JPH04314056A - Original plate for electrophotographic lithographic printing - Google Patents

Abstract

PURPOSE:To obtain the original plate which has excellent electrostatic characteristics, reproduces the copied images faithful to an original picture, does not generate the scumming uniform over the entire surface and dotty scumming as an offset original plate and has an excellent desensitizing property by incorporating a specific resin and nonaq. solvent type dispersion resin particles into a photoconductive layer. CONSTITUTION:This original plate contains the resin of 1X10<3> to 2X10<4>weight average mol.wt. which contains >=30wt.% specific repeating unit expressed by formula I and is constituted by bonding a polar group, such as -PO3H2, to one terminal of the main chain of the polymer. The plate contains the nonaq. solvent type dispersion resin particles obtd. by bringing a monomer contg. a functional group forming at least one group among a thiol group, sulfo group, amino group, etc., into polymn. reaction in the presence of a resin for stabilizing dispersion having a subtd. group contg. a silicon atom and/or fluorine atom. In the formula I, a1, a2 denote a hydrogen atom, halogen atom, cyano group or hydrocarbon group; R03 denotes a hydrocarbon group. A water-retaining property is improved in this way and excellent printed images and high printing resistance are obtd. even under severe conditions.

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 original plate having layers, the following resin [A] is used as the binder resin in the photoconductive layer.
), and further contains in the photoconductive layer at least one of the following non-aqueous solvent-based dispersed resin particles having a particle diameter that is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles. This is achieved by an electrophotographic lithographic printing original plate characterized by the following.

[0016] The resin [A] is 1×103 to 2×1
It has a weight average molecular weight of 04, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and has -PO3 H2, - at the end of the polymer main chain.
SO3 H, -COOH, -P(=O)(OH)R01
[R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group]] [the above -P(=O)(OH)R0
1 is

[0017]

[C4]

[0018] is shown. ] and a cyclic acid anhydride-containing group;

[0019]

[C5]

[However, in the above formula (I), a1,
a2 each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R03 represents a hydrocarbon group] The non-aqueous solvent-based dispersed resin particles are soluble in the non-aqueous solvent, but become insolubilized by polymerization. group and -P
(=Z0)(-Z0-H)R'1 group [Z0 represents an oxygen atom or a sulfur atom. R' 1 is -Z0
-H, hydrocarbon or -Z0 -R' 2 (R' 2
represents a hydrocarbon group) is substituted with a monofunctional monomer (C) containing at least one functional group that forms at least one group of It is characterized by copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the solvent, which comprises at least a repeating unit containing a group.

Furthermore, the resin [A] preferably has the general formula (
As the copolymer component represented by I), the following general formula (Ia)
and at least one of the aryl group-containing methacrylate components represented by the following general formula (Ib) (
(hereinafter referred to as resin [A']) is preferred.

[0022]

[C6]

[However, in the above formulas (Ia) and (Ib), T1 and T2 each independently represent a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, -COR04
or -COOR05 (R04 and R05 each have 1 carbon number
~10 hydrocarbon groups), L1 and L2
each represents a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and a benzene ring] In addition, in the present invention, the non-aqueous solvent-based dispersed resin particles have a higher-order network structure. It may be formed.

Furthermore, the dispersion stabilizing resin in the present invention contains at least one polymerizable double bond group represented by the following general formula (II) in the polymer chain. These are particularly preferred.

[0025]

[C7]

[In general formula (II), V0 is -O
-, -COO-, -OCO-, -(CH2)p -O
CO-,-(CH2)p-COO-,SO2-,
-CONR1 -, -SO2 R1, -C6 H4
-(-C6 H4 - is 1,2-, 1,3-, 1,4-
Represents a phenylene group. (same below), -CONHCOO-, or -CONHCO
represents NH-, (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 and b2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R2 or a carbide group. -COO- via hydrogen group
R2 (R2 represents a hydrogen atom or an optionally substituted hydrocarbon group)].

In the lithographic printing original plate of the present invention, the uppermost photoconductive layer contains at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin. This is a printing original plate that is treated with a chemical solution to make the surface hydrophilic and used as a lithographic printing original plate.

As mentioned above, the technique of containing hydrophilic resin particles in the photoconductive layer and the binder resin of the electrophotographic photoreceptor,
Techniques for using resins containing acidic groups in their side chains are known, but as in the present invention, functional groups that generate specific hydrophilic groups upon decomposition are used as the resin particles and binder resin to be included in the photoconductive layer. Non-aqueous solvent-based dispersed resin particles obtained by polymerizing the contained components in the presence of a dispersion stabilizing resin containing a substituent containing a silicon atom and/or a fluorine atom, and a polar group in the main chain of the polymer. Surprisingly, by using the low molecular weight resin [A] contained at one end, the above-mentioned problems that were unresolved by these known techniques alone can be solved, that is, water retention and printing durability can be improved. It was found that there was a dramatic improvement.

The photoconductive layer of the present invention comprises at least a photoconductive zinc oxide, a spectral sensitizing dye, and a specific copolymer component, and is a low-resistance polymer formed by bonding a specific polar group to one end of a polymer main chain. Molecular weight resin [A] and non-aqueous solvent-based dispersed resin particles containing specific hydrophilic groups by decomposition (hereinafter referred to as resin particles [L])
(sometimes abbreviated as ).

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, redox reaction,
The protected hydrophilic groups undergo chemical reactions such as photolysis reactions, resulting in formation of thiol groups, sulfo groups, amino groups, -P(=
Z0 )(-Z0 -H)R'1 group, converting from hydrophobic to hydrophilic, and fluorine atom and/or
Alternatively, by performing dispersion polymerization in the presence of a dispersion stabilizing resin containing at least a repeating unit containing a substituent containing at least one silicon atom, these polymers as a dispersion stabilizing resin containing a fluorine atom and/or a silicon atom can be prepared. A resin for dispersion stabilization that is formed by physicochemically adsorbing an insoluble component containing a functional group that generates a hydrophilic group upon decomposition, or that contains a polymerizable double bond group moiety represented by the formula (II) above. In this case, it is considered that both polymer components are chemically bonded, and this is thought to cause a migration/concentration phenomenon on the surface portion of the photoconductive layer.

[0031] 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 in at least one part of the polymer main chain. It is characterized by being a low molecular weight polymer with terminal bonds.

The photoconductive layer of the present invention includes photoconductive zinc oxide particles, a spectral sensitizing dye, and the resin particles [L] dispersed by the resin [A] containing at least the binder resin, Furthermore, after forming the photoconductive layer, the resin particles [L]
It quickly migrates to the surface portion of the surface layer and is concentrated near 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] formed by bonding a specific polar group to a specific position is adsorbed to the stoichiometric defects of the photoconductive zinc oxide, and the coating is applied to a state where the zinc oxide and the dye interact. Appropriate properties and adsorption conditions compensate for trapping of photoconductive zinc oxide and dramatically improve temperature characteristics, while sufficient dispersion of photoconductive zinc oxide suppresses agglomeration. This is thought to be due to

In particular, with conventional binder resins, when the type of spectral sensitizing dye changes, interactions such as adsorption are inhibited.
Satisfactory electrophotographic characteristics could no longer be obtained. However, when the resin [A] of the present invention is used, even dyes used for spectral sensitization for semiconductor laser light can satisfy extremely excellent electrophotographic properties.

[0035] As an original plate for an electrophotographic lithographic printing system, another important thing is that the non-image areas are made sufficiently hydrophilic by desensitization treatment and have a high water retention property that does not cause ink adhesion during printing. It is. In the lithographic printing original plate of the present invention, the resin particles [L] concentrated on the surface portion of the photoconductive layer generate the above-mentioned specific hydrophilic groups by desensitization treatment, thereby expressing hydrophilicity. The non-image area is sufficiently modified to be hydrophilic and exhibits sufficient water retention without causing scumming. Furthermore, the hydrophilization of the non-image areas in the present invention can also be carried out by desensitizing zinc oxide particles uniformly dispersed in the resin [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 desensitization treatment after forming the copy image. I was able to do that.

On the other hand, in the resin particles of the present invention, if the resin particles have a particle size larger than the zinc oxide particle size, the electrophotographic properties 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 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.

[0039] 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.

Further, in the present invention, the resin particles are made of a hydrophobic polymer component, that is, a dispersion stabilizing resin is bonded with 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.

Furthermore, when a heat and/or photocurable group is contained as one of the polymer components as the dispersion stabilizing resin, elution can be further suppressed by further chemically bonding with the binder resin. can do.

Furthermore, in the present invention, resin particles forming a higher-order mesh structure can further suppress dissolution in water, exhibit water swelling properties, and further improve water retention. In the present invention, the resin particles that do not form a 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.

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, making them insensitive. Since it exhibits hydrophilicity through the fat treatment, it can be added in a very small amount to produce the same effect (water retention) as the effect of known techniques.

Next, the photoconductive layer of the electrophotographic material of the present invention will be explained. The photoconductive layer of the present invention is characterized in that it contains at least one of the above resins [A] as a binder resin.

Resin [A] has a weight average molecular weight of 1
×103 to 2×104, preferably 3×103 to
The glass transition point of the resin [A] is preferably -30°C to 110°C, more preferably -20°C to
The temperature is 90°C.

If the molecular weight of the resin [A] is less than 103, the film-forming ability decreases 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 the 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.

[0048] 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.

[0049] 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 has 1 or more carbon atoms
18 optionally substituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc.), optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group,
allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7-12
optionally substituted aralkyl group (benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.) having 5 to 8 carbon atoms; optionally substituted cycloalkyl groups (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, (ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.).

More preferably, in the copolymer component corresponding to the repeating unit of the general formula (I), the 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, and 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 or more
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 -COR04
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), L1
and L2 are each a direct bond connecting -COO- and a benzene ring, or -(CH2)n1- (n1 represents an integer of 1 to 3), -CH2 OCO-, -CH2 CH2 O
A linking group having 1 to 4 linking atoms such as CO-, -(CH2O)m1- (m1 represents an integer of 1 or 2), -CH2CH2O-, and more preferably a direct bond or bond. A linking group having 1 to 2 atoms can be mentioned.

Formula (Ia) used in the resin [A] of the present invention
) or (Ib) are listed below. However, the scope of the present invention is not limited thereto. (a-1) below
In (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, and R10 to R13 are all -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 hydrogen atom, -Cl,
Represents either -Br or -I.

[0057]

[Chemical formula 8]

[0058]

[Chemical formula 9]

[0059]

[Chemical formula 10]

[0060]

[Chemical formula 11]

[0061]

[Chemical formula 12]

[0062]

[Chemical formula 13]

[0063]

[Chemical formula 14]

[0064]

[Chemical formula 15]

[0065]

[Chemical formula 16]

[0066]

[Chemical formula 17]

Next, the polar group bonded to one end of the polymer main chain of the low molecular weight resin [A] will be explained. The polar group is -PO3 H2, -SO3 H, -COOH, -P
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.

