for 3 hours. After cooling, reprecipitate into 2 liters of a mixed solution of methanol/water (9/1), collect the precipitate by decantation,
Dry under reduced pressure. The yield of the waxy copolymer obtained was 78 g, and the weight average molecular weight was 6.3 x 103.

Next, specific examples of manufacturing the dispersion stabilizing resin and resin particles will be described. Production example 1 of resin for dispersion stabilization: [P
-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate, and 200 g of toluene was heated to a temperature of 75° C. while stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation A.I.B.N.) 1
．． 0g was added and stirred for 4 hours, and further A. I. B. N. 0.
5 g was added and stirred for 4 hours. Next, 5 g of methacrylic acid and 1 g of N,N-dimethyldodecylamine were added to the reaction mixture.
．． 0g of t-butylhydroquinone and 0.5g of t-butylhydroquinone were added thereto, and the mixture was stirred at a temperature of 110°C for 8 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, a slightly brownish oil was collected, and then dried. Yield: 73g, weight average molecular weight: 3.6 x 10
It was 4.

0287]

[C77]

[0288] Production example 2 of resin for dispersion stabilization: [P-2] 2
-100 g of ethylhexyl methacrylate, 1 part of toluene
A mixed solution of 50 g and isopropanol was heated to 75° C. with stirring under a nitrogen stream. 2,2'-
2g of azobis(4-cyanovaleric acid) (abbreviated as A.C.V.) was added and reacted for 4 hours, and further A.C.V. C. V. 0.8 g was added and reacted for 4 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, and the oil was collected and dried.

[0289] 50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate, and 150 g of tetrahydrofuran.
A mixed solution of 8 g of dicyclohexylcarbondiimide (D.C.C.), 0.2 g of 4-(N,N-dimethylamino)pyridine, and 20 g of methylene chloride was added dropwise to the mixture at a temperature of 25 to 30°C. 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 1 liter of methanol to collect the oily matter. Furthermore,
This oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 1 liter of methanol, and the oily substance was collected and dried. Yield: 32g, weight average molecular weight: 4
．． It was 2×104.

0290]

[C78]

Production Example 3 of Dispersion Stabilizing Resin: [P-3] A mixed solution of 96 g of butyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. A. I. B. N. 1.0
g was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100° C. for 12 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol to obtain 82 g of an oily substance. The weight average molecular weight was 8 x 103.

0292

[C79]

Production Example 4 of Dispersion Stabilizing Resin: A mixed solution of 100 g of P-4n-butyl methacrylate, 4 g of β-mercaptopropionic acid and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. To this A. I.
B. N. 1 g was added and reacted for 6 hours. After cooling the reaction mixture and setting the temperature to 25°C, 10 g of 2-hydroxyethyl methacrylate, 8 g of dicarboxycarbondiimide (D.C.C.), and 0.2 g of 4-(N,N-dimethylamino)pyridine were added. A mixed solution of 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 out the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol, and the oily matter was collected by filtration. Furthermore,
This oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 2 liters of methanol, and the oily substance was collected and dried. Yield: 68g, weight average molecular weight: 6
．． It was 6×103.

0294

[C80]

[0295] Production examples 5 to 12 of resin for dispersion stabilization: P-5
~P-12 In Production Example 4, 100 g of n-butyl methacrylate
Each resin was produced in the same manner as in Production Example 4, except that the monomer groups corresponding to Table 3 below were used instead. The weight average molecular weight of each resin was in the range of 5.5 x 103 to 7 x 103.

0296

[Table 9]

[0297] Production examples 13 to 16 of dispersion stabilizing resin: P-
13 to P-16 Each resin was produced in the same manner as in Production Example 4, except that compounds corresponding to Table 4 were used instead of 2-hydroxymethacrylate. The weight average molecular weight of each resin was in the range of 6 x 103 to 7 x 103.

