JPH04366848A - Original plate for electrophotographic planographic printing - Google Patents

Abstract

PURPOSE:To improve dark charge holdability and photosensitivity by incorporating and specific resin as a binder resin into the original plate and incorporating the nonaq. solvent type dispersing resin particles having the particle sizes smaller than the max. particle size of photoconductive zinc oxide particles into a photoconductive layer. CONSTITUTION:This original plate contains the resin which has 1X10<3> to 2X10<4> weight average mol.wt., contains >=30wt.% repeating unit expressed by formula I and contains the polar group selected from -PO3H2-, -SO3H and cyclic acid anhydride-contg. group, etc., as the binder resin. In the formula I, a1, a2 denote a hydrogen atom, halogen atom, cyano group, etc.; R3 denotes a hydroarbon group. Further, the plate contains the nonaq. solvent type dispersing resin particles having the particle sizes smaller than the max. particle size of the photoconductive zinc oxide particles in the photoconductive layer. These resin particles are obtd. by bringing a monofunctional monomer which is soluble in the nonaq. solvent but is insolubilized therein when polymerized and contains a functional group forming a thio group, phosphono group, etc., when decomposed into a polymn. reaction in the nonaq. solvent in the presence of the resin for stabilizing dispersion soluble in the solvent.

Description

[Detailed description of the invention]

0001

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

0002

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

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset original 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 has water resistance, and the surface conductive layer with the image does not separate during printing, and it absorbs well with dampening water, and the non-image area is sufficiently coated to prevent staining even if the number of prints increases. retaining hydrophilicity;
It is necessary to have the following performance.

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

[0005]

[Problems to be Solved by the Invention] However, even if the above-mentioned resin is said to be effective in improving desensitization property, when actually evaluated, it is still not satisfactory in terms of scumming and printing durability. It wasn't. Furthermore, JP-A-1-232356,
Publications No. 1-261657 describe that adding resin particles containing hydrophilic groups to the photoconductive layer is effective in improving water retention.

[0006] It has been confirmed that water retention can be significantly improved by improving these photoconductive compositions. However, when we evaluate it in more detail as a lithographic printing original plate, we find that during environmental changes (high temperature/high humidity or low temperature/low humidity),
Electrophotographic properties (particularly charge retention in the dark, photosensitivity, etc.) fluctuated, and there were cases in which stable and good copied images could not be obtained. This resulted in deterioration of the printed image of printed matter using this as a printing original plate, or a decrease in the scumming prevention effect.

[0007] Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate used as a digital direct lithography printing original plate, the time is longer than when the entire surface is simultaneously exposed using visible light. 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 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. In other words, object 1 of the present invention is to have excellent electrostatic properties (particularly dark charge retention and photosensitivity), to reproduce a copy image that is faithful to the original image, and to be able to reproduce a copy image that is faithful to the original image, as well as to prevent uniform background smudges over the entire surface as an offset master. An object of the present invention is to provide a lithographic printing original plate which does not cause even dotted background stains and has excellent desensitization properties. A second object of the present invention is to provide a lithographic printing original plate that produces clear and high-quality images even when the environment during copy image formation fluctuates, such as low temperature and low humidity, or high temperature and high humidity. A third object of the present invention is to provide a lithographic printing original plate that is not easily affected by the types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even in a scanning exposure method using semiconductor laser light.

0010

[Means for Solving the Problems] The present invention achieves the above object by providing at least one photoconductive layer containing photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin on a conductive support. The electrophotographic lithographic printing original plate contains at least one of the following resins [A] as the binder resin, and the photoconductive layer further contains particles having a maximum particle size equal to or larger than the maximum particle size of the photoconductive zinc oxide particles. This can be achieved by using an original plate for electrophotographic lithographic printing, which is characterized by containing at least one type of non-aqueous solvent-based dispersed resin particles described below having a particle size smaller than that.

Resin [A]: 1×103 to 2×104
It has a weight average molecular weight of 30% by weight or more as a polymer component of repeating units represented by the following general formula (I), and -PO3 H2, -SO at one end of the polymer main chain.
3H, -COOH,

embedded image A resin containing at least one polar group selected from [R1 represents a hydrocarbon group or -OR2 (R2 represents a hydrocarbon group)] and a cyclic acid anhydride-containing group. General formula (I)

embedded image [However, in the above general formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R3 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles: In a non-aqueous solvent, they are soluble in the non-aqueous solvent but become insolubilized by polymerization.
By decomposition, thiol group, phosphono group, amino group,

[Chemical 1
0. A polymer resin obtained by dispersing and polymerizing a monofunctional monomer (A) containing at least one functional group that forms a group in the presence of a dispersion stabilizing resin soluble in the solvent. particle. Furthermore, it is preferable that the resin particles form a high-order network structure.

Furthermore, the resin [A] preferably has the general formula (I)
The copolymer component represented by contains at least one of the aryl group-containing methacrylate components represented by the following general formula (Ia) or the following general formula (Ib). General formula (Ia)

[Chemical formula 11] General formula (Ib)

embedded image [However, in the above formula (Ia) or (Ib), T1
and T2 are each independently a hydrogen atom and a carbon number of 1 to 1
0 hydrocarbon group, chlorine atom, -COR4 or -COO
R5 (R4 and R5 each represent a hydrocarbon group having 1 to 10 carbon atoms), L1 and L2 each represent -C
Number of single bonds or connected atoms connecting OO- and benzene ring: 1
~Represents 4 linking groups]

[0013] Furthermore, the above-mentioned dispersion stabilizing resin in the present invention contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. These are particularly preferred. General formula (II)

[Chemical formula 13] [In general formula (II), V0 is

embedded image (where p represents an integer of 1 to 4, R6 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), a3,
a4 may be the same or different, and a4 may be a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-R7
or -COO-R7 (R7 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group]

The lithographic printing original plate of the present invention contains at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin in the photoconductive layer that is the uppermost layer, and the non-image area of the photoconductive layer is This is a printing original plate that is treated with a desensitizing liquid to make the surface hydrophilic and used as a lithographic printing original plate.

The photoconductive layer of the present invention consists of photoconductive zinc oxide, a spectral sensitizing dye, and a specific copolymer component as a binder resin, and is a low molecular weight resin [A] having a polar group at the end of the main chain.
and non-aqueous solvent-based dispersed resin particles (hereinafter sometimes abbreviated as resin particles).

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

[0017] Furthermore, the resin particles contain at least a monofunctional monomer (A) containing a protected form of a specific hydrophilic group such as a thiol group, which has become insoluble in the non-aqueous solvent through a polymerization reaction. It is composed of a polymer component and a polymer component of a dispersion stabilizing resin that is soluble in the nonaqueous solvent and is physicochemically adsorbed and/or chemically bonded during this reaction. the above(
II) In the case of a dispersion stabilizing resin containing a polymerizable double bond group moiety represented by the formula, both polymer components are chemically bonded. In addition, in the insoluble polymer component of the resin particles, the protected functional groups undergo a chemical reaction through a hydrolysis reaction, a redox reaction, a photolysis reaction, etc. due to the desensitization treatment, and the above-mentioned specific hydrophilic groups are generated. , the properties of the particles are changed from hydrophobic to hydrophilic.

Another feature of the present invention is that the binder 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 -PO3 H2
,-SO3H,-COOH,

[Chemical formula 15] A polymer component having at least one polar group selected from [R1 represents a hydrocarbon or -OR2 (R2 represents a hydrocarbon)] and a cyclic acid anhydride-containing group is It is composed of a polymer bonded at a specific position, that is, at one end of the polymer main chain.

The photoconductive layer of the present invention contains photoconductive zinc oxide particles, a spectral sensitizing dye, and the resin particles. Due to the action of the resin [A] contained as a binder resin, the zinc oxide particles are The resin particles are further finely divided and uniformly dispersed, and the resin particles are also uniformly dispersed. Furthermore, the interaction between the zinc oxide particles and the spectral sensitizing dye takes place sufficiently, and in particular, even when the type of the dye changes, all the dyes sufficiently interact with the zinc oxide particles that are photoconductors. It is possible to form a state in which it is possible to For example, when using spectral sensitization for semiconductor laser light, which has been attracting particular attention in recent years, this interaction is not sufficient with known binder resin systems, and the actual electrophotographic properties (such as charge retention in the dark, photosensitivity, etc.) are not sufficient. etc.), and the captured copy image also deteriorates to the point where it is no longer of any practical use. The details of such a phenomenon are unknown. However, the system of the present invention is extremely superior in that such a phenomenon does not occur.

The reason for this is that in the present invention, when zinc oxide particles and spectral sensitizing dyes are dispersed in the coexistence of resin particles and resin [A], specific polar groups are bonded to specific positions. The polar groups of the low molecular weight resin [A] and the monodisperse, microscopic resin particles that produce specific polar groups (such as thiol groups) upon decomposition are based on the stoichiometric ratio of the photoconductive zinc oxide. It adsorbs to defects, and the coating and adsorption state of the surface of the zinc oxide particles is properly performed, which compensates for the trapping of photoconductive zinc oxide and dramatically improves the humidity characteristics. It is presumed that the particles are sufficiently dispersed and agglomeration is suppressed.

In the lithographic printing original plate of the present invention, the dispersion state even down to the microscopic state of the photoconductive zinc oxide including the spectral sensitizing dye is controlled for the first time by the appropriate presence of both the resin particles and the resin [A]. This is thought to have improved the electrophotographic properties (particularly the actual imaging performance) and made it possible to stably maintain good performance even under harsh conditions of high temperature and high humidity or low temperature and low humidity.

In other words, in this method, if the electrophotographic characteristics do not exhibit excellent performance, background smear will occur in the non-image area and the original reproducibility of the image area will deteriorate when copying images are formed, resulting in poor image quality of the printed matter. Therefore, it is particularly important that the non-image area be made sufficiently hydrophilic by the desensitizing treatment and have high water retention so as to prevent ink from adhering during printing. In the lithographic printing original plate of the present invention, the zinc oxide particles are desensitized by the desensitization treatment solution, and the resin particles are desensitized to generate hydrophilic groups from specific protected hydrophilic groups. By exhibiting hydrophilicity, the photoconductive layer is characterized in that it has a function of further improving water retention in the non-image area. It is presumed that the above-mentioned effects dramatically improve the water retention properties of the non-image areas of the printing master plate of the present invention. Furthermore, as mentioned above, resin [A
] It is thought that the particles to be made hydrophilic are dispersed in the photoconductive layer in an appropriate state, so that the hydrophilization of the zinc oxide particles and resin particles progresses easily, quickly and sufficiently.