[0072] These polar groups may be bonded directly to the terminal end of the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but specific examples include -[C(d1)(d2
)] - (d1 and d2 may be the same or different, and each represents a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.),
OH group, cyano group, alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl (representing a group, etc.),
-(CH(d3)-CH(d4))]-(d3, d
4 represents the same content as d1 and d2), -C6 H
10-, -C6 H5-, -O-, -S-, -N(d
5)-[d5 represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group) , octyl group, decyl group, dodecyl group, 2
-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorofer group, methoxyphenyl group, butylphenyl group)],
-CO-, -COO-, -OCO-, -(d5)CO
N-, -SO2 N(d5)-, -SO2 -, -N
HCONH-, -NHCOO-, -NHSO2 -, -
CONHCOO-, -CONHCONH-, heterocycle (any 5- to 6-membered ring containing at least one type of O, S, N, etc. as a hetero atom, or a condensed ring thereof; for example, a thiophene ring, a pyridine ring, (furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or -Si(d6)(d7)-(d6, d7
may be the same or different, and may be a hydrocarbon group or -Od8
(d8 is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones listed for d5) alone or in combination.

Furthermore, preferably, the binder resin [A] is a copolymer component represented by the above general formula (I) [general formula (Ia)
or (Ib)], and as polymer components copolymerized therewith, -PO3 H2, -S
Contains 0.05 to 10% by weight of a copolymerization component containing at least one polar group selected from O3H, -COOH, -P(=O)(OH)R01, and a cyclic acid anhydride-containing group. is preferable in terms of further improving electrostatic properties.

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

The copolymer components containing these polar groups are:
For example, any vinyl compound containing a polar group that can be copolymerized with a monomer corresponding to a repeating unit represented by general formula (I) [including general formulas (Ia) and (Ib)] may be used. For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (published in 1986). Specifically, acrylic acid, α and/or β
Substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form) body, β-chloro body, β-bromo body,
α-chloro-β-methoxy form, α,β-dichloro form, etc.)
, methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2
-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinyl benzenesulfonic acid,
Vinyl sulfonic acid, vinyl phosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester dielectrics and amide derivatives of these carboxylic acids or sulfonic acids, compounds containing the polar group in the substituent, etc. It will be done.

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

[0077]

[Chemical formula 18]

[0078]

[Chemical formula 19]

[0079]

[C20]

[0080]

[C21]

[0081]

[C22]

[0082]

[C23]

[0083]

[C24]

[0084]

[C25]

[0085]

[C26]

[0086]

[C27]

[0087]

[C28]

[0088]

[C29]

[0089]

[C30]

[0090]

[Chemical formula 31]

[0091]

[C32]

[0092]

[Chemical formula 33]

[0093]

[C34]

[0094]

[C35]

[0095]

[C36]

[0096]

[C37]

[0097]

[C38]

[0098]

[C39]

0099

[C40]

[0100]

[C41]

[0101]

[C42]

[0102]

[C43]

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

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, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (e.g. dimethyl ester, diethyl ester, etc.)
, acrylamides, methacrylamides, styrenes (e.g. styrene, vinyltoluene, chlorostyrene,
hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

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

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

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

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

The amount of these chain transfer agents or polymerization initiators is 0.5 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers. The low molecular weight resins [A] (including [A']) as described above are preferably used in combination with known resins for conventional photoconductive zinc. The ratio of the low molecular weight resin [A] to other resins is preferably 5-50/95-50 (weight ratio).

In the present invention, the ratio of photoconductive zinc oxide, resin (total binder resin) and resin particles [L] is 1
00/10 to 100/0.1 to 10 (weight ratio) is preferable. Further, it is preferable that the resin [A] accounts for 5 to 50% by weight of the total binder resin of 10 to 100%.

[0111] Other resins used in combination have a weight average molecular weight of 3 x 104 to 1 to 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, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) p. 9, edited by Koichi Nakamura, ""Practical Technology of Binders for Recording Materials" Chapter 10, C. H. C. Publishing (1985), D. Tatt,
S. C. Heidecker, Tappi, 49 (No.
．． 10), 439 (1966), E. S. Baltaz
ziR. G. Blanclotte etal,
Photo. Sci. Eng. , 16 (No. 5), 3
54 (1972), Nguyen Tran Khe, Isamu Shimizu, Eiichi Inoue, Journal of the Electrophotography Society 18 (No. 2), 22 (
1980), JP 50-51011, JP 53-5
4027, 54-20735, 57-202544
Materials disclosed in each publication are listed.

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

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

[0115]

[C44]

[In formula (III), V is -COO-, -O
CO-, -(CH2)h -OCO-, -(CH2)
h represents -COO-, -O- or -SO2-. However, h represents an integer of 1 to 4] In general formula (III), f3 and f4 represent the same content as a1 and a2 in formula (I).

R07 represents the same content as R03 in formula (I). As the medium to high molecular weight binder resin (hereinafter referred to as resin [B]) containing the polymer component represented by the general formula (III), for example, a random binder resin containing the polymer component represented by the formula (III) can be used. Polymer resin (Japanese Patent Application Laid-open No. 63-49
817, 63-220149, 63-220148
Publications, etc.), combined resins of the random copolymer and crosslinkable resin (JP-A-1-102573, etc.), formula (III)
A copolymer containing a polymer component represented by the formula and partially crosslinked in advance (JP-A-2-34860, JP-A-2-40660, etc.) and a monofunctional macromonomer consisting of a polymer component of a specific repeating unit. Graft-type block copolymers obtained by polymerization with monomers corresponding to the components represented by formula (V) (Japanese Patent Applications No. 1983-203933 and No. 63-207317, Japanese Patent Application No. 163796 and No. 1-1999) 212994
, 1-229379, and 1-189245, which the present inventors have already filed.

In the present invention, the resin [A] is a low molecular weight copolymer in which a methacrylate copolymer component having a specific substituent and a specific polar group are bonded to one end of the polymer main chain; Because it adsorbs to the stoichiometric defects of the photoconductor in the photoconductive layer and has a low molecular weight, it improves the coverage of the photoconductor surface and compensates for the trapping of the photoconductor. It was found that while the temperature characteristics were dramatically improved, the photoconductor was sufficiently dispersed and agglomeration was suppressed.

[0119] As a result, it has been found that it has excellent electrophotographic properties as an electrophotographic photoreceptor, and in particular, it exhibits extremely excellent performance even when a spectral sensitizing dye for semiconductor laser light is used. Ta.

[0120] If a medium to high molecular weight resin [B] is used in combination, the photoconductivity will be higher than that of the resin [A] alone, without impairing the high performance electrophotographic properties obtained by using the resin [A]. It was found that the mechanical strength of the layer could be sufficiently improved. That is, the adsorption and coating interaction between the photoconductor and the binder resin is properly performed, and the film strength of the coated conductive layer is maintained.

This is considered to be due to the following action of the binder resin according to the present invention. That is, in the present invention, resin [A] and resin [B] are used together as binder resins, and by specifying the weight average molecular weight of each resin and the content of polar groups in the resin, the photoconductor and the resin are combined. You can change the strength of the interaction. As a result, the resin [A], which has a stronger interaction, is selectively and appropriately adsorbed to the photoconductor, and the resin [B], which has a weaker interaction than the resin [A], is attached to the main chain of the polymer in the resin. Therefore, the polar groups bonded to specific positions interact gently with the photoconductor to the extent that the electrophotographic properties are not inhibited, and the molecular chains of resins [B] having long molecular chain lengths and graft molecular chain lengths are It is thought that the interaction was able to significantly improve both the electrophotographic properties and the mechanical strength of the film as described above.

[0122] Non-aqueous solvent-based dispersed resin particles (hereinafter sometimes referred to as resin particles [L]) used in the present invention will be described below.
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 have thiol groups, sulfo groups, amino groups and -P(=Z0)(-Z
0 -H)R' 1 group [Z0 represents an oxygen atom or a sulfur atom. R'1 represents -Z0-H, a hydrocarbon, or -Z0-R'2 (R'2 represents a hydrocarbon group). A polymer component [abbreviated as polymer component (C)] consisting of a monofunctional monomer (C) that becomes insoluble in the non-aqueous solvent after polymerization is treated with at least a fluorine atom and/or a silicon atom as a substituent. It is obtained by carrying out a polymerization reaction in the presence of a dispersion stabilizing resin that contains repeating units and becomes soluble in the non-aqueous solvent even after polymerization.

[0123] The resin particles used in the present invention have an average particle size equal to 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.

[0125] Note that the smaller the particle diameter of the resin particles, the larger the specific surface area, which brings about good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, 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.

[0126] In the present invention, resin particles that do not form a higher-order mesh structure as described above or resin particles that do form a higher-order mesh 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.

[0127] The molecular weight of the dispersed resin particles is 104 to 106
, preferably 104 to 5×105. As a polymerization component in the resin particles, the proportion of monomer (C) present is as follows:
The amount is 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the resin is composed only of the monomer (C) and the dispersion stabilizing resin.

[0128] Specifically, the solubility of the dispersion stabilizing resin of the present invention in the non-aqueous 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.

[0129] The weight average molecular weight of the dispersion stabilizing resin is 1 x 103 to 1 x 105, preferably 2 x 1
03 to 5×104, particularly preferably 3×103 to
It is 2×104.

[0130] 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 1×10 5 , the effect of the present invention, which improves water retention while satisfying electrophotographic properties when added to the surface layer, will be diminished.

[0131] 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 30% by weight of the total.
It is preferable that the content is 5 or more, more preferably 5
It is 0% by weight or more.

[0132] When the above-mentioned components of the present invention are less than 30% 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.

The dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the monomer (C) to be insolubilized as described above. [B] has polar groups bonded to specific positions in the polymer main chain in the resin that interact gently with the photoconductor to the extent that they do not inhibit electrophotographic properties, and that have long molecular chain lengths and grafts. It is thought that the interaction between the molecular chains of the resins [B] having the same molecular chain length made it possible to significantly improve both the electrophotographic properties and the mechanical strength of the film as described above.

Next, the resin particles [L] of the present invention will be explained in detail. At least one thiol group, sulfo group, amino group, -P(=
The functional group that generates at least one hydrophilic group (hereinafter sometimes simply referred to as a hydrophilic group-generating functional group) of one Z0 ) (-Z0 -H)R' group will be explained in detail.

The hydrophilic group-forming functional group of the present invention generates at least one hydrophilic group by decomposition, and the number of hydrophilic groups generated from one functional group may be one or two or more. The functional group that generates at least one thiol group upon decomposition (thiol group-generating functional group) will be described in detail below.

According to one preferred embodiment of the present invention, the thiol group-forming functional group-containing resin has, for example, the following general formula (C
-I) A resin containing at least one functional group represented by [-S-LA].