0298

[Table 10]

Production Example 17 of Dispersion Stabilizing Resin: A mixed solution of 80 g of P-17 hexyl methacrylate, 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was heated to 60° C. with stirring under a nitrogen stream. To this, 2,2'-azobis(isovaleronitrile) (abbreviation: A.I.V.N.) 0
．． 8g was added and reacted for 4 hours, and then A. I. V. N 0
．． 4 g was added and reacted for 4 hours. During this reaction, the temperature was 25
After cooling to ℃, 4 g of methacrylic acid was added and D.C. was added under stirring.
C. C. A mixed solution of 6 g, 0.1 g of 4-(N,N-dimethylamino)pyridine, and 15 g of methylene chloride was added dropwise over 1 hour, and the mixture was stirred for an additional 3 hours. Next, water 10
After stirring for 1 hour and filtering off the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol to collect the oily matter. Furthermore, this oily substance was dissolved in 150 g of benzene, and after filtering off the insoluble matter, it was reprecipitated again into 1 liter of methanol, and the oily substance was collected and dried. Yield: 56g, weight average molecular weight: 8x10
It was 3.

0300]

[Chemical formula 81]

[0301] Production examples 18 to 22 of dispersion stabilizing resin: P-
18 to P-22 By performing the reaction shown in Production Example 17, the following Table-5
Each of these dispersion stabilizing resins was synthesized. The weight average molecular weight of each resin was in the range of 6 x 103 to 9 x 103.

0302]

[Table 11]

0303]

[Table 12]

Production Example 1 of Resin Particles: [L-1] A mixed solution of 10 g of dispersion stabilizing resin [P-17] and 200 g of n-octane was heated to 60° C. with stirring under a nitrogen stream. To this, 47 g of the following monomer [C-1], 3 g of the following monomer [D-1], 5 g of ethylene glycol dimethacrylate, A. I. V. N. 0.5g and n-octane 24
0 g of the mixed solution was added dropwise over 2 hours, and the reaction was continued for 2 hours. Furthermore, A. I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. The latex had an average particle size of 0.18 μm. {: Particle size measurement using CAPA-500 [Horiba, Ltd.]}

0305]

[C82]

[0306] Production examples 2 to 11 of resin particles: [L-2] to
[L-11] In Production Example 1 of resin particles, monomers [C-1] and [
Resin particles were produced in the same manner as in Production Example 1, except that the present monomer shown in Table 6 below was used instead of [D-1]. The average particle size of each particle was within the range of 0.65 to 0.30.

0307]

[Table 13]

0308

[Table 14]

0309]

[Table 15]

Production Example 12 of Resin Particles: [L-12] Dispersion Stabilizing Resin AA-6 [manufactured by Toagosei Co., Ltd. Macromonomer: Macromonomer having methyl methacrylate as a repeating unit: Weight average molecular weight 1.5×104 ] A mixed solution of 7.5 g and 133 g of methyl ethyl ketone was heated to 60° C. with stirring under a nitrogen stream. To this, the following monomer [
C-12] 20 g, the following monomer [D-11] 5 g, diethylene glycol dimethacrylate 5 g, A. I. V. N
．． A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour. I. V. N. 0.25g was added and reacted for 2 hours. After cooling, the average particle size of the obtained dispersion was 0.25 μm through a 200 mesh nylon cloth.
Met.

0311]

[Chemical formula 83]

Production Example 13 of Resin Particles: [L-13] A mixed solution of 7.5 g of dispersion stabilizing resin P-20 and 230 g of methyl ethyl ketone was heated for 60 hours while stirring under a nitrogen stream.
Warmed to ℃. To this, 22 g of monomer [C-12], 3 g of monomer [D-7], 15 g of acrylamide, A. I. V
．． N. A mixed solution of 0.5 g and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. Furthermore, A. I. V. N. After adding 0.25 g and reacting for 2 hours, the resulting dispersion was cooled and passed through a 200 mesh nylon cloth, and the average particle size of the obtained dispersion was 0.20 μm. Production example 14 of resin particles: [L-14] 46 g of monomer [C-12], 4 g of monomer [D-7], 2 g of ethylene glycol diacrylate, 8 g of dispersion stabilizing resin P-19, and dipropyl ketone 200g of dipropyl ketone heated to 60℃ under a nitrogen stream
was added dropwise to the solution over 2 hours while stirring. As is 1
After the time reaction, A. I. V. N. 0.3 g was added and reacted for 2 hours. After cooling, the resulting dispersion was passed through a 200 mesh nylon cloth, and the average particle size of the resulting dispersion was 0.25 μm. Production examples 15 to 25 of resin particles: [L-15] to [L-25
] In Production Example 14 of Resin Particles, resin particles [L
-15] to [L-25] were produced. The polymerization rate of each particle was 95 to 98%, and the average particle size was 0.15 to 0.25 μm.