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 or thin lines, or background fog in the non-image area may occur. Specifically, the resin particles of the present invention have a maximum particle size of 2 μm or less, preferably 0.5 μm or less. The average particle diameter of the particles is 0.8 μm or less, preferably 0.5 μm or less. Note that the smaller the particle size of the resin particles, the larger the specific surface area, which brings about good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, molecules It is preferable to use particles with a diameter of 0.001 μm or more, since this will be similar to the case of dispersion, and the effect of particles on improving water retention will be diminished.

Further, in the present invention, the resin particles are 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. The anchor effect of this part prevents it from being eluted with dampening water during printing.
Good printing characteristics can be maintained even when printing a large number of sheets. Furthermore, when the polymer component of the dispersion stabilizing resin contains a photo- and/or thermosetting functional group, chemical bonds are formed, making it possible to further suppress elution. Furthermore, in the present invention, resin particles forming a high-order network structure can further suppress dissolution in water, exhibit water swelling properties, and further improve water retention.

In the present invention, the resin particles that do not form a higher-order network structure or the resin particles that do have a higher-order network structure (hereinafter simply referred to as network resin particles) are photoconductive oxidized resin particles. It is preferably used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of zinc. If the amount of resin particles or network resin particles is less than 0.01 part by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 10 parts 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.

Next, the photoconductive layer of the electrophotographic material of the present invention will be explained in more detail. The photoconductive layer of the present invention is
It is characterized by containing at least one of the following resins [A] as a binder resin. The binder resin [A] is 30% by weight of a specific polymer component represented by the following general formula (I).
-PO3H at one end of the polymer main chain
2,-SO3H,-COOH,

[R1 is a hydrocarbon group, -OR2 group (R2 is a hydrocarbon group), a polar group selected from a cyclic acid anhydride group (hereinafter referred to as
It is a low molecular weight resin formed by bonding cyclic acid anhydrides (also referred to as polar groups). General formula (I)

[Formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group, and R3 represents a hydrocarbon group]

In the resin [A], the weight average molecular weight is 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. When the molecular weight of the resin [A] is less than 103, the film forming ability decreases and sufficient film strength cannot be maintained.
On the other hand, if the molecular weight is larger than 2 x 104, even if the resin of the present invention is used, it will not work under harsh conditions of high temperature and high humidity, low temperature and low humidity, especially in photoreceptors using near-infrared to infrared spectral sensitizing dyes. The fluctuations in dark decay retention and photosensitivity become somewhat large, and the effect of the present invention in obtaining stable copied images is diminished.

The proportion of the polymer component corresponding to the repeating unit of general formula (I) in the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the copolymer component containing a polar group is 0.5 to 20% by weight, preferably 1 to 10%
Weight%. If the amount of the polar group-containing component in the resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the amount of the polar group-containing component is more than 20% by weight, the dispersibility decreases no matter how low the molecular weight is, and furthermore, background smudge increases when used as an offset master.

Further, as the low molecular weight resin [A], 2 represented by the above-mentioned general formula (Ia) or general formula (Ib) is used.
Contains a methacrylate component having a specific substituent at position and/or 6-position, an unsubstituted benzene ring, or an unsubstituted naphthalene ring, with a polar group bonded to one end Particularly preferred is a resin [A] (hereinafter, this low molecular weight product will be referred to as a resin [A']). Formula (Ia) and/or formula (
The proportion of the methacrylate copolymer component corresponding to the repeating unit Ib) is 30% by weight or more, preferably 50 to 9% by weight.
7% by weight, the proportion bonded to one end of the polymer main chain is 0.5 to 15% by weight based on 100 parts by weight of resin [A'],
Preferably it is 1 to 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-R3', or a carbonized -CO via hydrogen group
O-R3'(R3' represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, specifically, represents the same content as that described for R3 below). -COO-R via the above hydrocarbon
Examples of the hydrocarbon in the 3' group include a methylene group, an ethylene group, a propylene group, and the like. R3 represents a hydrocarbon group, specifically an alkyl group, an aralkyl group, or an aromatic group, preferably an aralkyl group or an aromatic group, which is a hydrocarbon group containing a benzene ring or a naphthalene ring. That is, R3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, Tetradecyl group, 2-
chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, etc.), optionally substituted with 2 to 18 carbon atoms Alkenyl group (
For example, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.)
, an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, naphthylmethyl group, 2
-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), substituted optional 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.).

In the copolymer component corresponding to the repeating unit of the general formula (I) which is a methacrylate component having such a substituent R3, it is more preferable to use the following general formula (
Ia) and/or a polymer component represented by a methacrylate component containing a specific aryl group represented by general formula (Ib). General formula (Ia)

[Chemical formula 18] General formula (Ib)

[Formula (Ia) and (Ib), T1 and T2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COR4, -COOR5 (
R4 and R5 each represent a hydrocarbon group having 1 to 10 carbon atoms. L1 and L2 each represent a direct bond connecting -COO- and a benzene ring or a linking group having 1 to 4 linking atoms]

In formula (Ia), T1 and T2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, and a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), aralkyl groups having 7 to 9 carbon atoms (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, silyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group) ), and -COR
4 and -COOR5 (preferred examples of R4 and R5 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), -CH2OCO-, -CH2CH2
A linking group having 1 to 4 linking atoms, such as OCO-, -(CH2)m1- (m1 represents an integer of 1 or 2), -CH2CH2O-, and more preferably a direct bond or a bonding atom. One to two linking groups can be mentioned.

Formula (Ia) used in the resin [A] of the present invention
Specific examples of copolymer components corresponding to the repeating units represented by ) or (Ib) are listed below. However, the scope of the present invention is not limited thereto. (a-1) below
~ (a-20), n is an integer of 1 to 4, m is 0 or an integer of 1 to 3, p1 is an integer of 1 to 3, R8 ~ R1
1 is -Cn H2n+1 or -(CH2)m
-C6 H5 (however, n and m are the same as above), X1
and X2 may be the same or different, and are a hydrogen atom, -
Represents either Cl, -Br, or -I. (a-1)

[C20] (a-2)

[C21] (a-3)

[C22] (a-4)

[C23] (a-5)

[C24] (a-6)

[C25] (a-7)

[C26] (a-8)

[C27] (a-9)

[C28] (a-10)

[C29] (a-11)

[C30] (a-12)

[Chemical formula 31] (a-13)

[C32] (a-14)

[Chemical formula 33] (a-15)

[C34] (a-16)

[C35] (a-17)

[C36] (a-18)

[C37] (a-19)

[C38] (a-20)

[C39]

Next, the specific polar group-containing polymer component contained in the low molecular weight resin [A] will be explained. The polar group is -PO3 H2, -SO3 H, -CO
Oh,

It is preferably at least one selected from embedded image and cyclic acid anhydride-containing groups.

[0036]

[Chemical Formula 41] Group means that the above R1 is a hydrocarbon group or -OR2 group (R
2 represents a hydrocarbon group), specifically R1 represents an aliphatic group having 1 to 22 carbon atoms (e.g. methyl group, ethyl group,
Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2-methoxymethyl 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 ary 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, acetyl group) phenyl group, butoxyphenyl group, etc.), and R
2 has the same content as R1.

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic anhydride, aromatic dicarboxylic anhydride, Things can be mentioned. Examples of aliphatic dicarboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, and cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo[2,2,2
] Octadicarboxylic acid anhydride rings, etc., and these rings may be substituted with, for example, halogen atoms such as chlorine atoms or bromine atoms, or alkyl groups such as methyl groups, ethyl groups, butyl groups, hexyl groups, etc. good. Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. is, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group,
It may be substituted with an alkoxycarbonyl group (eg, a methoxy group, an ethoxy group, etc.).

These polar groups may be directly bonded to one 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:

[Chemical formula 42] (d1 and d2 may be the same or different, and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group, a cyano group, an alkyl group (methyl group, ethyl group, 2-chloroethyl group) , 2-hydroxyethyl group, propyl group,
butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group),

[C4
3] (d3 and d4 represent the same content as d1 and d2),

[C44] -O-, -S-,

[Chemical formula 45] [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) 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, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.)], -C
O-, -COO-, -OCO-,

embedded image -SO2 -, -NHCONH-, -NHCOO-, -
NHSO2-, -CONHCOO-, -CONHCON
H-, heterocycle (any 5- to 6-membered ring containing at least one type of O, S, N, etc. as a heteroatom, or a condensed ring thereof; for example, a thiophene ring, a pyridine ring, a furan ring, an imidazole ring) ring, piperidine ring, morpholine ring, etc.) or

[Chemical formula 47] (d6 and d7 may be the same or different and represent a hydrocarbon group or -Od8 (d8 is a hydrocarbon group). These hydrocarbon groups include the same ones listed for d5. Examples include a linking group composed of a single linking group or a combination of these linking groups.

Furthermore, the low molecular weight resin [A] of the present invention ([A
']) is the general formula (I) (Ia) and/or
Alternatively, monomers other than these may be contained together with monomer (Ib) as a copolymerization component. Furthermore, the binder resin [A] preferably contains a copolymerization component represented by the above general formula (I) [including those represented by the general formula (Ia) or (Ib)], as well as a polymer copolymerized therewith. As a component, -P
O3 H2 -, -SO3 H-, -COOH-,

embedded image (R1′ means the same as R1 above) and a cyclic acid anhydride group. , is preferable in terms of further improving electrostatic properties. The specific polar group represents the same content as the polar group bonded to one end of the polymer main chain described above.

In the resin [A], the proportions of the polar groups contained as copolymer components and the polar groups bonded to one end of the polymer main chain are determined by It differs depending on the type and amount of the binder resin, resin particles, spectral sensitizing dye, chemical sensitizer, or other additives, and it is preferable to adjust the ratio as desired. What is important is that the total amount of both polar group-containing components is used within the range of 0.5 to 15% by weight. What is important in the resin [A] of the present invention is that the proportion of the specific polar group-containing component in 100 parts by weight of the total component amount of the resin [A] is in the range of 0.5 to 10% by weight as described above. being within the
Furthermore, in the resin [A], when it is present both in the polymer main chain component of the resin [A] and at one end of the main chain, it is arbitrarily divided within the range of the above-mentioned abundance ratio. Preferably, the proportion in the main chain component is 1.0 higher than that in the terminal component.
Therefore, the ratio is between 0.1 and 1.0.