General formula (C-I): [-S-LA] In the formula, LA is -Si(RA 1 )(RA 2 )(R
A3), -CO-RA4, -CO-RA5,
-CO-O-RA 6 , -CS-O-RA 7 , -
S-RA8, -CS-N(RA9)(RA1
0) or

[0138]

[C45]

represents [0139]. However, RA 1 , RA 2
and RA 3 may be the same or different, and each represents a hydrocarbon group or -O-RA'(RA' represents a hydrocarbon group), and RA 4 , RA 5 , RA 6
, RA 7 , RA 8 , RA 9 , RA 10
, RA 11 , RA 12 and RA 13 each independently represent a hydrocarbon group, and Y1 represents an oxygen atom or a sulfur atom.

[0140] The functional group of the above general formula [-S-LA] is
Thiol groups are produced by decomposition, and will be explained in more detail below. LA is −Si(RA 1 )(
RA 2 )(RA 3 ), when R
A 1 , RA 2 and RA 3 may be the same or different, preferably a hydrogen atom, an optionally substituted linear or branched 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, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (e.g., cyclopentyl group, cyclohexyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), or optionally substituted aromatic group ( For example, a phenyl group, a naphthyl group, a chlorophenyl group, a tolyl group, a methoxyphenyl group, a methoxycarbonylphenyl group, a dichlorophenyl group, etc.) or -O-RA'(RA' represents a hydrocarbon group, specifically the above-mentioned RA1, R.A.
2 and RA 3 ).

LA is -CO-RA 4 , -CO-R
A5, -CO-O-RA6, -CS-O-RA
7 or -S-RA 8 ,
RA 4 , RA 5 , RA 6 , RA 7 , R
Each of A 8 is preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (e.g. methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, ethyl group, propyl group). , n-butyl group, hexyl group, 3-chloropropyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexylfluoro-i-propyl group, octyl group,
decyl 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.), substituted Aryl groups having 6 to 12 carbon atoms (e.g. phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.) represent.

LA is -CS-N(RA 9 )(RA
10), RA 9 and RA
Each of 10 may be the same or different, and preferred examples represent the substituents preferred in RA 4 to RA 8 above.

[0143] LA is

[0144]

[C46]

In the case where Y1 represents an oxygen atom or a sulfur atom. RA 11, RA 12, R
A 13 may be the same or different, and preferably represents a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms.

[0146] As a preferable example, the above-mentioned RA 4 to RA
8 represents the same content. p represents an integer of 5 or 6. Another preferred thiol group-forming functional group-containing resin of the present invention is a resin containing at least one thiirane ring represented by general formula (C-II) or general formula (C-III).

[0147]

[C47]

In formula (C-II), RA 14 and RA 15 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, it represents a hydrogen atom or a substituent selected as preferred for RA 4 to RA 8 above.

In formula (C-III), XA represents a hydrogen atom or an aliphatic group. Preferably, the aliphatic group represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.).

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

[0151]

[C48]

In formula (C-IV), YA represents an oxygen atom or an -NH- group. RA 16, RA 17,
and RA 18 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, it represents a hydrogen atom or a substituent selected as preferred for RA 4 to RA 8 above.

RA 19 and RA 20 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or -O-RA
''(RA'' represents a hydrocarbon group). Preferably, it represents the preferred substituent among the above RA 1 to RA 3 .

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

Examples of functional groups having at least two thiol groups that are sterically close to each other and simultaneously protected with one protecting group include the following general formula (C-V),
Those represented by (C-VI) and (C-VII) can be mentioned.

[0156]

[C49]

[0157] In formulas (C-V) and (C-VI), ZA represents a carbon-carbon bond or a chemical bond that directly connects C-S bonds, which may be via a heteroatom (provided that a sulfur atom The number of atoms in between is within 4). Furthermore, one of the -(ZA...C)- bonds may represent only a simple bond, for example, as shown below.

[0158]

[C50]

In formula (C-VI), RA 21, R
A22 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or -O-RA''(RA'' represents a hydrocarbon group). In formula (C-VI), RA 21
and RA 22 may preferably be the same or different and are hydrogen atoms, optionally substituted alkyl groups having 1 to 12 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, 2- methoxyethyl group, octyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), carbon atoms having 5 to 7 carbon atoms Alicyclic group (e.g. cyclopentyl group, cyclohexyl group) or optionally substituted aryl group (e.g. phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group, etc.) or -O-
RA''(RA'' has the same meaning as the hydrocarbon group in RA 21 and RA 22).

In formula (C-VII), RA 23,
RA 24, RA 25, and RA 26 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above RA 21, RA
It represents the same meaning as the hydrocarbon group preferred in No. 22.

General formulas (C-I) to (C-I) used in the present invention
The monomer (C) containing at least one functional group represented by C-VII) can be used, for example, in "Reactive Polymers" by Yoshio Iwakura and Keisuke Kurita, pp. 230-237 (Kodansha: published in 1977), published by Nippon Kagaku. “New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [III]” Chapter 8, pp. 1700-1
713 pages (Maruzen Co., Ltd., published in 1978), J. F. W
．． McOmie “Protective Group
s in Organic Chemistry
” Chapter 7 (Plenum Press. 1973), S. Patai “The Chemistry”
of the thiol group P
art2” Chapters 12 and 14 (John Wile
y & Sons, 1974), etc. can be applied.

More specifically, general formulas (C-I) to (C
Examples of the monomer containing the functional group -VII) include the following compounds.

[0163]

[C51]

[0164]

[C52]

[0165]

[C53]

[0166]

[C54]

[0167]

[C55]

[0168]

[C56]

[0169]

[C57]

[0170]

[C58]

[0171]

[C59]

[0172]

[C60]

[0173]

[C61]

Next, at least one -P(
=Z0)(-Z0-H)R'1 group, for example, a functional group that generates a group of the following general formula (C-VIII) or (C-IX) will be explained in detail.

[0175]

[C62]

In formula (C-VIII), RB is a hydrocarbon group or -ZB 2 -RB' (where RB'
represents a hydrocarbon, and ZB 2 represents an oxygen atom or a sulfur atom).

QB 1 represents an oxygen atom or a sulfur atom. ZB 1 represents an oxygen atom or a sulfur atom. In formula (IX), QB 2 , ZB 3 and ZB
Each of 4 independently represents an oxygen atom or a sulfur atom.

Preferably, RB is an optionally substituted alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group,
propyl group, butyl group) or -ZB2-RB'(
Here, ZB 2 represents an oxygen atom or a sulfur atom.

RB' represents the same content as RB. QB 1 , QB 2 , ZB 1 , ZB 3 ,
Each ZB 4 independently represents an oxygen atom or a sulfur atom.

By the above decomposition, formula (C-VIII) is obtained.
Examples of the functional group that generates a phospho group represented by (C-IX) include functional groups represented by general formulas (X) and/or (XI).

[0181]

[C63]

In formulas (C-X) and (C-XI),
QB 1 , QB 2 , ZB 1 , ZB 3 , Z
B 4 and RB represent the contents as defined in formulas (C-VIII) and (C-IX), respectively.

LB 1 , LB 2 and LB 3 are each independently -[C(RB 1 )(RB 2
)]n −XB 1 ,

[0184]

[C64]

-Si(RB 3 )(RB 4 )(R
B5), -CO-RB6, -CS-RB7
, -CO-O-RB8, -CS-O-RB9,
-S-RB 10,

[0186]

Represents [Chemical 65]. LB 1 to LB 3 are −[C(RB 1
)(RB2)]n-XB1 or

0187
]

[C66]

In the case where RB 1 , RB
2 may be the same or different and represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.) or a methyl group. XB 1 and XB 2 are electron-withdrawing groups (here, the electron-withdrawing group is a substituent whose Hammett's substituent constant shows a positive value, such as a halogen atom, -COO-, -CO-, -SO2 -, -CN-
, -NO2, etc.), preferably a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.)
, -CN-, -CONH2, -NO2 or -SO2
RB''(RB'' is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a benzyl group, a phenyl group,
represents a hydrocarbon group such as tolyl group, xylyl group, mesityl group, etc. n represents 1 or 2. Furthermore, XB
When 1 is a methyl group, RB 1 and RB 2
represents a methyl group and n=1.

LB 1 to LB 3 are -Si(RB
3) (RB 4 )(RB 5 ), RB 3 , RB 4 and RB 5 may be the same or different, preferably a hydrogen atom, an optionally substituted straight atom having 1 to 18 carbon atoms; Chain or branched alkyl group (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.), substitution alicyclic groups that may be substituted (e.g., cyclopentyl group, cyclohexyl group, etc.), aralkyl groups having 7 to 12 carbon atoms that may be substituted (e.g., benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), substituted aromatic groups (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or -O-RB''' (
RB'' represents a hydrocarbon group, and specifically represents the substituents of RB 3 , RB 4 and RB 5 described above.

LB 1 to LB 3 are -CO-RB
6, -CS-RB7, -CO-O-RB8,
When representing -CS-O-RB9 or -S-RB10, RB6, RB7, RB8
, RB 9 and RB 10 each independently represent a hydrocarbon group. Preferably an optionally substituted carbon number of 1 to 6
linear or branched alkyl groups (e.g. methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, ethyl group, propyl group, hexyl group) , t-butyl group, hexafluoro-i-propyl group, etc.), 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.), an optionally substituted aryl group having 6 to 12 carbon atoms (e.g. phenyl group, tolyl group, xylyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group) , chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

[0191] Furthermore, LB 1 to LB 3

0192
]

[C67]

In the case where YB 1 and Y
B2 represents an oxygen atom or a sulfur atom. Monomer (C) containing at least one functional group used in the present invention
can be synthesized by introducing a protecting group according to a conventionally known method. A similar synthetic reaction can be used to introduce the protecting group. in particular,
J. F. W. McOmie “Protective
groups in Organic Chem
istry” Chapter 6 (Plenum Press, 1
973) or the method described in "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., 1978), etc., a synthetic reaction similar to the method for introducing a protecting group into a hydroxyl group, or a method of introducing a protecting group into a hydroxyl group, or a method of introducing a protecting group into a hydroxyl group, or a method of introducing a protecting group into a hydroxyl group, as described in S. Patai “The Chemi”
Try of the Triol Gro
upPart 2” Chapters 13 and 14 (Wiley
-Interscience (published in 1974), T. W.
Greene “Protective groups
in Organic Synthesis” No. 6
Chapter (Wiley-Interscience 198
It can be produced by a synthetic reaction similar to the method for introducing a protecting group into a thiol group as described in 1999).

[0194] The following examples are given as specific examples of compounds that can serve as repeating units of polymeric components containing functional groups of the general formula (C-X) and/or (C-XI) used as protective groups. Can be done.

[0195]

[C68]

[0196]

[C69]

[0197]

[C70]

[0198]

[C71]

Next, amino groups, such as -NH
Examples of functional groups that generate 2 groups and/or -NHRc groups include the following general formulas (C-XII) to (C-XIV
) can be mentioned.