0313]

[Table 16]

[0314] Production examples 26 to 31 of resin particles: [L-26
] ~ [L-31] In Production Example 12 of resin particles, dispersion stabilizing resin AA-
Particles were produced in the same manner as in Production Example 12, except that each dispersion stabilizing resin shown in Table 8 below was used instead of Sample 6. The average particle size of each particle was in the range of 0.20 to 0.25.

0315]

[Table 17]

[0316] Production examples 32 to 35 of resin particles: [L-32
] ~ [L-35] Production Example 1 except that in Production Example 13 of resin particles, each compound in Table 9 below was used instead of the monomer [C-12] acrylamide and the reaction solvent: methyl ethyl ketone.
Each particle was manufactured in the same manner as in Example 3. The average particle size of each particle was in the range of 0.15 to 0.30.

0317]

[Table 18]

Example 1 and Comparative Examples A to B Example 1 6 g (as solid content) of resin [A-8], 33 g (as solid content) of resin [B-1] having the following structure, 200 g of photoconductive zinc oxide Methine dye [I] with the following structure 0.018g
, 0.15 g of salicylic acid, and 300 g of toluene in a 7×1 homogenizer (manufactured by Nippon Seiki Co., Ltd.).
03 r. p. m. Dispersion was carried out for 10 minutes at a rotation speed of . Dispersed resin particles [L-1] 1.0g (as solid content)
, add 0.01 g of phthalic anhydride, and rotate at 1×103
r. p. m. Dispersion was performed for 1 minute. This dispersion for forming a photosensitive layer was applied to conductively treated paper using a wire bar so that the dry adhesion amount was 25 g/m2, dried at 100°C for 30 seconds, and further heated at 120°C for 1 hour. Then, an electrophotographic light-sensitive material was prepared by leaving it in a dark place for 24 hours at 20° C. and 65% RH.

0319]

[Chemical formula 84]

0320]

[Chemical formula 85]

Comparative Example A In Example 1, 6 g of resin [A-4] and resin [B-
1] An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 39 g of resin [B-1] was used instead of 33 g. Comparative Example B Comparative dispersed resin particles: [LR-1] Resin particle production example 1: [L-1], monomer [C
-1] instead of 47g and [D-1] 3g [C-1]
Synthesis was carried out in the same manner as in Production Example 1, except that the amount was changed to 50 g. The average particle size of the obtained latex was 0.17 μm.

0322]

[C86]

Comparative photoreceptor Example 1 was prepared in the same manner as in Example 1, except that 1 g of resin particles [LR-1] (as solid content) was used instead of 1 g of resin particles [L-1]. An electrophotographic light-sensitive material was produced.

Film properties (surface smoothness), electrostatic properties, desensitization properties of the photoconductive layer (represented by contact angle with water of the photoconductive layer after desensitization treatment), and printing of these photosensitive materials I looked into gender. Printability was determined using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using developer ELP-T to form an image through exposure and development, followed by desensitization. It was investigated using a printing board. (The printing machine used was Hamadastar 800SX manufactured by Hamadastar Co., Ltd.)
The above results are summarized in Table-10.

0325]

[Table 19]

[0326] The implementation of the evaluation items listed in Table 10 is 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 - Model SP-428, manufactured by Kawaguchi Electric Co., Ltd.). After allowing it to stand for 10 seconds, the surface potential V10 at this time was measured. Next, the potential V120 was measured after being allowed to stand still in the dark for 120 seconds, and the retention of the potential after dark decay for 120 seconds, that is, the dark decay retention rate [DR
R (%)] [(V120 /V10) x 100 (%)
].