The polar group-containing copolymer component of the present invention is
For example, any vinyl compound containing a polar group that can be copolymerized with a monomer corresponding to a repeating unit represented by general formula (I) [including general formulas (Ia) and (Ib)] may be used. For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (published in 1986). Specifically, acrylic acid, α and/or β
Substituted acrylic acid (e.g. α-acetoxy 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, ester derivatives of these carboxylic acids or sulfonic acids, compounds containing the polar group in the substituent of amide derivatives, 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 CH2 COOCH3,
R12 represents an alkyl group having 1 to 4 carbon atoms, R13 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. (b-1)

[C49] (b-2)

[C50] (b-3)

[C51] (b-4)

[C52] (b-5)

[C53] (b-6)

[C54] (b-7)

[C55] (b-8)

[C56] (b-9)

[C57] (b-10)

[C58] (b-11)

[C59] (b-12)

[C60] (b-13)

[C61] (b-14)

[C62] (b-15)

[C63] (b-16)

[C64] (b-17)

[C65] (b-18)

[C66] (b-19)

[C67] (b-20)

[C68] (b-21)

[C69] (b-22)

[C70] (b-23)

[C71] (b-24)

[C72] (b-25)

[C73] (b-26)

[C74] (b-27)

[C75] (b-28)

[C76] (b-29)

[C77] (b-30)

[C78] (b-31)

[C79] (b-32)

[C80] (b-33)

[Chemical formula 81] (b-34)

[C82] (b-35)

[Chemical formula 83] (b-36)

[Chemical formula 84] (b-37)

[Chemical formula 85] (b-38)

[C86] (b-39)

[Chemical formula 87] (b-40)

[Chemical formula 88] (b-41)

[Chemical formula 89] (b-42)

[C90] (b-43)

[Chemical formula 91] (b-44)

[C92] (b-45)

[C93] (b-46)

[C94] (b-47)

[C95] (b-48)

[C96] (b-49)

[C97] (b-50)

[C98] (b-51)

[C99] (b-52)

[Chemical formula 100]

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 these other monomers do not exceed 30% by weight in the resin [A].

In resin [A], a method for bonding a polar group to one end of the polymer main chain is a method in which various reagents are reacted with the end of a living polymer obtained by conventionally known anionic or cationic polymerization ( A method of radical polymerization using a polymerization initiator and/or a chain transfer agent containing a specific polar group in the molecule (a method of radical polymerization), or a method of ionic polymerization as described above A method of converting a polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) at the end obtained by a radical polymerization method into the specific polar group of the present invention by a polymer reaction. It can be easily produced by synthetic methods. Specifically, P. Dreyfuss, R. P. Quirk
, Encycle. Polym. Sci. Eng
．． , 7, 551 (1987), Yoshiki Chujo and Yuya Yamashita, Dyes and Medicines 30, 232 (1985), Akira Ueda and Susumu Nagai, Chemistry and Industry 60, 57 (1986), and other reviews and references cited therein. It can be manufactured by the method described in .

Specifically, the chain transfer agent used is:
For example, mercapto compounds (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid, 2
-Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptoacetic 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-mercaptobutane Sulfonic 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-mercaptoethyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, etc.), or iodination containing the above polar groups or substituents Examples include alkyl compounds (eg, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Examples of the polymerization initiator containing the polar group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid) and 4,4'-azobis(4-cyanovaleric acid). valeric acid chloride), 2,2'-azobis(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol), 2,2'-azobis[2-methyl-N
-(2-hydroxylethyl)-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.

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

[0049] Other resins used in combination have a weight average molecular weight of 3 x 104 to 1 x 106, preferably 5 x 104.
It is a medium to high molecular weight substance of ~5x105. Further, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C. For example, Ryuji Shibata and Jiro Ishiwata, Kobunshi, Vol. 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8)
), page 9, edited by Koichi Nakamura, "Practical technology of binders for recording materials", Chapter 10, C. H. C. Publication (published in 1985),
D. Tatt, S. C. Heidecker
, Tappi, 49 (No. 10), 439
(1966), E. S. Baltazzi, R.
．． G. Blanclotte et al., P.
hot. Sci. Eng. 16 (No. 5), 3
54 (1972), Nguyen Tran Khe, Isamu Shimizu, Eiichi Inoue, Journal of the Electrophotography Society 18 (No. 2), 22 (1)
980), JP 50-51011, JP 53-54
Examples include materials disclosed in Publications No. 027, No. 54-20735, and No. 57-202544. Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and its derivatives, Polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers, Acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, itaconic acid diester polymers and copolymers, maleic anhydride Acid copolymers, acrylamide copolymers, methacrylamide copolymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, amide resins, hydroxyl- and carboxyl-modified polyester resins, butyral resins, polyvinyl acetal resins, cyclized rubber-methacrylic Acid ester copolymers, cyclized rubber-acrylic ester copolymers, copolymers containing a heterocycle that does not contain a nitrogen atom (heterocycles include, for example,
(furan ring, tetrahydrofuran ring, thiophene ring, dioxane ring, dioxofuran ring, lactone ring, benzofuran ring, benzothiophene ring, 1,3-dioxetane ring, etc.), epoxy resins, and the like.

Furthermore, a medium to high molecular weight resin to be used in combination satisfies the above-mentioned physical properties and is preferably one 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). General formula (III)

embedded image [In formula (III), V1 is -COO-, -OCO-,
-(CH2)h -OCO-, -(CH2)h -
Represents COO-, -O- or -SO2-. However, h represents an integer of 1 to 4] In general formula (III), b1
and b2 represent the same contents as a1 and a2 in formula (I). R14 represents the same content as R3 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) may be used. Polymer resin (JP-A-63-4981
7, No. 63-220149, No. 63-220148, etc.), combined resins of the random copolymer and crosslinkable resin (Japanese Patent Application Laid-open No. 1-102573, etc.), graft type copolymers (Japanese Patent Application Publication No. 1-102573, etc.), 53064, 2-56558, etc.), medium to high molecular weight substances described in the specifications of the respective publications, etc.) can be mentioned.

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, and the polar group 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 the temperature characteristics were dramatically improved. As a result, it has been found that it has excellent electrophotographic properties as an electrophotographic photoreceptor, and in particular, exhibits extremely excellent performance even when a spectral sensitizing dye for semiconductor laser light is used.

[0052] If a medium to high molecular weight resin [B] is used in combination, the photoconductivity will be improved compared to the case of only the resin [A] without impeding 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 effect of the binder resin according to the present invention. That is, in the present invention, resin [A] and resin [B] are used together as the binder resin,
By specifying the weight average molecular weight (M) of each resin and the content of polar groups in the resin, the strength of the interaction between the photoconductor and the resin can be changed. 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. , the polar groups bonded to specific positions interact gently with the photoconductor to the extent that electrophotographic identification is not inhibited, and the molecular chains of the resin [B] having long molecular chains and graft molecular chains also interact with each other. By that,
As mentioned above, it is considered that both the electrophotographic properties and the mechanical properties of the film were significantly improved.

Next, the non-aqueous solvent dispersed resin particles used in the present invention will be explained in detail. The resin particles of the present invention are
It is manufactured by so-called non-aqueous dispersion polymerization. The monofunctional monomer (A) used in the present invention, which is soluble in a non-aqueous solvent but becomes insolubilized by polymerization, contains at least one thiol group, phosphono group, or sulfo group when decomposed. A functional group that generates a hydrophilic group (hereinafter sometimes simply referred to as a hydrophilic group-generating functional group) such as an amino group will be explained. The hydrophilic group-generating 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.

Hereinafter, at least one thio-
The functional group that generates a thiol group (thiol group-generating functional group) will be explained in detail. According to one preferred embodiment of the present invention, the thiol group-generating functional group-containing monomer has the following general formula (
IV) Contains at least one functional group represented by [-S-LA]. General formula (IV): [-S-LA] where LA is,

embedded image However, RA 1 , RA 2 and RA 3 may be the same or different, and each represents a hydrocarbon group or -O-R
AI (RAI represents a hydrocarbon group), RA 4
, RA 5 , RA 6 , RA 7 , RA 8
, RA 9 and RA 10, RA 11, RA 12
, RA 13 each independently represents a hydrocarbon group.

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

In the case where RA 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 (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group) , octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (e.g. cyclopentyl group, cyclohexyl group, etc.), optionally substituted alicyclic group Aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aromatic groups (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxy phenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or -O-RAI
(RAI represents a hydrocarbon group, specifically the above RA
1 , RA 2 , and RA 3 ).

[0056] LA is

embedded image or when representing -S-RA 8 , RA 4
, RA 5 , RA 6 , RA 7 , and RA 8 are each preferably a linear or branched alkyl group having 1 to 12 carbon atoms (e.g., methyl group, trichloromethyl group, trifluoromethyl group, methoxy methyl group,
Ethyl group, propyl group, n-butyl group, hexyl group, 3
-chloropropyl group, phenoxymethyl group, 2,2,2
-trifluoroethyl group, t-butyl group, hexafluoro-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) group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.), an optionally substituted aryl group having 6 to 12 carbon atoms (e.g. phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group) group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

[0057] LA is

In the case where RA 9 and RA 10 may be the same or different, preferred examples include the substituents preferred for RA 4 to RA 8 above.

[0058] LA is

In the case where Y1 represents an oxygen atom or a sulfur atom. RA 11 , RA 12 and RA 13 may be the same or different and preferably represent a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted. Preferred examples have the same content as RA 4 to RA 8 above. Further, p2 represents an integer of 5 or 6.

Other preferred thiol group-forming functional group-containing monomers of the present invention are those containing at least one thiirane ring represented by general formula (V) or general formula (VI). General formula (V)

[Chemical formula 107] General formula (VI)

embedded image In formula (V), RA 14 and RA 15 may be the same or different, and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above RA 4 to RA 7
represents the preferred substituents. In formula (VI), 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 monomer of the present invention is a monomer containing at least one sulfur atom-containing heterocyclic group represented by general formula (VII). General formula (VII)

In formula (VII), YA is an oxygen atom or -NH-
represents a 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, a hydrogen atom or the RA 4
〜RA 7 represents a preferable substituent. RA 1
9 and RA 20 may be the same or different and represent a hydrogen atom, a hydrocarbon group, or -O-RAII (RAII represents a hydrocarbon group). Preferably, the RA 1
〜RA 3 represents a preferable substituent.

According to yet another preferred embodiment of the present invention, the thiol group-forming functional group-containing monomer is a monomer in which at least two thiol groups located sterically close to each other are simultaneously protected with one protecting group. A monomer 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 those represented by the following general formulas (VIII), (IX), and (X). can be mentioned. General formula (VIII)

[Chemical formula 110] General formula (IX)

[Chemical formula 111] General formula (X)

[Chemical Formula 112] In formula (VIII) and formula (IX), ZA represents a carbon-carbon bond or a chemical bond that directly connects C-S bonds, which may be via a heteroatom (provided that atoms between sulfur atoms (The number must be within 4). Furthermore, one of the −(ZA・
...C) -The bond represents only a simple bond, and may be as shown below, for example.

In formula (IX), RA 21 and RA 22 may be the same or different, and represent a hydrogen atom, a hydrocarbon group, or -O
-RAII (RAII represents a hydrocarbon group). In formula (IX), RA 21 and RA 22
are preferably the same or different and include a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, octyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, methylbenzyl group, etc.) group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic group having 5 to 7 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.), or optionally substituted aryl group (e.g., phenyl group, chlorophenyl group, methoxyphenyl group) , methylphenyl group, cyanophenyl group, etc.) or -O-RAII (
RAII is synonymous with the hydrocarbon group in RA 21 and RA 22). In formula (X), RA 2
3, 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,
It represents the same meaning as the hydrocarbon group preferred in RA 22.