[0200]

[C72]

In formula (C-XII) and formula (C-XIV), Rc 0 is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group). group, hexyl group, octyl group, decyl group, dodecyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 2-cyanoethyl group, 2
-methoxyethyl group, 2-ethoxyethyl group, 2-methoxycarbonylethyl group, 3-methoxypropyl group, 6
-chlorohexyl group, etc.), alicyclic groups having 5 to 8 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, 3- Phenylpropyl group, 1-
phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group, methylbenzyl group, etc.), optionally substituted aryl groups having 6 to 12 carbon atoms (e.g. phenyl group, chlorophenyl group, dichlorophenyl group, tolyl group, xylyl group) group, mesityl group, chloromethyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group, etc.).

Preferably, when Rc 0 represents the hydrocarbon group, hydrocarbon groups having 1 to 8 carbon atoms are mentioned. In the functional group represented by formula (C-XII), Rc
1 represents an optionally substituted aliphatic group having 2 to 12 carbon atoms, and more specifically Rc 1 represents the following formula (C-XV
) represents a group represented by

[0203]

[C73]

In formula (C-XV), A1 and A2 each represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, methoxymethyl group, ethoxymethyl group, 2-
Methoxyethyl group, 2-chloroethyl group, 3-bromopropyl group, cyclohexyl group, benzyl group, chlorobenzyl group, methoxybenzyl group, methylbenzyl group, phenethyl group, 3-phenylpropyl group, phenyl group, tolyl group, xylyl group , mesityl group, chlorophenyl group, methoxyphenyl group, dichlorophenyl group, chloromethylphenyl group, naphthyl group, etc.), and Yc represents a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.), a cyano group, or a group having 1 to 1 carbon atoms. 4 alkyl group (e.g. methyl group,
ethyl group, propyl group, butyl group), aromatic groups that may contain substituents (e.g. phenyl group, tolyl group, cyanophenyl group, 2,6-dimethylphenyl group, 2,4,
6-trimethylphenyl group, heptamethylphenyl group,
2,6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2-propylphenyl group, 2-butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group, etc.) or -SO2 -Rc 6 (Rc 6 represents the same content as the hydrocarbon group of Yc), etc. n represents 1 or 2.

More preferably, when Yc is a hydrogen atom or an alkyl group, a1 and a2 on the carbon adjacent to the oxygen atom of the urethane bond represent a substituent other than a hydrogen atom. When Yc is not a hydrogen atom or an alkyl group, A1 and A2 may be any of the groups listed above.

That is, −[C(A1)(A2)]n
In -Yc, preferred examples include the case where a group containing at least one electron-withdrawing group is formed or the case where the carbon adjacent to the oxygen atom of the urethane bond forms a sterically bulky group. It is something.

Rc 1 is an alicyclic group {for example, a monocyclic hydrocarbon group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclohexyl group, 1-methylcyclobutyl group, etc.) or Crosslinked cyclic hydrocarbon groups (bicyclooctane group, bicyclooctene group, bicyclononane group, tricycloheptane group, etc.)}
represents.

In the general formula (C-XIII), Rc
2 and Rc 3 may be the same or different and each represents a hydrocarbon group having 1 to 12 carbon atoms, specifically,
It represents the same content as the aliphatic group or aromatic group in Yc of formula (C-XII).

In the general formula (C-XIV), Xc 1
and Xc 2 may be the same or different and each represents an oxygen atom or a sulfur atom. Rc4, Rc
5 may be the same or different, each having 1 to 8 carbon atoms
represents a hydrocarbon group, specifically represents an aliphatic group or an aromatic group in Yc of formula (C-XII).

Specific examples of the functional groups of formulas (C-XII) to (C-XIV) are shown below.

[0211]

[C74]

[0212]

[C75]

[0213]

[C76]

[0214]

[C77]

[0215]

[C78]

The amino group (
For example, a functional group that generates -NH2 group and/or -NHR group), for example, the above general formulas (C-XII) to (C-XIV
The monomer (C) containing at least one functional group selected from the group of Published by Maruzen Co., Ltd.), J. F. W. McOmie P
protective groups in or
ganic Chemistry” Chapter 2 (Plen
um Press 1973), “Prote
active groups in Organi
c Synthesis Chapter 7 (John Wi.
ley & Sons, 1981).

Furthermore, examples of the functional group that generates at least one sulfo group upon decomposition include the general formula (C-X
VI) or (C-XVII).

General formula (C-XVI) -SO2 -O
-RD 1 General formula (C-XVII) -S
O2 -S-RD 2 RD 1 in formula (C-XVI)
is-[C(RD3)(RD4)]n-YD
,

[0219]

[C79]

or represents -NHCORD 7 . formula(
In C-XVII), RD 2 represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms which may have a substituent.

[0221] The above general formula (C-XVI), (C-XVI
The functional group I) generates a sulfo group upon decomposition, and will be explained in more detail below. RD 1 is - [
When representing C(RD3)(RD4)-YD, RD3 and RD4 may be the same or different, and each has a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 ~6 alkyl groups (
For example, it represents a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). YD has 1 or more carbon atoms
18 optionally substituted alkyl groups (e.g. methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, trifluoromethyl group, methanesulfonylmethyl group, cyanomethyl group, 2-methoxyethyl group, ethoxymethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2-methoxycarbonylethyl group, 2-propoxycarbonylethyl group, methylthiomethyl group, ethylthiomethyl group, etc.), optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, etc.), aryl group which may contain a substituent having 6 to 12 carbon atoms (e.g. phenyl group, naphthyl group, nitrophenyl group, dinitrophenyl group, cyanophenyl group, trifluoromethylphenyl group) group, methoxycarbonylphenyl group, butoxycarbonylphenyl group, methanesulfonylphenyl group,
benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group, etc.) or -
CO-RD 8 (RD 8 represents an aliphatic group or an aromatic group, and specifically represents the same substituent as the above YD). n represents 0, 1 or 2. More preferably, substituents:
-[C(RD3)(RD4)]n-YD includes a functional group containing at least one electron-withdrawing group. Specifically, when n is 0 and YD is a hydrocarbon group that does not contain an electron-withdrawing group as a substituent,
-[C(RD3)(RD4)]n- contains at least one halogen atom. Also n
is 0, 1 or 2, and YD contains at least one electron-withdrawing group. Furthermore, when n=1 or 2, -CO-RD
8 Ya-[C(RD3)(RD4)]-CO
-RD 8 and the like.

Another preferred substituent is -SO
At least two hydrocarbon groups are substituted on the carbon atom adjacent to the oxygen atom in 2-O-RD, or
When n=0 or 1 and YD is an aryl group, examples include cases where the aryl group has substituents at the 2-position and the 6-position.

[0223] RD 1 is

[0224]

[C80]

In the case where ZD represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by the general formula (C-XVIII) or (C-XIX).

[0226]

[Chemical formula 81]

In formula (C-XVIII), RD 9 , R
D10 may be the same or different, and each represents a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
Octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group,
2-(methanesulfonyl)ethyl group, 2-(ethoxyoxy)ethyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, 3
-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), optionally substituted alkenyl groups having 3 to 18 carbon atoms (e.g. allyl group, 3-methyl-2 -propenyl group, etc.), RD 1 is -N=C (RD 5 )
(RD 6 ), RD 5 , R
D 6 is a hydrogen atom, an aliphatic group (specifically RD
3 , RD 4 ) or an aryl group (specifically, RD 3 , RD 4 ). However, both RD 5 and RD 6 do not represent hydrogen atoms.

When RD 1 represents -NHCORD 7 , RD 7 represents an aliphatic group or an aryl group, and specifically represents the same content as that of RD 3 and RD 4 . In formula (C-XVII), RD
2 represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms which may have a substituent.

More specifically, the above formula (C-XVI)
It represents the same content as the aliphatic group or aryl group in YD represented by. General formula used in the present invention [-SO
2 -O-RD 1 ] or [-SO2 -O-RD
Monomer (C) containing at least one functional group selected from group 2] can be synthesized based on knowledge of conventionally known organic reactions.

For example, J. F. W. McOmie, “P.
protective groupsin Orga
nic Chemistry”; Prenum P
ress (published in 1973), T. W. Greene, “
Protective groupsin Org
anic Synthesis” John W.
It can be synthesized in the same manner as the carboxyl group protection reaction of Iley & Sons (published in 1980).

More specifically, general formula (C-XVI)-SO
2 -O-RD 1 or general formula (C-XVII)-S
The following examples can be given as the functional group of O2-O-RD2, but the scope of the present invention is not limited thereto.

[0232]

[C82]

[0233]

[Chemical formula 83]

[0234]

[Chemical formula 84]

[0235]

[Chemical formula 85]

[0236]

[C86]

[0237] The resin particles [L] of the present invention are monomers [C]
It may also be polymerized in the coexistence of other monomers. Any other monomer may be used as long as it can be copolymerized with monomer [C] and the copolymer becomes a polymer insoluble in the non-aqueous solvent.

Other monomers that can be copolymerized with these monomers include vinyl aliphatic carboxylates or allyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate, etc. , esters or amides of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, α-olefins , acrylonitrile, methacrylonitrile, and vinyl group-substituted heterocyclic compounds such as N-vinylpyrrolidone.

The amount of these other monomers is 60 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total polymer components to be insolubilized. When the amount of other monomers exceeds 60 parts by weight, the effect of improving water retention as an original plate for offset printing decreases.

Next, in the non-aqueous solvent-based dispersed resin particles of the present invention, the soluble dispersion-stabilizing resin that stabilizes the dispersion of the resin particles in the non-aqueous solvent will be described. The dispersion stabilizing resin used in the present invention is characterized by containing a substituent containing a fluorine atom and/or a silicon atom in the polymer.

[0241] These repeating units having a substituent containing a fluorine atom and/or a silicon atom will be explained. Examples of the chemical structure of the repeating unit include those obtained from radical addition polymerizable monomers, those consisting of a polyester structure, or those consisting of a polyether structure, and the side chains in the repeating units of these polymer structures, Any material may be used as long as it contains a fluorine atom and/or a silicon atom.

Examples of the fluorine atom-containing substituent include -C h F 2h+1 (h represents an integer of 1 to 12), -(CF 2 ) j CF2 H (j is 1 to 1)
), -C 6 Hl 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).

[0243] 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.

[0244] However, R 3 , R 4 , R 5
represent a hydrocarbon group or an -OR9 group (R9 represents the same content as the hydrocarbon group of R3), which may be the same or different and may be substituted.

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,
Represents the same symbol content as R 3 , R 4 , R 5 .