[0327] Furthermore, the surface of the photoconductive layer is -
After charging to 500V, irradiate it with monochromatic light with a wavelength of 780nm, calculate the time until the surface potential V10 attenuates to 1/10, and calculate the exposure amount E1/10 (erg/cm2).
) is calculated. The environmental conditions during imaging were I (20°C, 65%
RH) and II (30°C, 80% RH). Note 3) Imaging properties: Each photosensitive material was left for one day and night under the following environmental conditions. Next -
A gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780
45erg/cm on the surface of the photosensitive material using
2. After exposure at a pitch of 25 μm and a scanning speed of 330 m/sec under an irradiation dose of Images (fogging, image quality) were visually evaluated. Note 4) Raw plate water retention: Each photosensitive material itself (original plate without plate making: i.e., abbreviated as raw plate) is treated with desensitizing treatment liquid ELP manufactured by Fuji Photo Film Co., Ltd.
Using an aqueous solution prepared by diluting -EX twice with distilled water, the sample was passed through an etching machine once, and then immersed in a desensitizing solution E-1 having the following formulation for 3 minutes. Next, these plates were printed using Hamadastar Model 8005X manufactured by Hamadastar Co., Ltd., and the presence or absence of background smear on the 50th printed matter after printing was visually evaluated. Desensitization treatment liquid: E-1 Monoethanolamine
60g
Neosoap (manufactured by Matsumoto Yushi Co., Ltd.)
8g
benzyl alcohol
Dilute 100g with distilled water to make a total volume of 1.0 liters, and then dilute with potassium hydroxide.
Adjusted to H10.5. Note 5) Background stains on printed matter: After making each photosensitive material in the same manner as in Note 3) above,
After passing through an etching machine once using LP-EX, these offset master original plates were printed using a solution prepared by diluting E-1 5 times with water as a dampening solution, and the background of the printed material was The number of prints until stains could be visually identified was determined.

[0328] The electrostatic properties of the present invention and Comparative Example B were good, and in terms of actual imaging performance, the copied images were all clear in quality. However, in Comparative Example A, the photosensitivity was lowered, and the imaging performance was affected by loss of thin lines, characters, and thin line portions with low density, and blurring.

[0329] When each of these photoreceptors was desensitized and the degree of hydrophilization of the non-image area (green plate water retention) was evaluated, Comparative Example B showed significant scumming due to printing ink adhesion.
The non-image area was not made sufficiently hydrophilic.

[0330] Furthermore, when the lithographic plate of the present invention was actually printed after being subjected to a desensitization treatment after plate making, 10,000 prints with clear images and print quality were obtained without any occurrence of scumming. On the other hand, Comparative Example A using resin particles but not using resin [A]
Due to poor reproducibility of the photographic image, the printed matter was inferior to the printed material. Although known resins and resin particles are used,
In Comparative Example B, in which the amount of resin particles used was reduced to the same amount as in the photoreceptor of the present invention, scumming occurred after about 3,000 sheets were printed.

As described above, the electrophotographic lithographic printing original plate in which the hydrophilicity of the non-image area has sufficiently progressed and does not cause background fog, is
It was only the one of the present invention. Example 2 In Example 1, 6 g of resin [A-8], 6 g of resin [B-1]
] 33 g, and instead of 1.0 g of resin particles [L-1], 4 g of resin [A-17], and resin [B-2] 3 having the following structure.
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 5.0 g of resin particles [L-26] and 0.8 g of resin particles [L-26] were used.

0332]

[Chemical formula 87]

[0333] Each characteristic was measured in the same manner as in Example 1. The following are particularly harsh environmental conditions (30°C, 80% RH).
) shows the measurement results below.

[0334] Electrostatic characteristics V10:
-660VD. R. R: 82% E1/10: 27erg/cm2 E
1/100: 48erg/cm2 Imaging performance: Very good (◎) Raw plate water retention:
〃 (◎) Background stains on printed matter: No background stains up to 10,000 sheets However, in the desensitization treatment, desensitization treatment liquid E-2 with the following formulation was used in place of E-1 used in Example 1. .