The above general formula (
The monomer (A) containing at least one functional group represented by IV) to (X) is, for example, "Reactive Polymer" by Yoshio Iwakura and Keisuke Kurita, pages 230 to 237 (Kodansha: published in 1977), Edited by the Chemical Society of Japan, "New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [III]" Chapter 8, pp. 1700-1713 (Maruzen Co., Ltd., 1978), J. F
．． W. McOmie “Protective Gro
Upsin Organic Chemistry”
Chapter 7 (Plenum Press. Published in 1973)
, S. Patai “The Chemistry o”
f the thiol group Part 2
” Chapters 12 and 14 (John Wiley & So.
ns, published in 1974), etc. can be applied.

More specifically, general formulas (IV) to (X)
Examples of the monomer (A) containing the functional group include the following compounds. (1)

[Chemical formula 114] (2)

[Chemical formula 115] (3)

[Chemical formula 116] (4)

[Chemical formula 117] (5)

[Chemical formula 118] (6)

[Chemical formula 119] (7)

[Chemical formula 120] (8)

[Chemical formula 121] (9)

[Chemical formula 122] (10)

[Chemical formula 123] (11)

[Chemical formula 124] (12)

[Chemical formula 125] (13)

[Chemical formula 126] (14)

[Chemical formula 127] (15)

[Chemical formula 128] (16)

[Chemical formula 129] (17)

[Chemical formula 130] (18)

[Chemical formula 131] (19)

[Chemical formula 132] (20)

[Chemical formula 133] (21)

[Chemical formula 134] (22)

[Chemical formula 135] (23)

[Chemical formula 136] (24)

[Chemical formula 137] (25)

[Chemical formula 138] (26)

[Chemical formula 139] (27)

[Chemical formula 140] (28)

[Chemical formula 141] (29)

[Chemical formula 142] (30)

[Chemical formula 143] (31)

[Chemical formula 144] (32)

[Chemical formula 145] (33)

[Chemical formula 146] (34)

[Chemical formula 147] (35)

[Chemical formula 148] (36)

[Chemical formula 149] (37)

[Chemical formula 150] (38)

[Chemical formula 151] (39)

[Chemical formula 152] (40)

[Chemical formula 153] (41)

[Chemical formula 154] (42)

[Chemical formula 155] (43)

[Chemical formula 156] (44)

[Chemical formula 157] (45)

[Chemical formula 158]

Next, the functional group which produces at least one phosphono group, such as a group of the following general formula (XI) or (XII) upon decomposition, will be explained in detail. General formula (XI)

[Chemical formula 159] General formula (XII)

embedded image In formula (XI), RB is a hydrocarbon group or -ZB
2 -RBI (here RBI indicates hydrocarbon, ZB
2 represents an oxygen atom or a sulfur atom). Q
B 1 represents an oxygen atom or a sulfur atom. ZB 1
represents an oxygen atom or a sulfur atom. In formula (XII), QB 2 , ZB 3 and ZB 4 each independently represent an oxygen atom or a sulfur atom. Preferably,
RB is an optionally substituted alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group)
or -ZB 2 -RBI (here, ZB 2 represents an oxygen atom or a sulfur atom. RBI represents the same content as RB) QB 1 , QB 2 , ZB 1 , Z
B 3 and ZB 4 each independently represent an oxygen atom or a sulfur atom.

By decomposition as above, formula (XI) or (X
Examples of the functional group that generates the phosphono group represented by II) include functional groups represented by the general formula (XIII) and/or (XIV). General formula (XIII)

[Chemical formula 161] General formula (XIV)

embedded image In formulas (XIII) and (XIV), QB 1
, QB 2 , ZB 1 , ZB 3 , ZB 4 and RB represent the contents as defined in formulas (XI) and (XII), respectively. LB 1 , LB 2 and LB
3 are each independent of each other.

[Chemical formula 163] represents. LB 1 to LB 3 are

In the case where RB 1 to RB 2 may be the same or different, hydrogen atoms, halogen atoms (
For example, it represents a chlorine atom, bromine atom, 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 substituent constant shows a positive value, such as a halogen atom,

[Chemical formula 165], etc.), preferably a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), -CN-,
-CONH2 , -NO2 or -SO2 RBII
(RBII represents a hydrocarbon group such as methyl, ethyl, propyl, butyl, hexyl, benzyl, phenyl, tolyl, xylyl, mesityl, etc.)
represents. n represents 1 or 2. Further, when XB 1 is a methyl group, RB 1 and RB 2 are methyl groups and n=1.

[0066] LB 1 to LB 3 are

In the case where RB 3 , RB 4 and RB
5 may be the same or different, preferably a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group). group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g. cyclopentyl group, cyclohexyl group, etc.), Aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.), optionally substituted aromatic groups (e.g. phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxy phenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or -O-RB
III (RBIII represents a hydrocarbon group, specifically,
Examples include the substituents of RB 3 , RB 4 , and RB 5 above.

[0067] LB 1 to LB 3 are

In the case where RB 6 , RB 7 , RB
8 , 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.).

[0068] Furthermore, LB 1 to LB 3

[Chem.168
] In the case where YB 1 and YB 2 represent an oxygen atom or a sulfur atom.

At least one functional group used in the present invention
The species-containing monomer 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. Specifically, J. F. W. McOmie “Pro
tective groups in Organic
Chemistry Chapter 6 (Plenum Pre
ss, published in 1973), 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).
A synthetic reaction similar to the method for introducing a protecting group into a hydroxyl group described in S. et al. Patai “The
Chemistry of the Triol
Group Part 2” Chapters 13 and 14 (W
Iley-Interscience (1974), T. W. Greene “Protective g
roups in Organic Synthes
is” Chapter 6 (Wiley-Interscience
It can be produced by a synthetic reaction similar to the method for introducing a protecting group into a thiol group as described in J. E., 1981).

The following examples can be given as specific examples of compounds that can serve as repeating units of polymeric components containing functional groups of general formulas (XIII) and/or (XIV) used as protective groups. (1)

[Chemical formula 169] (2)

[Chemical formula 170] (3)

[Chemical formula 171] (4)

[Chemical formula 172] (5)

[Chemical formula 173] (6)

[Chemical formula 174] (7)

[Chemical formula 175] (8)

[Chemical formula 176] (9)

[Chemical formula 177] (10)

[Chemical formula 178] (11)

[Chemical formula 179] (12)

[Chemical formula 180] (13)

[Chemical formula 181] (14)

[Chemical formula 182] (15)

[Chemical formula 183] (16)

[Chemical formula 184] (17)

[Chemical formula 185] (18)

[Chemical formula 186]

Next, amino groups, such as -NH
Examples of the functional group that generates the 2 group and/or the -NHRC group include groups represented by the following general formulas (XV) to (XVII). General formula (XV)

embedded image General formula (XVI)

[Chemical formula 188] General formula (XVII)

embedded image In formula (XV) and formula (XVII), RC 0 is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group). 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, mesityl group, chloromethyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group, etc.). Preferably RC 0
When represents the hydrocarbon group, examples thereof include hydrocarbon groups having 1 to 8 carbon atoms.

In the functional group represented by formula (XV), R
C 1 represents an optionally substituted aliphatic group having 2 to 12 carbon atoms, and more specifically, RC 1 represents the following formula (XVII
Represents a group represented by I). Formula (XVIII)

embedded image In formula (XVIII), a6 and a7 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, a methyl group, an ethyl group). 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.) , YC is a hydrogen atom, a halogen atom (e.g. fluorine atom, chlorine atom, etc.), a cyano group,
Alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), aromatic groups which 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, a6 and a7 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, a6
and a7 may be any of the groups listed above. That is,

In [Chemical Formula 191], 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. This shows that.

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 (XVI), RC 2 and RC 3 may be the same or different and each represents a hydrocarbon group having 1 to 12 carbon atoms.
It represents the same contents as the aliphatic group or aromatic group in YC of V). In general formula (XVII), XC 1 and XC 2 may be the same or different and each represents an oxygen atom or a sulfur atom. RC4 and RC5 may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, specifically,
It represents an aliphatic group or an aromatic group in YC of formula (XV).

Specific examples of the functional groups of formulas (XV) to (XVII) are shown below. (1)

[Chemical formula 192] (2)

[Chemical formula 193] (3)

[Chemical formula 194] (4)

[Chemical formula 195] (5)

[Chemical formula 196] (6)

[Chemical formula 197] (7)

[Chemical formula 198] (8)

[Chemical formula 199] (9)

[C200] (10)

[C201] (11)

[C202] (12)

[C203] (13)

[C204] (14)

[C205] (15)

[C206] (16)

[C207] (17)

[C208] (18)

[C209] (19)

[Chemical formula 210] (20)

[Chemical formula 211] (21)

[C212] (22)

[Chemical formula 213] (23)

[Chemical formula 214] (24)

[Chemical formula 215] (25)

[Chemical formula 216] (26)

[C217] (27)

[C218]

The amino group (
For example, the monomer containing at least one kind of functional group that generates -NH2 group and/or -NHR group, for example, a functional group selected from the group of general formulas (XV) to (XVII) above, is a monomer containing, for example, Nippon Chemical "New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds [V]", p. 2555 (published by Maruzen Co., Ltd.), edited by J. F. W. McOmie “Protecti
ve groups in Organic Chem
istry” Chapter 2 (PlenumPress 19
(published in 1973), “Protective groups
in Organic Synthesis” Chapter 7 (
John Wiley & Sons, published in 1981).

Furthermore, examples of the functional group that generates at least one sulfo group upon decomposition include those represented by the general formula (XIX
) or (XX). General formula (XIX) -SO2 -O
-RD1 General formula (XX) -SO
2 -S-RD 2 In formula (XIX), RD 1 is

embedded image Or represents -NHCORD 7 . In formula (XX), RD
2 represents an aliphatic group having 1 to 18 carbon atoms which may be substituted, or an aryl group having 6 to 22 carbon atoms which may have a substituent.

The functional groups of the above general formulas (XIX) and (XX) produce sulfo groups upon decomposition, and will be explained in more detail below. RD 1 is

In the case where RD 3 and RD 4 are the same or different, hydrogen atom, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.) or alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). YD is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, trifluoromethyl group) 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 groups having 2 to 18 carbon atoms (e.g. vinyl group, allyl group, etc.) ), an 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, methoxycarbonylphenyl group,
butoxycarbonylphenyl group, methanesulfonylphenyl group, benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group, etc.) or

embedded image (RD 8 represents an aliphatic group or an aromatic group, and specifically represents the same substituent as the above YD 2 ). n represents 0, 1 or 2. More preferably, substituents:

In the formula, a functional group containing at least one electron-withdrawing group is mentioned. Specifically, when n is 0 and YD is a hydrocarbon group that does not contain an electron-withdrawing group as a substituent,

embedded image contains at least one halogen atom. Further, n is 0, 1 or 2, and YD contains at least one electron-withdrawing group. Furthermore, when n=1 or 2,

embedded image 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.