[0247] Next, specific examples of the repeating unit having a substituent containing a fluorine atom and/or a silicon atom as described above are shown below. Here, a represents H or CH3, and R
f is −CH 2 Ch C 2h+1 −(CH 2
) 2 −(CF2 ) j CF2 H ,
R 1 ′, R 2 ′, R 3 ′ are C 1 -
12 alkyl group, R'' is -Si(CH3)
3, h is an integer from 1 to 12, and j is from 1 to 11.
p represents an integer of 1 to 3, l represents an integer of 1 to 5, q represents an integer of 1 to 20, r represents an integer of 30 to 1
represents an integer of 50, and t represents an integer of 2 to 12. However, the scope of the present invention is not limited thereto.

[0248]

[Chemical formula 87]

[0249]

[Chemical formula 88]

0250]

[Chemical formula 89]

[0251]

[C90]

0252]

[Chemical formula 91]

0253]

[C92]

0254]

[C93]

0255]

[C94]

0256]

[C95]

0257]

[C96]

[0258]

[C97]

0259]

[C98]

0260]

[C99]

[0261]

[Chemical formula 100]

0262]

[Chemical formula 101]

Further, the dispersion stabilizing resin may contain other components together with the fluorine atom- and/or silicon atom-containing component. Other copolymerized components may be any components that copolymerize with the corresponding polymer, and examples of the corresponding monomers include α-olefins, styrenes, acrylonitrile, methacrylonitrile, Vinyl-containing heterocycles (heterocycles include, for example, pyran ring, pyradoline ring, imidazole ring, pyridine ring, etc.), vinyl group-containing carboxylic acids and their esters (for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
(maleic acid and its esters, etc.), vinyl group-containing carboxamides (eg, acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.).

In the dispersion stabilizing resin of the present invention, the fluorine atom and/or silicon atom-containing polymer component is at least 30 parts by weight, preferably at least 50 parts by weight, based on 100 parts by weight of the total polymer of the resin.

[0265] Furthermore, the dispersion stabilizing resin of the present invention contains photo- and/or thermosetting functional groups 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.

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 component will be explained below.

0267]

[Chemical formula 102]

In the general formula (II), V 0 is -O
-, -COO -, -OCO -, -CH2 OCO
-, -CH2 COO -, -SO2 -, -CON
R1 -, -SO2 NR1 - or -C 6 H 4
- represents.

In addition to a hydrogen atom, R 1 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-methoxycarbonylethyl group, 2
-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g. 2-bromopropyl group, etc.),
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro benzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (for example, 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.).

When V0 represents -C 6 H 4 -, 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, ethyl, propyl, butyl, chloromethyl, methoxymethyl, etc.)
, alkoxy groups (eg, methoxy group, ethoxy group, propioxy group, butoxy group, etc.).

b 1 and b 2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, (methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R 2 or COOR2 via a hydrocarbon (R 2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group) represents a formula group or an aryl group, which may be substituted, and specifically represents the same content as described for R 1 above.

-COO-R 2 via the above hydrocarbon
Examples of the hydrocarbon group include a methylene group, an ethylene group, a propylene group, and the like. More preferably, in general formula (II), V 0 is -COO-, -O
CO -, -CH2 OCO -, -CH2 COO
-, -O -, -CONH-, -SO2 NH- or -
Represents C 6 H 4 -, b 1 and b 2 may be the same or different, and represent a hydrogen atom, a methyl group,
-COOR2 or -CH2 COOR2,
(R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc.). Still more preferably, any one of b 1 and b 2 One or the other always represents a hydrogen atom.

Specifically, as the polymerizable double bond group component represented by the general formula (II), CH2 = CH-
CO-O-, CH2=C(CH3)-CO-O
-, C(CH3)H=CH-CO-O-, CH2
=C(CH2COOCH3)-CO-O-
, CH2=C(CH2COOH)-CO-O-
, CH2=CH-CONH-, CH2=C(CH
3)-CONH-, C(CH3)H=CH-C
ONH-, CH2=CH-O-CO-, CH2
=CH-CH2-O-CO-, CH2=CH-O-
, CH2=C(COOH)-CH2-CO-O-
, CH2=C(COOCH3)-CH2-CO-
O-, CH2=CH-C6H4-, etc. are mentioned.

[0274] The polymerizable double bond group moiety represented by the above-mentioned general formula (II) is located at one end of the main chain of a polymer containing at least a repeating unit having a substituent containing a fluorine atom and/or a silicon atom. and are bonded directly or via any linking group. Specifically, the connecting group is a divalent organic residue, -O-, -S-
, -Nq1 -, -SO-, -SO2 -, -COO
-, -OCO-, -CONHCO-, -NHCONH
-, -CONq2 -, -SO2 Nq3 - and -S
composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from i(q4)(q5)- Represents an organic residue. Here, q1 to q5 are expressed by the formula (II
) represents the same content as R 1 in ).

As a divalent aliphatic group, for example, -C(q
6 ) (q 7) −, − C (q6 ) = C (q
7) −, −(C≡C)−, −C 6 H 10−,

0276]

[Chemical formula 103]

{q6 and q7 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 -NR10-, R10 is an alkyl group having 1 to 4 carbon atoms, -CH2
Cl or -CH2Br}.

[0278] 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.

[0280] Specifically, the above polymerizable double bond group-containing moiety is bonded only in the polymer chain, or has a polymerizable double bond group only at one end of the main chain of the polymer chain. A polymer to which a containing moiety is bonded (hereinafter abbreviated as a monofunctional polymer [M]) can be mentioned. Specific examples of the portion composed of the polymerizable double bond group component represented by the general formula (II) of the monofunctional polymer [M] and an organic residue linked thereto include the following. However, it is not limited to these. However, in each example below, P 1 is -H
, -CH3, -CH2COOCH3, -Cl,
-Br or -CN, P2 is -H or -CH3
, X represents -Cl or -Br, and n is 2 to 12
represents an integer of 1 to 4, and m represents an integer of 1 to 4.

0281]

[Chemical formula 104]

0282]

[Chemical formula 105]

0283

[Chemical formula 106]

0284

[Chemical formula 107]

0285]

[Chemical formula 108]

0286]

[Chemical formula 109]

The monofunctional polymer [M] of the present invention can be produced by conventionally known synthesis methods. for example,
■ 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 or cationic polymerization, ■
Polymers with terminal reactive groups bonded by radical polymerization using a polymerization initiator and/or chain transfer agent containing reactive groups such as carboxyl groups, hydroxyl groups, and amino groups in the molecule and various A monofunctional polymer [M
], and (2) a method using 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. It will be done.

Specifically, P. Dreyfuss &
R. P. Quirk, Encycle. Polym. S
ci. Eng. , 7, 551 (1987), P. F. R
empp, E. Franta, Adv. Polym
．． Sci. , 58, 1 (1984), V. Perce
c, Appl. Poly. Sci. , 285, 9
5 (1984), R. Asami, M. Takar
i, Makromol. Chem. Suppl. ,1
2, 163 (1985), P. Rempp. et
al, Makromol. Chem. Suppl. ，
8, 3 (1984), Yuji Kawakami, Chemical Industry, 38, 5
6 (1987), Yuya Yamashita, Kobunshi, 31,988 (1
982), Shiro Kobayashi, Polymers, 30,625 (198
1), Toshinobu Higashimura, Japan Adhesive Association Journal, 18,536 (1)
982), Koichi Ito, Polymer Processing, 35,262 (1
986), 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.

Furthermore, when the dispersed resin particles of the present invention have a wire structure, as described above, the intermolecular bonding of the polymer (C) comprising the polar group-containing monofunctional monomer (C) as a polymer component It is bridged and forms a high-order mesh structure, making it sparingly soluble or insoluble in water.

[0290] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (1) a method of crosslinking a polymer containing the polymer component (C) with various crosslinking agents or curing agents; (2) a method of carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (C); a method of forming a wire structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and This can be carried out by a method such as a method in which a polymer containing a component containing a reactive group is crosslinked by a polymerization reaction or a polymer reaction.

[0291] As the crosslinking agent in the above method (2), compounds which are commonly used as crosslinking agents can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
Compounds described in "Polymer Data Handbook Basic Edition" edited by the Society of Polymer Science, Baifukan (1986), published by Taiseisha (1981), 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.

[0293] In addition, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polymerizable functional group of a polyfunctional oligomer that is caused to coexist in the method (2) above can be used. Specifically, the group is CH2=CH-CH2
-, CH2 = CO-O, CH2 = CH -, C
H2 = C(CH3)-CO-O-, C(CH3
)H=CH-CO-O-, CH2=CH-CONH-
, CH2=C(CH3)-CONH-, CH(CH
3)=CH-CONH-, CH2=CH-O-
CO-, CH2=C(CH3)-O-CO-, C
H2=CH-CH2-O-CO-, CH2=C
H-NHCO-, CH2=CH-CH2-NHCO
-, CH2 = CH-SO2 -, CH2 = CH-
CO-, CH2=CH-O-, CH2=CH-S
- and so on. 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 polyhydroxyphenol (such as hydroquinone, 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, vinylamides 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, allyl aminocarbonyl ester derivatives or amide derivatives containing vinyl groups such as propionic acid (e.g. vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate) , allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl acrylate methyloxycarbonyl ethylene ester, 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 chemical bonds and bridging between polymers by the reaction of the reactive groups between the polymers in the above method It can be carried out. Specifically, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (published in 1976)
It is described in detail in books such as . For example, polymer reactions involving combinations of functional groups in Group A (hydrophilic group polymer components) and Group B (polymers containing components containing reactive groups) in the table below are usually well known. This is one of the methods. Note that R21 and R22 in Table 1 are hydrocarbon groups, and are represented by the above formula (
It represents the same content as the hydrocarbon of R1 in II).

0298

[Table 1]

As described above, the mesh-dispersed resin particles of the present invention consist of a polymer component (C) containing a polar group and a polymer component [M] containing a repeating unit having a substituent containing a fluorine atom and/or a silicon atom. It is a particle of a polymer containing the following and having a structure in which the molecular chains are highly cross-linked.

[0300] 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. Method (2) using a monomer is preferred.

[0301] 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.

[0303] By synthesizing dispersed resin particles using a dispersion polymerization method in these non-aqueous solvent systems, the average particle size of the resin particles can easily be 1 μm or less, and the particle size distribution is very narrow and monodisperse particles can be obtained. It can be done.

Specifically, K. E. J. Barrett
“Dispersion Polymerizati
on 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. Walbr
idge, NATO. Adv. study. Inst
．． Ser. E. No. 67, 40 (1983), British Patent Nos. 893429 and 934038, U.S. Patent Nos. 1122397, 3900412, and 4606
989 specifications, JP-A-60-179751, JP-A-60
The method is disclosed in publications such as No.-185963.

[0305] The dispersion resin of the present invention consists of at least one of each of the monomer (C) and the monofunctional polymer [M],
When forming a wire structure, polyfunctional monomers (D) are allowed to coexist as necessary; in any case, the important thing is that the resin synthesized from these monomers does not dissolve in the non-aqueous solvent. If it is insoluble, a desired dispersed resin can be obtained.