[0335] Desensitizing treatment liquid: E-2 diethanolamine
80g
Nucor B4SN (manufactured by Japan Toray Kayaku Co., Ltd.) 8g Methyl ethyl ketone
Dissolve 100g in distilled water and bring the total amount to 1.
The volume was brought to 0 liters and the pH was adjusted to 10.0 with potassium hydroxide.

Each of the photosensitive materials of the present invention has chargeability,
It has excellent dark charge retention and photosensitivity, and even in harsh conditions of high temperature and high humidity (30° C., 80% RH), clear images with no background fog were obtained in actual copied images and printed matter. Examples 3 to 14 Resin particles “L” and resin [A] used in Example 1
, instead of resin [B], 0.9 g (as solid content) of the resin particles [L] of the present invention shown in Table 11 below and resin [A]
5g and 34g of resin [B-3] having the following structure were used.
Each photosensitive material was produced in the same manner as in Example 1.

[0337] The electrostatic properties and printing properties were evaluated in the same manner as in Example 2.

0338]

[Chemical formula 88]

0339]

[Table 20]

[0340] When the electrostatic properties and printing properties of each photosensitive material were measured in the same manner as in Example 2, all of them had excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images were also stable at high temperatures. Even under harsh humid conditions (30°C, 80% RH), clear images were produced without background fog or skipped fine lines.

[0341] Furthermore, when the performance of the offset lithographic plate precursors was evaluated after being desensitized, the water retention properties of the raw plates were good, and 10,000 sheets could be printed even after actual plate making. Example 15
and Comparative Examples C to D Resin of Example 15 [A-1] 6.0 g
, 34g of resin [B-4] with the following structure, 200g of zinc oxide
, uranine 0.02g, rose bengal 0.04g, bromophenol blue 0.03g, phthalic anhydride 0.2
A mixture of 5 g and 300 g of toluene was heated to 1×10 4 r.m. in a homogenizer. p. m. Dispersion was carried out for 5 minutes at a rotation speed of . 1.0 g (as solid content) of resin particles [L-24] was added to this, and the rotation speed was further increased to 1 x 103 r. p. m. Dispersion was performed for 1 minute. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/m2.
Dry at 100℃ for 3 minutes, then dry at 20℃ in the dark at 65%
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under RH conditions.

0342]

[Chemical formula 89]

Comparative Example C An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 1.0 g of resin particles [L-24] in Example 15 was not added. Comparative Example D In Example 15, 6 g of resin [A-1] and resin [B-
4] Instead of 34g, resin [R-2] 39 with the following structure
An electrophotographic light-sensitive material was produced in the same manner as in Example 15 except that g was used.

0344

[C90]

[0345] The film properties (surface smoothness), film strength, electrostatic properties, imaging properties, and environmental conditions of these photosensitive materials were measured at 30°C,
The electrostatic characteristics of the image pickup body at 80% RH were investigated. Furthermore,
When these photosensitive materials are used as original plates for offset masters, the photoconductive desensitization (water retention) and printability (
Background stains, printing durability, etc.) were investigated.

[0346] The above results are summarized in Table 12.

0347]

[Table 21]

[0348] Among the implementation modes of the evaluation items listed in Table 12, the following items were operated according to the following contents. 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 - Model SP-428, manufactured by Kawaguchi Electric Co., Ltd.). After this, the sample was left for 10 seconds, and the surface potential at this time was measured as V10. Then, the potential V70 was measured after being allowed to stand still in the dark for 60 seconds, and the retention of the potential after dark decay for 60 seconds, that is, the dark decay retention rate [D. R. R(
%)] was calculated as [(V70/V70)×100(%)]. In addition, after the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was then irradiated with visible light at an illuminance of 2.0 lux, and the time required for the surface potential V10 to attenuate to 1/10 was measured. From this, the exposure amount E1/10 (lux/second) is calculated. Similarly, find the time until V10 attenuates to 1/100, and then calculate the exposure amount E1/10.
0 (lux・sec) is calculated. Note 7) Imaging performance: Each photosensitive material and a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) were used for one day and night at room temperature and humidity (20℃, 6
5%), plate making is performed to form a copy image, and the image (fogging, image quality) of the obtained copy original plate is visually observed (this is referred to as I). Image quality II 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%).