[0081] RD 1 is

In the case where ZD represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by general formula (XXI) or (XXII). General formula (XXI)

[Chemical formula 226] General formula (XXII)

embedded image In formula (XXI), RD 9 and RD 10 may be the same or different, and each may be a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or a substituted carbon atom having 1 to 18 carbon atoms. Good alkyl groups (e.g. methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-
chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2-(methanesulfonyl)ethyl group, 2-(ethoxyoxy)ethyl group),
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.),
an optionally substituted alkenyl group having 3 to 18 carbon atoms (e.g. allyl group, 3-methyl-2-propenyl group, etc.),

0
082] RD 1 is

In the case where RD 5 and RD 6 represent a hydrogen atom, an aliphatic group (specifically, the same content as that of RD 3 and RD 4 ), or an aryl group (specifically, RD 3 , represents the same content as that of RD 4). However, both RD 5 and RD 6 do not represent hydrogen atoms. RD 1 is -NHCORD 7
In the case where RD 7 represents an aliphatic group or an aryl group, specifically, each represents the same content as that of RD 3 and RD 4 . In formula (XX), RD 2
represents an aliphatic group having 1 to 18 carbon atoms which may be substituted or an aryl group having 6 to 22 carbon atoms which may have a substituent. More specifically, YD represented by the above formula (XIX)
represents the same content as the aliphatic group or aryl group in .

General formula [-SO2-] used in the present invention
The monomer containing at least one functional group selected from the group O-RD1] or [-SO2-O-RD2] can be synthesized based on knowledge of conventionally known organic reactions. For example, J. F. W. McOmie, “Prot.
Active Groups in Organic
Chemistry”;PlenumPress(19
(published in 1973), T. W. Greene, “Protect
ive Groupsin Organic Sint
John Wiley & Sons (
It can be synthesized in the same manner as the carboxyl group protection reaction described in (1980).

More specifically, general formula (XIX)-SO2
-O-RD 1 or general formula (XX)-SO2 -O-
The following examples can be given as the functional group of RD 2 , but the scope of the present invention is not limited thereto. (1)

[Chemical formula 229] (2)

[Chemical formula 230] (3)

[Chemical formula 231] (4)

[Chemical formula 232] (5)

[Chemical formula 233] (6)

[Chemical formula 234] (7)

[Chemical formula 235] (8)

[Chemical formula 236] (9)

[Chemical formula 237] (10)

[Chemical formula 238] (11)

[Chemical formula 239] (12)

[Chemical formula 240] (13)

[Chemical formula 241] (14)

[Chemical formula 242] (15)

[Chemical formula 243] (16)

[C244] (17)

[Chemical formula 245] (18)

[Chemical formula 246] (19)

[Chemical formula 247] (20)

[C248] (21)

[Chemical formula 249] (22)

[Chemical formula 250] (23)

[Chemical formula 251] (24)

[Chemical formula 252] (25)

[Chemical formula 253] (26)

[Chemical formula 254] (27)

[Chemical formula 255] (28)

[Chemical formula 256] (29)

[Chemical formula 257] (30)

[Chemical formula 258] (31)

[Chemical formula 259] (32)

[Chemical formula 260] (33)

[Chemical formula 261]

[0085] The resin particles [L] of the present invention are monomer [A]
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 [A] 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, and acrylic acid. , esters or amides of unsaturated carboxylic acids such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, α-olefins, acrylonitrile, Examples include vinyl group-substituted heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone. The amount of these other monomers is 60 parts by weight or less, preferably 50 parts by weight, based on 100 parts by weight of the total polymer component to be insolubilized.
Parts by weight or less. 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, the dispersion stabilizing resin of the present invention will be explained. It is important that the dispersion stabilizing resin is solvated and soluble in the nonaqueous solvent, and plays a dispersion stabilizing effect in so-called nonaqueous dispersion polymerization. Specifically, for 100 parts by weight of the solvent, At least 5 at a temperature of 25°C
Any material may be used as long as it dissolves in weight%.

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

The dispersion stabilizing resin of the present invention may be any polymer as long as it is soluble in the non-aqueous solvent, but specifically,
K. E. J. Barrett “Dispers
ion Polymerization in Org
John Wiley anic
d Sons (published in 1975), R. Dowpen
co, D. P. Hart, Ind. Eng
．． Chem. Prod. Res. Develo
p. 12, (No. 1), 14 (1973), Toyokichi Tange, Japan Adhesive Association Journal 23 (1), 26 (1987)
), D. J. Walbridge, NATO.
Adv. Study Inst. Ser. E. N
o. 67, 40 (1983), Y. Sasakian
dM. Yabuta, Proc, 10th,
Int. Conf. Org. Coat. Sc
i. Technol, 10, 263 (1984) and other reviews include cited polymers.

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

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

embedded image In formula (XXIII), X3 represents the same content as V0 in formula (II), and details are described in the explanation of V0 in formula (II).

R15 is an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, dosaconyl group, 2-(N,N-dimethylamino)ethyl group, 2
-(N-morpholino)ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-(α-thienyl)ethyl group, 2-carboxyethyl group, 2-methoxycarbonylethyl group,
2,3-epoxypropyl group, 2,3-diacetoxypropyl group, 3-chloropropyl group, 4-ethoxycarbonylbutyl group, etc.), optionally substituted alkenyl groups having 3 to 22 carbon atoms (e.g. allyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group,
octadecenyl group, oleyl group, linoleyl group), optionally substituted aralkyl group having 7 to 22 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group,
2-naphthylmethyl group, 2-(2'-naphthyl)ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
methoxybenzyl group, dimethoxybenzyl group, butylbenzyl group, methoxycarbonylbenzyl group, etc.), optionally substituted alicyclic groups having 4 to 12 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chloro cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), carbon number 6 or more
22 optionally substituted aromatic groups (e.g. phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, anthranyl group, chlorophenyl group, bromophenyl group, butylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Octyloxyphenyl group, ethoxycarbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N,N-dibutylaminophenyl group, N
-methyl-N-dodecylphenyl group, thienyl group, hyranyl group, etc.). c1 and c2 are expressed by the formula (I
It represents the same content as a3 and a4 in formula (I), and details are described in the explanation of a1 and a2 in formula (I).

[0092] As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the above-mentioned components. Other polymer components include general formula (XXI
Any monomer may be used as long as it copolymerizes with the monomer corresponding to the component shown in II).
For example, α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (heterocycles include, for example, pyran ring, pyrrolidone ring, imidazole ring, pyridine ring, etc.), vinyl group-containing carboxylic acids (for example, acrylic acid, methacrylonitrile, acid, crotonic acid, itaconic acid, maleic acid, 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 polymer component represented by the general formula (XXIII) is at least 30 parts by weight, preferably at least 50 parts by weight, based on 100 parts by weight of the total polymer of the resin.

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

embedded image In general formula (II), V0 is -O-, -COO-
, -OCO-, -(CH2)p -OCO-, -(C
H2) p -COO-, -SO2 -,

embedded image represents -CONHCOO- or -CONHCONH- (p represents an integer of 1 to 4).

In addition to a hydrogen atom, R6 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (such as 2-bromopropyl group),
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) , or an optionally substituted aromatic group having 6 to 12 carbon atoms (
For example, 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.).

[0096] V0 is

When represented by the following formula, the benzene ring may have a substituent. Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group,
(propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, propioxy group, butoxy group, etc.), and the like.

a3 and a4 may be the same or different, preferably a hydrogen atom, a halogen atom (
For example, chlorine atom, bromine atom, etc.), cyano group, carbon number 1~
4 alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R7 or COOR7 via a hydrocarbon (R7 is a hydrogen atom or a carbon atom with 1 to 1 carbon atoms)
18 alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as explained for R6 above) .

Examples of the hydrocarbon in the -COOR7 group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like. More preferably, the general formula (
In II), V0 is -COO-, -OCO-,
-CH2 OCO-, -CH2 COO-, -O-, -
CONH-, -SO2 NH-, -CONHCOO- or

[Chemical formula 266], a3 and a4 may be the same or different and represent a hydrogen atom, a methyl group, -COOR7 or -CH2COOR7, (R7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, etc. Even more preferably, one of a3 and a4 always represents a hydrogen atom.

Specifically, as the polymerizable double bond group-containing moiety represented by the general formula (II),

[Chemical formula 267] etc.

[0100] These polymerizable double bond group-containing moieties are bonded directly to the main chain of the polymer chain or via an arbitrary linking group. Specifically, the connecting group is a divalent organic residue, -O-, -S-,

Represents an organic residue composed of a divalent aliphatic group, a divalent aromatic group, or a combination of these divalent residues, which may have a bonding group selected from . Here, d
1 to d5 represent the same content as R6 in formula (II).

As the divalent aliphatic group, for example,

[C269
] {e1 and e2 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 to 12
represents an alkyl group (eg, methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hesyl group, octyl group, nonyl group, decyl group, etc.). Q represents -O-, -S- or -NR16-, R16
is an alkyl group having 1 to 4 carbon atoms, -CH2Cl or -C
H2 represents Br}.

[0102] Examples of divalent aromatic groups include benzene ring groups, naphthalene ring groups, and 5- or 6-membered heterocyclic groups (the hetero atoms constituting the heterocycle are selected from oxygen atoms, sulfur atoms, and nitrogen atoms). containing at least one type of heteroatom). These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, etc.), and an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) as examples of the substituent. Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-
Examples include oxazoline rings.

[0103] Specifically, the polymerizable double bond group-containing moiety as described above is randomly bonded in the polymer chain, or
Or it is bonded only to one end of the main chain of the polymer chain. Preferably, a polymer in which a polymerizable double bond group-containing portion is bonded only to one end of the main chain of the polymer chain (hereinafter abbreviated as monofunctional polymer [M]) is used.