[0306] In order to produce the dispersed resin particles used in the present invention as described above, the monomer (C), the monofunctional polymer [M], and the polyfunctional monomer (D) are generally used. benzoyl peroxide, azobisisobutyronitrile, in a non-aqueous solvent,
The polymerization may be carried out by heating in the presence of a polymerization initiator such as butyllithium. Specifically, the methods include: (1) adding a polymerization initiator to a mixed solution of monomer (C), monofunctional polymer [M], and polyfunctional monomer (D); (2) adding a polymerization initiator to a nonaqueous solvent; , a method in which a mixture of the above-mentioned polymerizable compound and a polymerization initiator is added dropwise or arbitrarily, and the method is not limited to these methods, and any method can be used for production.

[0307] 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.

[0308] The amount of polymerization initiator is 0.1 to 5% by weight based on the total amount of polymerizable compounds. Also, the polymerization temperature is 50 to 180
℃, preferably 60 to 120℃. The reaction time is preferably 1 to 15 hours.

[0309] The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

Furthermore, other dispersion stabilizing resins may be used in combination. When other dispersion stabilizing resins are used in combination, the amount is preferably 50 parts by weight or less based on 100 parts by weight of the total dispersion stabilizing resin. If the amount of other dispersion stabilizing resin exceeds 50 parts by weight, the surface concentration property will be lowered and the water retention property will be deteriorated.

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 60% by weight of the photoconductive zinc oxide, preferably less than 40% by weight.

[0313] When the amount of other photoconductive materials exceeds 60% by weight,
The effect of improving the hydrophilicity of the non-image area as a lithographic printing original plate is weakened. As the photoconductive zinc oxide according to the present invention, those conventionally known in this type of technical field may be used, including not only so-called zinc oxide, but also zinc oxide treated with an acid, zinc oxide pretreated with a dye, etc. It may be kneaded and then ground again (so-called press treatment), and there is no particular limitation.

[0314] In the lithographic printing original plate of the present invention, the total amount of binder resin used for photoconductive zinc oxide is such that the ratio of binder resin to 100 parts by weight of photoconductive zinc oxide is 10 to 100 parts by weight. , preferably in a proportion of 15 to 50 parts by weight.

[0315] In the binder resin provided to the photoconductive layer,
The proportion of resin [A] and other binder resins is 5 to 90/95 to 5 by weight based on 100 parts by weight of the total binder resin.
Preferably the weight ratio is 10-60/90-40.

If the proportion of resin [A] used is less than 5 parts by weight, the electrophotographic properties will deteriorate, and especially when combined with a spectral sensitizing dye for semiconductor laser light, the effect will be significantly reduced. If the amount exceeds 90 parts by weight, the film strength of the photoconductive layer deteriorates, and when used as an original plate for offset printing,
This results in a decrease in printing durability.

[0317] The amount of resin particles [L] used in the present invention is preferably 0.1 to 30 parts by weight based on 100 parts by weight of all the binder resins. If the proportion of resin particles [L] used is less than 0.1 part by weight, the effect of improving water retention will be diminished. If the amount exceeds 30 parts by weight, the electrophotographic properties may deteriorate, which is particularly a concern when used for semiconductor laser light.

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 (No. 8)
Page 12, C. J. Young et al.: RCA Revi
ew 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 Journal pp. 66, 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35,
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, cited in reviews such as p. 208 (1972),
Examples include xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, sityryl dyes, etc.), phthalocyanine dyes (which may contain metals), 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.

[0321] Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region, JP-A-47-840, JP-A-47-44180, and JP-A-51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 361954, U.S. Patent No. 4175956
Specifications of each issue, “Research Disclosure
re'', 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

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

[0323] 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.

[0324] The thickness of the photoconductive layer is 1 to 100μ, especially 1
0 to 50μ is suitable.

[0325] When a photoconductive layer is used as the charge generation layer of a photoreceptor 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.

[0327] 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.

[0329] 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.

[0330] In order to produce printed matter using the electrophotographic printing original plate of the present invention, a copy image is formed on the electrophotographic printing original plate having the above-mentioned structure by a conventional method, and then the non-image area is desensitized. Created.

[0331] The desensitization treatment provided in the present invention includes a method in which the resin particles of the present invention are hydrolyzed by passing through a treatment liquid;
Examples include a method in which hydroxyl groups are generated by decomposition by redox reaction or light irradiation, or a method in which resin particles are hydrophilized and zinc oxide is desensitized with a desensitization treatment liquid. .

In the latter case, 1. 2. Desensitizing zinc oxide particles and resin particles at the same time; After desensitizing the zinc oxide particles, decomposition treatment is performed on the resin particles; 3. Any procedure can be used, such as decomposing the resin particles and then subjecting the zinc oxide particles to a desensitization reaction.

[0333] 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.

[0335] The method for desensitizing the resin particles, ie, the method for decomposing the protected hydrophilic groups, is arbitrarily selected depending on the decomposition reactivity of the protected hydrophilic 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 also possible, and known compounds can be used as these compounds, such as hydrazine hydrate, zincate, lipoic acid, hydroquinones, formic acid, etc. , thiosulfate, hydrogen peroxide, persulfate, quinones, and the like.

[0336] 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.

[0337] 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.

[0338] 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 specific functional groups by light irradiation, it is possible to add a step of light irradiation with "chemically active light" sometime after obtaining a toner image during plate making. Bye. That is, after electrophotographic development, light irradiation may be performed during fixing of the toner image, or other conventionally known fixing methods such as heat fixing, pressure fixing,
After fixing by solvent fixing or the like, light irradiation is performed.

[0340] 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 1 to 10 seconds is sufficient.

0341]

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

0342]

[Chemical formula 110]

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

0344

[Table 2]

0345]

[Table 3]

0346]

[Table 4]

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

0348

[Table 5]

0349]

[Table 6]

0350]

[Table 7]

Synthesis example 25 of resin [A]: [A-25] 1
-Naphthyl methacrylate 95.5g, methacrylic acid 0
．． 5g, toluene 150g and isopropanol 50g
The mixed solution was heated to 80° C. under a nitrogen stream. 4,4'-Azobis(4-cyano)valeric acid (abbreviated as A.C.
．． V. ) and stirred for 5 hours. Furthermore, A. C.
V. Add 1g of A. for 2 hours, then add A. C. V. 1g of
The mixture was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5 x 103.

0352]

[Chemical formula 111]

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

0354]

[Chemical formula 112]

Synthesis Example 27 of Resin [A]: [A-27] A mixed solution of 95 g of benzyl methacrylate, 4 g of thioglycolic acid, and 200 g of toluene was heated at a temperature of 75 g under a nitrogen stream.
Warmed to ℃.

0356 A. C. V. After adding 1.0 g of A. and reacting for 6 hours, further A. C. V. 0.4g of was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 7.8×10
It was 3.

0357]

[Chemical formula 113]

[0358] Next, specific examples of the production of dispersion stabilizing resin (monofunctional polymer) for resin particles and resin particles will be illustrated.

Production example 1 of dispersion stabilizing resin (monofunctional polymer): [M-1] 95 g of 2,2,2,2',2',2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid, and A mixed solution of 200 g of toluene was heated to 70° C. while stirring under a nitrogen stream. 1.0 g of azobisisobutyronitrile (abbreviated as A.I.B.N.) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine and t
-Add 0.5g of butylhydroquinone, temperature 100℃
The mixture was stirred for 12 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight of the polymer [M-1] was 4,000.

0360]

[Chemical formula 114]

Production example 2 of dispersion stabilizing resin (monofunctional polymer): [M-2] A mixed solution of 96 g of monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was added. , and heated to a temperature of 70° C. under a nitrogen stream. A. I. B. N.
1.0 g was added and reacted for 8 hours. The reaction solution was then cooled in a water bath to a temperature of 25°C, and 10 g of 2-hydroxyethyl methacrylate was added thereto. Dicyclohexylcarbonamide (abbreviation D.C.C.) 15g, 4
A mixed solution of 0.2 g of -(N,N-dimethylamino)pyridine and 50 g of methylene chloride was added dropwise with stirring over 30 minutes, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added and after stirring for 1 hour, the precipitated insoluble matter was filtered off, and the filtrate was reprecipitated into 1 liter of n-hexane. The precipitated viscous substance was collected by decantation, dissolved in 100 ml of tetrahydrofuran, and after filtering off the insoluble matter again, it was reprecipitated in 1 liter of n-hexane. The polymer obtained by drying the precipitated viscous material had a yield of 60 g and a weight average molecular weight of 5.2 x 103.

0362]

[Chemical formula 115]

0363]

[Chemical formula 116]

Production example 3 of dispersion stabilizing resin (monofunctional polymer): [M-3] A mixed solution of 95 g of monomer [MA-2] having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated with nitrogen. The mixture was heated to a temperature of 75° C. with stirring under a stream of air. 2 g of 4,4'-azobis(4-cyanovaleric acid) (abbreviation A.C.V.)
was added and reacted for 8 hours. After cooling, the resulting polymer was reprecipitated into 1 liter of methanol and dried. Next, this polymer 5
0 g and 11 g of 2-hydroxyethyl methacrylate,
It was dissolved in 150 g of benzotrifluoride, and the temperature was set to 25°C. Add D. to this mixture under stirring. C. C. 15g, 4-(
A mixed solution of 0.1 g of N,N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. After that, 3 g of formic acid was added and stirred for 1 hour. The precipitated insoluble matter was filtered off, and the filtrate was diluted with 80% methanol.
It was reprecipitated in 0 ml. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to obtain 30 g of a viscous substance. The weight average molecular weight of polymer [M-3] is 3
．． It was 3×104.

0365]

[Chemical formula 117]

0366]

[Chemical formula 118]

Production Examples 4 to 22 of dispersion stabilizing resin (monofunctional polymer): [M-4] to [M-22] In Production Example 2, other monomers were used instead of monomer (MA-1). mer (monomer corresponding to the polymer component listed in Table 4).
Each dispersion stabilizing resin [M] was produced in the same manner as in Production Example 2. Each weight average molecular weight is 4 x 103 ~ 6 x 108
Met.

0368

[Table 8]

0369]

[Table 9]

0370]

[Table 10]

0371]

[Table 11]

[0372] Production examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [M-23] to [M-30] In production example 2 of dispersion stabilizing resin, monomer (MA-1) and 2-
Each dispersion stabilizing resin [M] was produced in the same manner except that hydroxyethyl methacrylate was replaced with a compound corresponding to each of the polymers in Table 5 below. Each weight average molecular weight was 5 x 103 to 6 x 103.