The photoreceptors of Example 15 of the present invention and Comparative Example C had good electrostatic properties and good imaging properties. On the other hand, in Comparative Example D, the electrostatic properties deteriorated and were significantly affected especially when the environmental conditions changed, and even in actual copied images, background fog and breakage of characters and thin lines occurred.

On the other hand, among the desensitized original plates, only the one of the present invention had sufficient hydrophilicity in the non-image area and could print up to 10,000 sheets without any adhesion of printing ink or the like. In Comparative Example C, the hydrophilization was insufficient, and in Comparative Example D, the copied image was actually deteriorated in the original plate after plate making, and due to this influence, only unsatisfactory printed matter was obtained from the beginning of printing. There wasn't. Examples 16-29 In Example 15, 5 g (as solid content) of each resin [A] and 0.9 g (solid amount) of resin particles [L] in Table 13 below were used instead of resin [A] and resin particles [L]. (as quantity)
Also, as resin [B], resin [B-5] with the following structure
An electrophotographic light-sensitive material was produced in the same manner as in Example 15 except that 33.5 g was used.

0351]

[Chemical formula 91]

0352]

[Table 22]

[0353] Each photosensitive material is exposed to high temperature and high humidity (30°C,
Even under conditions of 80% RH), excellent electrostatic properties were obtained in the present invention.

[0354] 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 10,000 prints with clear image quality and no background smudge were obtained.

0355]

Effects of the Invention According to the present invention, an electrophotographic photoreceptor can be obtained which has excellent electrostatic properties and mechanical properties even under severe conditions. It is possible to print a large number of prints with extremely clear image quality.

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

Claims (4)

[Claims] 1. An original plate for electrophotographic lithography, comprising at least one photoconductive layer containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin on a conductive support. The photoconductive layer contains at least one of the following resins [A] as the binder resin, and the photoconductive layer further contains at least one of the following resins [A] with a maximum particle diameter of the photoconductive zinc oxide particles or larger. An original plate for electrophotographic lithographic printing, characterized in that it contains at least one type of non-aqueous solvent-based dispersed resin particles having a small particle size as described below. Resin [A]: 1 x 103
It has a weight average molecular weight of ~2 x 104 and has a repeating unit represented by the following general formula (I) as a polymer component.
weight% or more, -PO3 H 2 , -SO3 H
, -COOH, -P(=O)(OH)R01 [R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group]] and a cyclic acid anhydride-containing group. 0.5 to 0.5 as a polymer component having a polar group
15% by weight. [Formula (I) above, a 1 , a 2
each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R03 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles: A functional group that is soluble in a non-aqueous solvent but becomes insolubilized by polymerization, and that produces at least one hydroxyl group upon decomposition. A monofunctional monomer (C) containing at least one group, and a monofunctional monomer (C) containing a substituent containing a silicon atom and/or a fluorine atom and copolymerizable with the monofunctional monomer (C). Functional monomer (
Copolymer resin particles obtained by subjecting D) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. 2. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). The electrophotographic lithographic printing original plate according to claim 1, characterized in that it contains at least one of the following. [Formula (Ia) and (Ib) above, T1
and T2 are each independently a hydrogen atom and a carbon number of 1 to 1
0 hydrocarbon group, chlorine atom, -COR04 or -C
OOR05 (R04 and R05 each represent a hydrocarbon group having 1 to 10 carbon atoms), and L1 and L2 each represent -
Represents a single bond or a linking group with 1 to 4 linking atoms that connects COO- and a benzene ring] 3. The electrophotographic lithographic printing original plate according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order mesh structure. 4. Claim 1, wherein the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. The original plate for electrophotographic planographic printing according to any one of items 1 to 3. [In general formula (II), V0 is -O-, -COO
-, -OCO-, -(CH2) p OCO-, -(
CH2 ) p COO-, -SO2 -, -CONR
1 -, -SO2 NR1 -, -C6 H4 -, -
CONHCOO- or -CONHCONH- (where p represents an integer of 1 to 4, R1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b1,
b2 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R
2 or -COO-R2 (R2
represents a hydrogen atom or a hydrocarbon group that may be substituted]