General formula (II) of the above monofunctional polymer [M]
) The following are specific examples of the polymerizable double bond group-containing moiety and the moiety composed of an organic residue connected thereto, but the present invention is not limited thereto. However, in each of the following examples, P1 is -H, -CH3
, -CH2COOCH3, -Cl, -Br or -C
N, P2 represents -H or -CH3, X4
represents -Cl or -Br, n2 represents an integer of 2 to 12, and m2 represents an integer of 1 to 4. (c-1)

[Chemical formula 270] (c-2)

[Chemical formula 271] (c-3)

[Chemical formula 272] (c-4)

[Chemical formula 273] (c-5)

[Chemical formula 274] (c-6)

[Chemical formula 275] (c-7)

[Chemical formula 276] (c-8)

[Chemical formula 277] (c-9)

[Chemical formula 278] (c-10)

[Chemical formula 279] (c-11)

[Chemical formula 280] (c-12)

[Chemical formula 281] (c-13)

[Chemical formula 282] (c-14)

[Chemical formula 283] (c-15)

[C284] (c-16)

[Chemical formula 285] (c-17)

[C286] (c-18)

[Chemical formula 287] (c-19)

[Chemical formula 288] (c-20)

[Chemical formula 289] (c-21)

[Chemical formula 290] (c-22)

[Chemical formula 291] (c-23)

[Chemical formula 292] (c-24)

[Chemical formula 293] (c-25)

[Chemical formula 294] (c-26)

[Chemical formula 295] (c-27)

[Chemical formula 296] (c-28)

[Chemical formula 297] (c-29)

[Chemical formula 298] (c-30)

[Chemical formula 299]

Preferably, the dispersion stabilizing resin of the present invention contains a polymerizable double bond group moiety in the side chain of the polymer, and this polymer can be synthesized by a conventionally known method. For example, (1) a method of copolymerizing monomers containing two polymerizable double bond groups with different polymerization reactivity in the molecule;
■ After obtaining a polymer by copolymerizing a monofunctional monomer containing a reactive group such as a carboxyl group, hydroxyl group, amino group, or epoxy group in the molecule, reactions occur in the side chains of this polymer. A commonly known method is a method of introducing a polymer through a so-called polymer reaction, in which a reaction is performed with an organic low-molecular compound containing a polymerizable double bond group that contains another reactive group that can chemically bond with the group. Can be mentioned.

[0106] As the above method (1), for example, Japanese Patent Application Laid-Open No. 1986-
Examples include the method described in Japanese Patent No. 185962. As for the above method (■), specifically, Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (published in 1976), JP-A-6
It is described in detail in Japanese Patent Application No. 1-43757 and the specification filed as Japanese Patent Application No. 1-149305.

[0107] For example, a polymer reaction using a combination of a group A functional group and a group B functional group shown in Table 1 below is a commonly known method. Furthermore, R17 in Table-1,
R18 is a hydrocarbon group, and R6 in the above formula (II)
represents the same content as .

[Table 1]

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

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

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

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

[0112] That is, the dispersed resin particles of the present invention are non-aqueous particles consisting of a portion insoluble in a non-aqueous dispersion solvent consisting of the polymer component (A) and a polymer soluble in the solvent. When the latex has a network structure, the molecules of the polymer component (A) forming the portion insoluble in the solvent are bridged. As a result, the network resin particles become poorly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

[0113] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (a) the polymer component (A
) A method of crosslinking a polymer containing the following with various crosslinking agents or curing agents, (b) when carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (A),
A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and (c) the polymer component (A
) and a polymer containing a component containing a reactive group through a polymerization reaction or a polymer reaction.

[0114] As the crosslinking agent in the above method (a), compounds that are commonly used as crosslinking agents can be mentioned. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. Can be used.

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

[0116] Furthermore, in the method (b) above, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polyfunctional oligomer can be polymerized. Specifically, as a sexual functional group,

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

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

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

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is monomer (A)
and 10 relative to the total amount of other monomers coexisting with (A)
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 polymers in the method (c) above, it is possible to use a method similar to the reaction of ordinary organic low-molecular compounds. The same can be done. Specifically, it can be synthesized according to the same method as described in the method for synthesizing the dispersion stabilizing resin. In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can be easily obtained, so polyfunctional monomers are used as a method for forming a network structure. Method (b) using . As described above, the network-dispersed resin particles of the present invention consist of a polymer component containing a repeating unit containing a polar group, a repeating unit having a fluorine atom and/or a silicon atom-containing substituent, and a polymer component that is soluble in the non-aqueous solvent. These are polymer particles containing a polymer component and having a structure in which molecular chains are highly cross-linked.

[0121] 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 this organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone,
Ketones such as 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,
C6-14 aliphatic hydrocarbons such as dodecane, tridecane, cyclohexane, cyclooctane, benzene,
Examples include aromatic hydrocarbons such as toluene, xylene, and chlorobenzene, and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane, and trichloroethane. However, it is not limited to the compound examples described above.

[0122] By synthesizing dispersed resin particles in these non-aqueous solvent systems by dispersion polymerization, the average particle diameter of the resin particles can easily be 1 μm or less, and the particle size distribution is extremely narrow and monodisperse particles can be obtained. It can be done. Specifically, K. E. J. Barrett “Dispe.
rsion Polymerization in O
rganic Media” by John Wiley (
1975), Koichiro Murata, Polymer Processing, 23, 20 (
1974), Tsunetaka Matsumoto and Toyokichi Tange, Japan Adhesive Association Journal 9,
183 (1973), Toyokichi Tange, Japan Adhesive Association Journal 23,
26 (1987), D. J. Walbridge
, NATO. Adv. study. Inst.
Ser. E. No. 67, 40 (1983), British Patent Nos. 893429 and 934038, U.S. Patent Nos. 1122397, 3900412, and 460
6989 specifications, JP-A No. 60-179751, JP-A No. 60-179751
The method is disclosed in publications such as No. 0-185963.

[0123] The dispersion resin of the present invention is composed of at least one type each of monomer (A) and dispersion stabilizing resin, and when forming a network structure, a polyfunctional monomer (D
), and in any case, what is important is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, the desired dispersed resin can be obtained. More specifically, it is preferable to use the dispersion stabilizing resin in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight based on the monomer (A) to be insolubilized. Further, the molecular weight of the dispersed resin particles of the present invention is 104 to 106, preferably 104
~5×105.

[0124] In order to produce the dispersed resin particles used in the present invention as described above, the monomer (A), the dispersion stabilizing resin, and the polyfunctional monomer (D) are generally mixed in a non-aqueous solution. The polymerization may be carried out by heating in a solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of a monomer (A), a dispersion stabilizing resin, and a polyfunctional monomer (D), (ii) a method of adding a polymerization initiator to a nonaqueous solvent; , a method in which a mixture of the above-mentioned polymerizable compound and a polymerization initiator is added dropwise or arbitrarily, and the method is not limited to these methods, and any method can be used for production.

[0125] The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the nonaqueous solvent.
~50 parts by weight. The amount of polymerization initiator is 0.1 to 5% by weight of the total amount of polymerizable compounds. Also, the polymerization temperature is 30
The temperature is about 180°C, preferably 40 to 120°C. The reaction time is preferably 1 to 15 hours.

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

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Furthermore, other inorganic photoconductors such as titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, etc. may be used in combination. However, these other photoconductive materials account for no more than 40% by weight of the photoconductive zinc oxide, preferably no more than 20% by weight of the photoconductive zinc oxide. If the content of other photoconductive materials exceeds 40% by weight, the effect of improving the hydrophilicity of non-image areas as a lithographic printing original plate will be diminished.

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

In the present invention, various dyes are used alone or in combination as spectral sensitizers. For example, Harumi Miyamoto,
Hidehiko Takei: Imaging 1973 (No. 8) p. 12, C. J. Young et al., RCA Review 1
5, 469 (1954), Wataru Kiyota: Transactions of the Institute of Electrical Communication Engineers J63-C (No. 2), p. 97 (1980)
), Yuji Harasaki et al., Industrial Chemistry Journal 66, 78 and 1
88 pages (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 3
5, p. 208 (1972), carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g. oxonol dyes, merocyanine dyes,
cyanine dye, rhodacyanine dye, styryl dye, etc.)
, phthalocyanine dyes (which may contain metal), and the like.

More specifically, carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are mainly used in Japanese Patent Publication No. 51-4.
52, JP-A No. 50-90334, No. 50-114227
, 53-39130, 53-82353 publications,
U.S. Patent No. 3,052,540, U.S. Patent No. 4,054,45
Examples include those described in the specifications of each issue of No. 0, JP-A-57-16456, and the like.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include F. M. Hammer “The C”
yanine DyesandRelatedC
It is possible to use pigments described in US Pat. No. 3,047,384 and US Pat.
110591, 3121008, 3125447,
3128179, 3132942, 3622,3
17 specifications, British Patent No. 1226892, British Patent No. 130
9274, 1405898 specifications, Japanese Patent Publication No. 1974-
Examples include dyes described in JP-A No. 7814 and No. 55-18892.

[0132] 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. 3619154, U.S. Patent No. 417595
6 Specifications, “Research Disclo
Sure, 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers, such as chemical sensitizers, may be used in combination. For example, the previous review: Imaging 1
973 (No. 8), page 12, etc., of electron-accepting compounds (e.g., halogens, benzoquinones, chloranil, acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent Photoconductive Materials and Photosensitive Materials" Chapters 4 to 6 of ``Development and Practical Application of Phytochemistry'' (Japan Scientific Information Co., Ltd. Publishing Department (1986)) include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, etc. .

The amount of these various additives added is not particularly limited, but is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight.

The thickness of the photoconductive layer is 1 to 100 μm, especially 10 μm.
~50μ is suitable.

[0136] When a photoconductive layer is used as the charge generation layer of a photoreceptor with a stack of charge generation layer and charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.0μ. ．．
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. 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-vinyl 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. those that have been subjected to conductive treatment, such as those coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and preventing curling, etc.
One in which a water-resistant adhesive layer is provided on the surface of the support, one in which at least one or more precoat layer is provided on the surface layer of the support as necessary, and one in which a conductive plastic substrate on which Al or the like is vapor-deposited is made into paper. Laminated materials can be used. Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-1
1 (1975), Hiroyuki Moriga, "Introductory Chemistry of Special Papers", Kobunshi Publishing (1975), M. F. Hoover,
J. Macromol. Sci. Chem. A
-4(6), pages 1327-1417 (1970), etc. are used.

[0139] Printed matter using the electrophotographic original plate of the present invention is produced by forming a copy image on the electrophotographic original plate having the above-mentioned structure by a conventional method, and then subjecting the non-image area to a desensitizing process. be done. The desensitizing treatment used in the present invention is a method in which the resin particles of the present invention are hydrolyzed by passing through a treatment solution, decomposed by a redox reaction, or decomposed by light irradiation treatment to remove hydroxyl groups. Examples include a method in which zinc oxide is desensitized with a desensitizing treatment liquid along with a hydrophilic treatment of the resin particles. In the latter case, ■ carrying out a desensitization reaction on zinc oxide particles and resin particles at the same time, ■ carrying out a decomposition treatment on the resin particles after desensitizing the zinc oxide particles, and ■ carrying out decomposition treatment on the resin particles after decomposition treatment on the zinc oxide particles. It can be carried out by any procedure such as carrying out a desensitization reaction.