0373]

[Table 12]

0374]

[Table 13]

0375]

[Table 14]

[0376] Production example 31 of resin for dispersion stabilization: [M-31
] 30 g of octyl methacrylate, a monomer with the following structure (M
A-3) A mixed solution of 70 g of 3 g of glycidyl methacrylate and 200 g of benzotrifluoride was heated to a temperature of 75° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (A.I.B.N.) was added and reacted for 4 hours, and then A.I.B.N. I. B. N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110° C. for 8 hours. After cooling, it was reprecipitated into 2 liters of methanol, and a slightly brownish oil was collected and dried. The yield was 73 g, and the weight average molecular weight was 3.6 x 104.

0377]

[Chemical formula 119]

Production Example 32 of Dispersion Stabilizing Resin: M-32 A mixed solution of 80 g of the following monomer MA-4, 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol, and 300 g of tetrahydrofuran was heated at a temperature of 60°C while stirring under a nitrogen stream. Warmed to ℃. 2,2' to this
-Mazobis(isovaleronitrile) (abbreviation: A.I.V.
．． N. ) was added and reacted for 4 hours, and further A. I. V
．． N. 0.4 g was added and reacted for 4 hours. After cooling the reaction mixture to a temperature of 25° C., 4 g of methacrylic acid was added and D. C. C. 6g, 4-(N,N-dimethylamino)pyridine 0.1g and methylene chloride 1
5 g of the mixed solution was added dropwise over 1 hour, and the mixture was stirred for an additional 3 hours. Next, 10 g of water was added, and the mixture was stirred for 1 hour. After filtering off the precipitated insoluble matter, the filtrate was reprecipitated in 1 liter of methanol to collect the oily matter. Furthermore, this oil is mixed with benzene.
After dissolving in 150 g and filtering off insoluble matter, add 1 ml of methanol again.
The oil was collected and dried. Yield is 5
The weight average molecular weight was 8 x 103 at 6 g.

0379]

[Chemical formula 120]

[0380] Production examples 33 to 39 of resin for dispersion stabilization: M-
33-M39 By performing the reaction shown in Production Example 32, the following Table-6
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.

0381]

[Table 15]

0382

[Table 16]

0383

[Table 17]

Production Example 1 of Resin Particles: [L-1] 10 g of dispersion stabilizing resin [M-32] and 20 g of methyl ethyl ketone
0 g of the mixed solution was heated to 60° C. with stirring under a nitrogen stream. To this, 40 g of the following monomer [C-1], 10 g of ethylene glycol dimethacrylate, A. I. V.
N. A mixed solution of 0.5 g and 240 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was continued for 2 hours. Further 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 0.20 μm. (:
CAPA-500 (particle size measurement made by Horiba, Ltd.)

0385]

[Chemical formula 121]

[0386] Production examples 2 to 11 of resin particles: [L-2] to
[L-11] In Production Example 1 of resin particles, each monomer in Table 7 below was used instead of resin [M-32] and monomer [C-1]. Resin particles were produced in the same manner. The average particle size of each particle was within the range of 0.15 to 0.30 μm.

0387]

[Table 18]

0388

[Table 19]

0389]

[Table 20]

[0390] Production examples 13 to 23 of resin particles: [L-13
] ~ [L-23] Resin particles were produced in the same manner as in Production Example 1 of Resin Particles, except that in place of 2.5 g of ethylene glycol diacrylate, a polyfunctional compound shown in Table 8 below was used. L-
13] to [L-23] were produced. The polymerization rate of each particle was 95 to 98%, and the average particle size was 0.15 to 0.25 μm.

0391

[Table 21]

Production example 24 of resin particles: [L-24] 8 g of dispersion stabilizing resin [M-35] and 1 methyl ethyl ketone
30 g of the mixed solution was heated to 60° C. with stirring under a nitrogen stream. To this, 45 g of the following monomer [C-13], 5 g of diethylene glycol dimethacrylate, 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 0.25μ through a 200 mesh nylon cloth.
It was m.

0393

[Chemical formula 122]

Production Example 25 of Resin Particles: [L-25] A mixed solution of 7.5 g of dispersion stabilizing resin [M-26] and 230 g of methyl ethyl ketone was heated for 60 hours with stirring under a nitrogen stream.
Warmed to ℃. To this, 22 g of monomer [C-12], 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,
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 0.25 μm. Production example 26 of resin particles: [L-26] 42 g of the following monomer [C-14], 8 g of ethylene glycol diacrylate, 8 g of dispersion stabilizing resin [M-27]
and 230 g of dipropyl ketone under a nitrogen stream at a temperature of 60°C.
The solution was added dropwise over 2 hours to a solution of 200 g of dipropyl ketone heated to 2 hours with stirring. After reacting for 1 hour, A. I. V. 0.3 g of N 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 0.20 μm.

0395]

[Chemical formula 123]

[0396] Production examples 27 to 36 of resin particles: [L-27
] ~ [L-36] In Production Example 26 of resin particles, dispersion stabilizing resin [M-
Particles were produced in the same manner as in Production Example 12, except that each dispersion stabilizing resin shown in Table 9 below was used instead of [27]. The average particle size of each particle was in the range of 0.20 to 0.25.

0397]

[Table 22]

[0398] Production examples 37 to 42 of resin particles: [L-37
] ~ [L-42] In Production Example 25 of resin particles, monomer [C-12],
Acrylamide and reaction solvent: Particles were produced in the same manner as in Production Example 13, except that the compounds shown in Table 10 below were used instead of methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 to 0.30.

0399]

[Table 23]

0400]

[Table 24]

Example 1 and Comparative Examples A to B Example 1 6 g (as solid content) of resin [A-4], 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.

0402]

[Chemical formula 124]

0403]

[Chemical formula 125]

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 Manufacturing Example 1 of Resin Particles: In L-1, a resin having the following structure was used instead of 10 g of the dispersion stabilizing resin [M-32]. It was synthesized in the same manner as in 1. The average particle size of the obtained latex was 0.17 μm.

0405]

[Chemical formula 126]

Comparative photoreceptor Example 1 was used except that 1.0 g (as solid content) of resin particles [LR-1] was used instead of 1.0 g of resin particles [L-1] in Example 1. An electrophotographic light-sensitive material was produced in the same manner as described above. The film properties (surface smoothness), electrostatic properties, desensitization of the photoconductive layer (represented by the contact angle with water of the photoconductive layer after desensitization treatment), and printability of these photosensitive materials were investigated. Ta. 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 Hamada Star 800SX manufactured by Hamada Star Co., Ltd.) The above results are summarized in Table 11.

0407]

[Table 25]

[0408] The implementation of the evaluation items listed in Table 11 is as follows. Note 1) Smoothness of photoconductive layer: The smoothness (sec/cc) of the obtained photosensitive material was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air volume of 1 cc. It was measured. Note 2) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH (environmental conditions [I]), each photosensitive material was tested with a paper analyzer (Paper Analyzer-SP manufactured by Kawaguchi Electric Co., Ltd.).
-428 type) for 20 seconds at -6 kV, and then allowed to stand for 10 seconds, and the surface potential V10 at this time was measured. Next, the potential V130 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 [D. R. R. (
%)] was calculated as [(V130/V10)×100(%)].

[0409] Furthermore, corona discharge can cause the surface of the photoconductive layer to -
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.

[0410] Similar measurements were carried out under the conditions of a temperature of 30°C and a RH of 65%. (: Environmental conditions [II]) Note 3)
Imaging properties: Each photosensitive material was left for one day and night under environmental conditions I or II. Next, it is charged with -5kV and used as a light source with 2.8mW.
Output gallium-aluminum-arsenic semiconductor laser (
5 on the surface of the photosensitive material using an oscillation wavelength of 780 nm).
After exposure at a irradiation dose of 0 erg/cm3, a pitch of 25 μm, and a scanning speed of 330 m/sec, ELP-T (Fuji Photo Film Co., Ltd.) was used as a liquid developer.
Copied images obtained by developing and fixing the images were visually evaluated for fogging and image quality. Note 4) Water retention of raw plate: The degree of hydrophilicity due to desensitization treatment when a photosensitive material is used as a printing original plate was investigated under the following forced conditions.

[0411] Each photosensitive material itself (original plate without plate making:
That is, an aqueous solution prepared by diluting a desensitizing treatment liquid ELP-EX (produced by Fuji Photo Film Co., Ltd.) five times with distilled water was passed through an etching machine once. Further, this was immersed in a treatment solution E-1 having the following formulation at a temperature of 35° C. for 3 minutes. Next, these plates were printed using Hamada Star 8005X model manufactured by Hamada Star Co., Ltd., and 5
The presence or absence of scumming on the 0th printed sheet was visually evaluated. Desensitizing treatment liquid: E-1 Monoethanolamine
60g
Neosoap (manufactured by Matsumoto Yushi Co., Ltd.)
8g
benzol 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) Scratching of printed matter: After each photosensitive material was plate-made in the same manner as in Note 3) above, it was passed through an etching machine once using ELP-EX, and then the monoethanolamine-containing aqueous solution of Note 4) was applied. After soaking for 3 minutes, it was washed with water. These original plates for offset masters were printed using a 5-fold dilution of the monoethanolamine-containing liquid as a dampening solution, and the number of prints until background smear on the printed matter could be visually determined was determined.

As shown in Table 11, the photosensitive materials of the present invention and Comparative Example B had good smoothness and electrostatic properties of the photoconductive layer, and the actual copied images had no background fog and the quality of the copied images was clear. Ta.

[0413] Next, when used as an offset master original plate, a photosensitive material that was not made into a plate was desensitized by diluting the desensitization treatment solution under severe conditions, and the water retention was examined by actually printing. The product of the present invention showed good water retention without scumming from the beginning of printing, and even when the original plate actually made was used, 5,000 clear prints without scumming were obtained. On the other hand, in Comparative Example B, in which known comparative resin particles LR-1, which does not have a surface concentration effect, were added, the water retention was insufficient, and background stains on printed matter occurred from the beginning of printing and disappeared even after printing. It was never done.

[0414] In Comparative Example A, the electrostatic properties were significantly deteriorated, and a copy image that was satisfactory in terms of actual imaging performance could not be obtained. On the other hand, the water retention property as an offset master plate was almost good. However, the image quality of printed matter obtained from actual plate making is not satisfactory from the start of printing due to background stains in non-image areas during plate making or deterioration of image quality in image areas (missing thin lines, fine letters, etc.). I couldn't get anything.

From the above, it can be seen that an electrophotographic photoreceptor that satisfies the electrostatic properties and printing properties can be obtained only when both the resin [A] and the resin particles [L] of the present invention are used. Example 2 Resin [A-25] 5.5 g (as solid content), resin [B-2] having the following structure 32.5 g, resin particles [L-24]
2g (as solid content), methine dye [II
] An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except for 0.02 g.