[0140] 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 61-239158, 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 Publication No. 43-28 using a phytic acid compound as the main ingredient.
408, 45-24609, JP-A-51-10350
1, No. 54-10003, No. 53-83805, No. 5
3-83806, 53-127002, 54-44
901, 56-2189, 57-2796, 57
-20394, those described in Japanese Patent Publications No. 59-207290, Japanese Patent Publications No. 38-9665 and No. 39-2226, which use water-soluble polymers capable of forming metal chelates as main ingredients.
3, 40-763, 43-28404, 47-2
9642, JP 52-126302, JP 52-134
501, No. 53-49506, No. 53-59502, No. 53-104302, etc., and JP-A No. 53-10430 using a metal complex compound as the main ingredient.
1. Those described in Japanese Patent Publication Nos. 15313-1983 and 41924-1984, or those described in Japanese Patent Publications No. 13702 and 40 of 1982, using inorganic and organic acid compounds as main ingredients.
-10308, 46-26124, JP-A-51-11
Examples include those described in Publications No. 8501 and No. 56-111695.

[0141] As a method for desensitizing resin particles, that is, a method for decomposing a specific protected functional group of the present invention, method 1 is as follows.
It is arbitrarily selected depending on the decomposition reactivity of the particular protected functional group of the present invention. Acidic conditions of pH 1 to 6, pH
Examples include a method of hydrolyzing with an aqueous solution under alkaline conditions of 8 to 12. These pH adjustments can be easily carried out 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, sulfites, lipoic acid, hydroquinones, formic acid, Examples include thiosulfate, hydrogen peroxide, persulfate, and quinones.

[0142] The processing solution may contain other compounds in order to accelerate the reaction or improve the storage stability of the processing solution. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propargyl alcohol,
benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination of two or more.

[0143] 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.

The scope of the present invention is not limited to the above-mentioned specific compound examples. The processing conditions are: temperature 15~
The immersion time at 60°C is preferably 10 seconds to 5 minutes. Furthermore, as a method for decomposing a specific functional group by light irradiation, a step of irradiating it with "chemically active light" may be included sometime after the toner image is obtained during plate making. That is, after electrophotographic development, light irradiation may be performed during fixing of the toner image, or after fixing by other conventionally known fixing methods, such as heat fixing, pressure fixing, solvent fixing, etc., light irradiation may be performed. It performs irradiation. The "chemically active light" used in the present invention includes visible light, ultraviolet light,
Any of far ultraviolet rays, electron beams, X-rays, gamma rays, alpha rays, etc. may be used, but ultraviolet rays are preferred. More preferably, one that can emit light within a wavelength range of 310 nm to 500 nm is preferred, and a high-pressure or ultra-high pressure mercury lamp or the like is generally used. Light irradiation treatment is usually 5cm
Irradiation for 10 seconds to 10 minutes from a distance of ~50 cm can be sufficient.

[0145]

[Examples] Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. Synthesis example 1 of binder resin [A]: [A-1] 96 g of benzyl methacrylate, 4 g of thiosalicylic acid, and 20 g of toluene
After heating 0 g of the mixed solution to a temperature of 75°C under a nitrogen stream, 2,2'-azobisisobutyronitrile (abbreviated as A.I.
．． B. N. ) was added and reacted for 4 hours. Furthermore, A. I. B. N. 0.4g was added for 2 hours, and then further A. I. B. N. 0.2g of was added and stirred for 3 hours. The Mw of the obtained copolymer [A-1] was 6.8 x 103. Resin [A-1]

[Chemical formula 301]

Synthesis Examples 2 to 13 of Binder Resin [A]: [A-
2] to [A-13] In Synthesis Example 1 of Resin [A], the monomers shown in Table 2 below were used in place of 96 g of benzyl methacrylate, and the other procedures were carried out in the same manner as in Synthesis Example 1, and the results shown in the table below were carried out. -2 each resin [A
-2] to [A-13] were synthesized. Mw of each resin [A]
was 6.0×103 to 8×103.

[Table 2]

[Table 3]

[Table 4]

Synthesis Examples 14 to 24 of Binder Resin [A]: [A
-14] to [A-24] In Synthesis Example 1 of Resin [A], the methacrylates and mercapto compounds shown in Table 3 below were used instead of 96 g of benzyl methacrylate and 4 g of thiosalicylic acid, and 150 g of toluene was used instead of 200 g of toluene. The reaction was carried out in the same manner as in Synthesis Example 1 except that 50 g of isopropanol was used.
Each resin [A-14] to [A-24] shown in Table 3 below was synthesized. The Mw of each copolymer resin [A] obtained was 6.8×
It was 103.

[Table 5]

[Table 6]

[Table 7]

Synthesis Example 25 of Binder Resin [A]: [A-25
] 95.5 g of 1-naphthyl methacrylate, 0.5 g of methacrylic acid, 150 g of toluene, and 50 g of isopropanol
The mixed solution of g was heated to a temperature of 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. 1 g of was added and stirred for 3 hours. Mw of the obtained polymer
was 7.5×103. Resin [A-25]

[C302]

Synthesis Example 26 of Binder Resin [A]: [A-26
] Methyl methacrylate 50g and methylene chloride 150g
The mixed solution 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 flowing carbon dioxide into the mixture at a flow rate of 10 ml/cc for 10 minutes with stirring, cooling was stopped and the reaction mixture was left stirring until it reached room temperature. Next, this reaction mixture was mixed with 50 cc of 1N hydrochloric acid.
reprecipitated into a solution dissolved in 1 liter of methanol,
A white powder was collected by filtration. This powder was washed with water until it became neutral, and then dried under reduced pressure. Yield: 18g, Mw: 6.5×1
It was 03. Resin [A-26]

[C303]

Synthesis Example 27 of Binder Resin [A]: [A-27
] Benzyl methacrylate 95g, thioglycolic acid 4g
A mixed solution of 200g of toluene and 200g of toluene was heated at a temperature of 7
Warmed to 5°C. A. C. V. After adding 1.0 g and reacting for 6 hours, further A. C. V. Add 0.4g 3
Stir for hours. The Mw of the obtained copolymer was 7.8×10
It was 3. Resin [A-27]

[C304]

Production Example 1 of Dispersion Stabilizing Resin: [P-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate and 200 g of toluene was heated to 75° C. with stirring under a nitrogen stream. A. I. B. N
．． 1.0g was added and stirred for 4 hours, and then A. I. B.
N. 0.5 g was added and stirred for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110° C. for 8 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, a slightly brownish oil was collected, and then dried. Yield 73g, weight average molecular weight (Mw
) 3.6×104. Resin [P-1]

[C305]

[0152] Production example 2 of resin for dispersion stabilization: [P-2] 2
- 100 g of ethylhexyl methacrylate, 1 part of toluene
A mixed solution of 50 g and isopropanol was heated to 75° C. with stirring under a nitrogen stream. 2,2'-
Azobis (4-cyanovaleric acid) (abbreviation A.C.V.)
2g of A. was added and reacted for 4 hours, and then A. C. V. 0.8
g was added and reacted for 4 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, and the oil was collected and dried. 50 g of the obtained oil, 6 g of 2-hydroxyethyl methacrylate
, dicyclohexylcarbondiimide (D.C.C.) was dissolved in a mixture of 150 g of tetrahydrofuran.
8 g, 4-(N,N-dimethylamino)pyridine 0.
A mixed solution of 2g and 20g of methylene chloride was heated to a temperature of 25-3.
The mixture was added dropwise at 0°C, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added to this reaction mixture and stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol, and the oily matter was collected by filtration. Furthermore, this oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 1 liter of methanol, and the oily substance was collected and dried. The yield was 32 g, and the Mw was 4.2 x 104. Resin [P-2]

[C306]

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

[C307]

Production example 4 of dispersion stabilizing resin: [P-4]n
A mixed solution of 100 g of -butyl methacrylate, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. To this A.
I. B. N. 1 g was added and reacted for 6 hours. After cooling the reaction mixture and setting the temperature to 25°C, 10 g of 2-hydroxyethyl methacrylate and D. C. C. 8
g, 0.2 g of 4-(N,N-dimethylamino)pyridine
and 20g of methylene chloride at a temperature of 25-30℃.
The mixture was added dropwise, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added to this reaction mixture and stirred for 1 hour. After filtering out the precipitated insoluble matter, the filtrate was reprecipitated into 1 liter of methanol, and the oily matter was collected by filtration. Furthermore, this oily substance was dissolved in 200 g of tetrahydrofuran, and after filtering off insoluble matter, it was reprecipitated again in 2 liters of methanol, and the oily substance was collected and dried. The yield was 68 g and Mw was 6.6 x 103. Resin [P-4]

[C308]

Production Examples 5 to 12 of dispersion stabilizing resin: [P-
5] to [P-12] In Production Example 4, 100 g of n-butyl methacrylate
Each resin [P] was produced in the same manner as Production Example 4, except that the monomer group corresponding to Table 4 below was used instead. The Mw of each resin [P] was in the range of 5.5 x 103 to 7 x 103.

[Table 8]

Production Examples 13 to 16 of dispersion stabilizing resin: [P
-13] to [P-16] Each resin [P] was prepared in the same manner as in Production Example 4, except that a compound corresponding to Table 5 below was used instead of 2-hydroxymethacrylate. was manufactured. The Mw of each resin [P] was in the range of 6 x 103 to 7 x 103.

[Table 9]

[0157] Production example 17 of resin for dispersion stabilization: [P-17
] A mixed solution of 97 g of octyl methacrylate, 3 g of glycidyl methacrylate, and 200 g of benzotrifluoride was heated to a temperature of 75° C. while stirring under a nitrogen stream. A. I. B. N. 1.0 g was added and reacted for 4 hours. Furthermore, A. I. B. N. 0.5 g was added and reacted for 4 hours. Next, to this reaction mixture was added 5 g of methacrylic acid, N,
1.0 g of N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 110°C for 8 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, a slightly brownish oil was collected, and then dried. The yield was 73 g, and the weight average molecular weight (Mw) was 3.6 x 104. Resin [P-17]

[C309]

[0158] Production example 18 of resin for dispersion stabilization: [P-18
] A mixed solution of 85 g of butyl methacrylate, 15 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol, and 300 g of tetrahydrofuran was heated to a temperature of 60° C. while stirring under a nitrogen stream. In this, 2,2'-azobis(isovaleronitrile) (abbreviation: A.I.V.N.)
0.8g was added and reacted for 4 hours, and then A. I. V. N.
0.4 g was added and reacted for 4 hours. After cooling the reaction mixture to a temperature of 25° C., 4 g of methacrylic acid was added and D. C. C. A mixed solution of 6 g, 0.1 g of 4-(N,N-dimethylamino)pyridine, and 15 g of methylene chloride was added dropwise over 1 hour, and the mixture was stirred for an additional 3 hours. Next, 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 into 1 liter of methanol to collect the oily matter. Furthermore, this oily substance was dissolved in 150 g of benzene,
After filtering off the insoluble matter, the mixture was reprecipitated again into 1 liter of methanol to collect the oily matter and dried. Yield is 56g and Mw 8×1
It was 03. Resin [P-18]

[Chemical formula 310]

Production Examples 19 to 25 of dispersion stabilizing resin: [P
-19] to [P-25] By performing the reaction shown in Production Example 18, the following Table-6
Each of these dispersion stabilizing resins was synthesized. Mw of each resin is 6×
It was in the range of 103 to 9×103.