0416]

[Chemical formula 127]

0417]

[Chemical formula 128]

The electrophotographic properties and printing suitability of the obtained photosensitive material were measured in the same manner as in Example 1, and the following results were obtained. Electrostatic characteristics (30℃, 80%RH) V10: -620VD. R. R.
: 83% E1/10 : 28erg/cm2 Imaging performance I (20°C, 65%RH): Good II
(30℃, 80%RH): Good water retention:
◎ Good printing durability: Both electrostatic properties and printability were good, as it was printed over 5,000 sheets. Examples 3 to 22 5 g each (as solid content) of resin [A] shown in Table 12 below,
2 g of resin particles [L] (as solid content), 33 g of resin [B-3] with the following structure, and 0.01 g of methine dye [III]
Each photosensitive material was prepared in the same manner as Resin 1 except for 8 g.

0419]

[Chemical formula 129]

0420]

[Chemical formula 130]

0421]

[Table 26]

[0422] Electrostatic properties, imaging properties, and printing properties are shown in Example 1.
The evaluation was performed in the same manner as above. However, in evaluating the printing characteristics, instead of the resin particle desensitization treatment liquid E-1 of Example 1, a treatment liquid E-2 having the following formulation was used.

[0423] Desensitizing treatment liquid: E-2 diethanolamine
60g
Neosoap (manufactured by Matsumoto Yushi Co., Ltd.)
10g
Methyl ethyl ketone
Dissolve 70g in distilled water to make a total volume of 1 liter, and adjust to pH 1 with potassium hydroxide.
It was adjusted to 0.5.

[0424] Each of the photosensitive materials showed almost the same properties as Example 1 in terms of electrostatic properties, imaging properties, and printing properties, giving very good results. Example 23 and Comparative Example C 5 g of resin [A-1], 34 g of resin [B-4] with the following structure
, resin particles [L-6] 1.2g, zinc oxide 200g, uranine 0.02g, rose bengal 0.04g, bromophenol blue 0.03g, phthalic anhydride 0.20g
and 300 g of toluene in a homogenizer,
Rotation speed 1×104 r. p. m. Dispersion was carried out for 5 minutes to prepare a photosensitive layer-forming product, which was coated on electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/m 2 and dried at 110° C. for 1 minute. Then, in the dark at 20℃, 6
The electrophotographic photoreceptor shown in Table 13 below was prepared by leaving it for 24 hours under the condition of 5% RH.

0425]

[Chemical formula 131]

Comparative Example C In Example 23, 5 g of resin [A-1] and resin [B-
4] An electrophotographic photoreceptor was produced in the same manner as in Example 23, except that 40 g of resin [B-4] was used instead of 34 g, and resin particles [L-6] were omitted.

The characteristics of each photoreceptor were examined in the same manner as in Example 1, and the results are listed in Table 13.

0428]

[Table 27]

[0429] In the above measurements, the electrostatic properties and imaging properties were carried out in the same manner as in Example 1, except that the following operations were followed. Note 7) Method for measuring E1/10 of electrostatic properties: After the surface of the photoconductive layer is charged to -400 V by corona discharge, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux,
The time required for the surface potential (V10) to attenuate to 1/10 is determined, and the exposure amount E1/10 (lux/second) is calculated from this. Note 8) Imaging properties: After each photosensitive material was left for one day and night under the following environmental conditions, it was plate-made using a fully automatic plate-making machine ELP-404V (manufactured by Fuji Photo Film Co., Ltd.) using ELP-T as a toner. The copied images were visually evaluated for fogging and image quality. Environmental conditions during imaging were 20°C and 65%
RH(I) and 30°C, 80% RH(II).

As shown in Table 13, the photosensitive material of the present invention exhibited good electrostatic properties and imaging properties. However, resin [
In Comparative Example C, which does not use A], there was no significant difference in electrostatic properties, but when we actually captured and evaluated the copied images, we found that there was a decrease in image quality (decreased density), especially in high temperature and high humidity. , thin lines/missing characters) slightly occurred.

[0431] When used as an offset master original plate, the present invention had good water retention and printing durability of up to 5,000 sheets. However, Comparative Example C, which did not contain resin particles, did not have sufficient water retention under forced hydrophilic conditions, and when it was actually desensitized and printed under normal conditions, background smudges occurred in non-image areas. No visible prints were obtained.

From the above, only the photosensitive material of the present invention was able to maintain excellent performance in both electrostatic properties and printing properties. Examples 24 to 31 In Example 23, 5 g of resin [A] shown in Table 14 below (
Each photosensitive material was prepared in the same manner as in Example 23 except that the resin particles [L] were 1 g (as solid content), the resin [B] was 34 g.

0433]

[Table 28]

[0434] All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and actual copied images are
Even under harsh conditions (30°C, 80% RH), it provided clear images without background fog or skipped fine lines.

[0435] Further, when printing was performed as an offset master original plate, a printed matter with clear image quality and no scumming was obtained even after printing 5,000 sheets. Example 32 Resin [A-10] 6g, resin [B-5] 29 with the following structure
．． 2g, resin [B-6] 4g, photoconductive zinc oxide 200
g, a mixture of 0.020 g of dye [III] having the following structure, 0.18 g of salicylic acid, and 300 g of toluene was heated in a homogenizer at a rotation speed of 6×10 3 r.g. p. m. The mixture was dispersed for 10 minutes. Add 0.9 resin particles [L-10] to this dispersion.
g (as solid content), 0.01 g of 3,3',5,5'-benzophenonetetracarboxylic dianhydride and 0.005 g of o-chlorophenol were added, and the number of revolutions was 1 x 10.
3 r. p. m. Dispersion was performed for 1 minute. The dry adhesion amount of this dispersion for forming a photosensitive layer was 25 g/m2 on electrically conductive treated paper.
It was coated with a wire bar so that Then in the dark 2
An electrophotographic light-sensitive material was prepared by leaving it for 24 hours under conditions of 0° C. and 65% RH.

0436]

[Chemical formula 132]

0437]

[Chemical formula 133]

0438]

[Chemical formula 134]

[0439] This photosensitive material was passed once through an etching processor using ELP-FX (manufactured by Fuji Photo Film Co., Ltd.), and then a desensitizing treatment liquid (E-
3) for 5 minutes for desensitization treatment.

[0440] Desensitizing treatment liquid (E-3) Diethanolamine
52g
Nucor B4SN (Nippon Nyukazai Co., Ltd.)
) 10g methyl ethyl ketone
80g of these were dissolved in distilled water and adjusted to pH 10.5 with sodium hydroxide to make a total volume of 1.0 liters.

[0441] Place a drop of 2 μl of distilled water on this,
The formed contact angle with water was measured with a goniometer and was found to be 10° or less. The contact angle before the desensitization treatment was 106°, clearly indicating that the surface layer of the photosensitive material was made very well hydrophilic.

[0442] On the other hand, this electrophotographic light-sensitive material was
was made into a plate using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using a developer to form a toner image, which was desensitized under the same conditions as above and used as an offset master and as a dampening solution. A solution obtained by diluting the above E-3 50 times with water was used to print on high-quality paper using an offset printing machine (Model 52, manufactured by Sakurai Seisakusho Co., Ltd.).

[0443] The number of prints that could be printed without causing problems with scumming in the non-image areas and image quality in the image areas was 5,000. Furthermore, this photosensitive material was heated at (45°C, 75%RH)
) After being left under the environmental conditions for 3 weeks, the same treatment was performed, but there was no difference at all from before. Example 33 In Example 1, 2.0 g of resin particles [L-12] (as solid content) was used instead of 1.0 g of resin particles [L-1].
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that .

Next, in the same manner as in Example 1, a plate was made using ELP-404V using ELP-T developer. This version is 40
Using a 0W high-pressure mercury lamp as a light source, 5
It was irradiated with light for a minute. Furthermore, using a desensitizing treatment solution prepared by diluting ELP-EX twice with water, it was passed through an etching processor once. The non-image area of each printing master plate subjected to the desensitization treatment in this manner was sufficiently hydrophilized with a contact angle with water of 10° or less. Furthermore, when printing was carried out in the same manner as in Example 1, even on the 5,000th print, the printed matter had clear image quality without background smearing. Examples 34 to 37 In Example 32, 29.2 g of resin [B-5] was
5 g, and each resin particle [L] in Table 15 below was changed to 5 g (as solid content) instead of 0.8 g of the resin particle [L-10]. An electrophotographic light-sensitive material was produced.

0445]

[Table 29]

[0446] In the same manner as in Example 1, 5 g of polymethyl methacrylate particles (particle size 0.3 μm) were dispersed as toner particles in 1 liter of Isopar H (Esso Standard) using a fully automatic plate making machine ELP404V, and the charge was adjusted. When a plate was made using a liquid developer prepared by adding 0.01 g of soybean oil lecithin as an agent, the density of the obtained master original plate for offset printing was 1.0 or more and the image quality was clear.

[0447] Further, the master original plate after plate making was immersed for 30 seconds in a desensitizing liquid (E-4) prepared according to the following formulation, and then washed with water to perform a desensitizing process. Desensitizing treatment liquid (E-4) Boric acid

55g Neo Soap (Matsumoto Yushi (
Co., Ltd.) 8g
benzyl alcohol
80g of these were dissolved in distilled water to make a total volume of 1.0 liters, and the solution was adjusted to pH 11.0 with sodium hydroxide. The contact angle of the non-image area with distilled water was 10° or less, indicating that it was sufficiently hydrophilized. When these original plates for offset printing were printed using a printing machine, the printed matter after printing 5,000 copies had no fog in the non-image area and the image was clear.

0448]

According to the present invention, it is possible to obtain an original plate for electrophotographic lithographic printing which has excellent printed images and high printing durability even under severe conditions. Further, the lithographic printing 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]: has a weight average molecular weight of 1 x 103 to 2 x 104, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and has a polymer main chain fragment. At the end, -PO3 H2, -SO3 H, -
At least one polar group selected from COOH, -P(=O)(OH)R01 [R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group]] and a cyclic acid anhydride-containing group A resin made by combining [In formula (I) above, a1 and a2 each represent 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: in a non-aqueous solvent, they are soluble in the non-aqueous solvent but become insolubilized by polymerization;
Thiol groups, sulfo groups, amino groups and -P(
=Z0)(-Z0-H)R'1 group [Z0 represents an oxygen atom or a sulfur atom. R' 1 is -Z0
-H, hydrocarbon, or -Z0 -R' 2 (R'2 represents a hydrocarbon group)]
The monofunctional monomer (C) containing at least one functional group that forms one group is soluble in the solvent, and contains at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom. Copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin. 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 -COO
R05 (R04 and R05 each represent a hydrocarbon group having 1 to 10 carbon atoms), and L1 and L2 each represent -CO
The number of single bonds or connected atoms connecting O- and the benzene ring is 1 or more
Represents 4 linking groups] 3. The electrophotographic lithographic printing original plate according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 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,
Halogen atom, cyano group, hydrocarbon group, -COO-R2
or -COO-R2 (R2 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group]