[Table 10]

[Table 11]

Production Example 1 of Resin Particles: [L-1] 10 g of dispersion stabilizing resin [P-1] and 200 g of methyl ethyl ketone
The mixed solution of g was heated to 60° C. with stirring under a nitrogen stream. To this, 40 g of the following monomer [A-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. Furthermore, A. I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. The latex had an average particle size of 0.20 μm. (C
Particle size measurement using APA-500 manufactured by Horiba, Ltd.). Monomer [A-1]

[Chemical formula 311]

[0161] Production examples 2 to 12 of resin particles: [L-2] to
[L-12] In Production Example 1 of resin particles, the same procedure as Production Example 1 was carried out except that each compound in Table 7 below was used instead of resin [P-18] and monomer (A-1). Resin particles were produced. The average particle size of each particle was within the range of 0.15 to 0.30 μm.

[Table 12]

[Table 13]

[0162] Production examples 13 to 23 of resin particles: [L-13
] ~ [L-23] Resin particles [L-13] were produced in the same manner as in Production Example 1, except that the polyfunctional compound shown in Table 8 below was used in place of ethylene glycol dimethacrylate in Production Example 1 of Resin Particles. ]
~[L-23] was produced. The polymerization rate of each particle is 95~
In 98% of cases, the average particle size was 0.15-0.25 μm.

[Table 14]

Production example 24 of resin particles: [L-24] 8 g of dispersion stabilizing resin [P-21] 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 (A-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 through a 200 mesh nylon cloth was 0.
．． It was 25 μm. Monomer (A-13)

[Chemical formula 312]

Production Example 25 of Resin Particles: [L-25] A mixed solution of 7.5 g of dispersion stabilizing resin [P-12] and 230 g of methyl ethyl ketone was heated at 60° C. with stirring under a nitrogen stream.
It was heated to To this, 25 g of the monomer (A-10),
Acrylamide 15g, A. I. V. N. 0.5g
A mixed solution of 200 g of methyl ethyl ketone and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. Furthermore, A. I.
V. N. After adding 0.25 g and reacting for 2 hours, the resulting dispersion was cooled and passed through a 200 mesh nylon cloth, and the average particle size of the obtained dispersion was 0.25 μm.

Production Example 26 of Resin Particles: [L-26] 42 g of the following monomer (A-14), 8 g of ethylene glycol diacrylate, 8 g of dispersion stabilizing resin [P-23] and 230 g of dipropyl ketone were heated with nitrogen. The temperature was heated to 60° C. under an air stream. This was added dropwise to a solution of 200 g of dipropyl ketone over 2 hours while stirring. After reacting for 1 hour,
Furthermore, A. I. V. N. 0.3 g was added and reacted for 2 hours. After cooling, the resulting dispersion was passed through a 200 mesh nylon cloth and the average particle size was 0.20 μm. Monomer (A-14)

[Chemical formula 313]

[0166] Production examples 27 to 36 of resin particles: [L-27
] ~ [L-36] In Production Example 26 of resin particles, dispersion stabilizing resin [P-
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 [23]. The average particle size of each particle was in the range of 0.20 μm to 0.25 μm.

[Table 15]

[0167] Production examples 37 to 42 of resin particles: [L-37
] ~ [L-42] In Production Example 25 of resin particles, monomer (A-10),
Particles were produced in the same manner as in Production Example 13, except that the compounds shown in Table 10 below were used in place of acrylamide, the reaction solvent, and methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 μm to 0.30 μm.

[Table 16]

[Table 17]

Example 1 and Comparative Examples A and B Example 1 Resin [A-4] 6 g (as solid content), Resin [B-1] having the following structure 30 g (as solid content), Photoconductive zinc oxide 200 g , methine dye [I] with the following structure 0.018
g, salicylic acid 0.15 g, and toluene 300 g in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) in a 7×1
03 r. p. m. Dispersion was carried out for 10 minutes at a rotation speed of . 4 g (as solid content) of dispersed resin particles [L-1] was added to this, and the rotation speed was further increased to 1 x 103 r. p. m. Dispersion was performed for 1 minute. This dispersion for forming a photosensitive layer was applied to electrically conductively treated paper using a wire bar so that the dry adhesion amount was 25 g/m 2 , and dried at 100° C. for 3 minutes. Then heat at 20℃ in the dark.
, by leaving it for 24 hours under the condition of 65% RH,
An electrophotographic material was created. Resin [B-1]

[Chemical formula 314] Methine dye [I]

[Chemical formula 315]

Comparative Example A An electrophotographic material was prepared in the same manner as in Example 1 except that 4 g of resin particles [L-1] were removed.

Comparative Example B 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 36 g of resin [B-1] was used instead of 30 g.

Film properties (surface smoothness), electrostatic properties, desensitization properties of the photoconductive layer (represented by contact angle with water of the photoconductive layer after desensitization treatment), and printing of these photosensitive materials I looked into gender. Printability was determined using a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using developer ELP-T to form an image through exposure and development, followed by desensitization. It was investigated using a printing board. (The printing machine used was Hamadastar 800SX manufactured by Hamadastar Co., Ltd.)
The above results are summarized in Table-11.

[Table 18]

[0172] 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: Temperature 20°C, 65%
A paper analyzer (
Kawaguchi Electric Co., Ltd. Paper Analyzer-SP-428
After corona discharge was performed for 20 seconds at -6 kV using a mold), the sample was left to stand for 10 seconds, and the surface potential at this time was measured as V10. Then, the potential V after leaving it in the dark for 120 seconds
120 and the potential retention after dark decaying for 120 seconds, that is, the dark decay retention rate [DRR (%)] [(
V120/V10)×100(%)]. In addition, after the surface of the photoconductive layer was charged to -500V by corona discharge, it was irradiated with monochromatic light with a wavelength of 780 nm, and the surface potential (
The time required for V10) to attenuate to 1/10 is determined, and the exposure amount E1/10 (erg/cm2) is calculated from this. Furthermore, as in the E1/10 measurement, due to corona discharge -
After charging to 500V, irradiate with monochromatic light with a wavelength of 780nm, calculate the time until the surface potential (V10) attenuates to 1/100, and from this, the exposure amount E1/100 (er
g/cm 2 ). The environmental conditions at the time of imaging are I
(20℃, 65%RH) and II (30℃, 80%RH)
) was carried out.

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,
Gallium-aluminum with 2.8mW output as a light source
Using an arsenic semiconductor laser (oscillation wavelength 780 nm),
Under a irradiation dose of 50 erg/cm2 on the surface of the photosensitive material, a pitch of 25 μm and a scanning speed of 330 m/sec.
After the speed exposure, the copied image was developed using ELP-T (manufactured by Fuji Photo Film Co., Ltd.) as a liquid developer and fixed, and the resulting copied image was visually evaluated for fogging and image quality.

Note 4) Water retention of raw plate: The degree of hydrophilization caused by desensitization treatment when a photosensitive material is used as a printing original plate was investigated under the following forced conditions. Each photosensitive material itself (original plate without plate making, abbreviated as "raw plate") is etched using an etching machine using an aqueous solution prepared by diluting the desensitizing treatment liquid ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) five times with distilled water. It was circulated. Furthermore, this was mixed with a solution (E-1) in which 0.5 mol monoethanolamine was diluted in 1 liter of distilled water.
immersed in water for 3 minutes. Next, these plates were printed using Hamadastar Model 8005X manufactured by Hamadastar Co., Ltd., and the presence or absence of background smear on the 50th printed matter after printing was visually evaluated.

[0176] Note 5) Background stains on printed matter: After each photosensitive material was plate-made in the same manner as in Note 3) above, it was passed through an etching machine once using ELP-EX, and then the molar ethanol of Note 4) was used. It was immersed in an amine-containing aqueous solution (E-1) for 3 minutes and then washed with water. These offset master plates were used as dampening water using ELP-FX (Fuji Photo Film Co., Ltd.).
The number of prints until the background stains on the prints could be visually determined was determined.

As shown in Table 11, the photosensitive materials of the present invention and Comparative Example A 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. Next, when used as an offset master original,
When photosensitive materials that are not used for plate making were subjected to desensitizing treatment under severe conditions by diluting the desensitizing treatment liquid and then actually printed to examine their water retention properties, the material of the present invention showed good results with no background smudges from the beginning of printing. It exhibited excellent water retention properties, and even using an actual master plate, 10,000 clear prints without background stains were obtained. On the other hand, Comparative Example A, in which no resin particles for promoting hydrophilicity were added, had insufficient water retention, and background stains on printed matter occurred from the beginning of printing and were not resolved even after printing.

[0178] In Comparative Example B, 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, regarding water retention as an offset original plate, ink adhesion was significant and staining was noticeable. This is due to the fact that the hydrophilicity is not sufficiently made; in fact, even when printing with an original plate that has been made hydrophilic under normal desensitization conditions, the background smearing of the printed matter is significant, and the copied image cannot be reproduced on the original plate after plate making. It had deteriorated and no satisfactory printing master prints could be obtained from the press run.

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 30 g, resin particles [L-12] 4.
5g (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. Resin [B-2]

[C316] Methine dye [II]

embedded image The electrophotographic properties and printability of the obtained photosensitive material were measured in the same manner as in Example 1, and the following results were obtained. Electrostatic properties (30°C, 80%RH); V10: -650V DRR: 81% E1/10: 30erg/cm2 Imaging properties
I (20℃, 65%RH); Good II (30℃
, 80%RH); Good water retention; ○
Good printing durability; both electrophotographic properties and printability were good, as it was printed over 10,000 sheets.

Examples 3 to 18 5 g each (as solid content) of resin [A] shown in Table 6 below, 4 g (as solid content) of resin particles [L], 31 g of resin [B-3] having the following structure, and methine dye [III] 0.01
Each photosensitive material was prepared in the same manner as in Example 1 except for 8 g. Resin [B-3]

[Chemical formula 318] Methine dye [III]

[Image Omitted] For each photosensitive material, electrostatic properties,
Examined print suitability. The results are shown in Table-12.

[Table 19]

[0182] The electrostatic properties are as shown in Table 12, at 30°C.
, showed very good results even under harsh conditions of 80% RH. The actual imaging performance was also good, the water retention as an original plate for offset masters was also good, and the printing durability was up to 10,000 sheets.

Example 19 and Comparative Example C Resin [A-1] 6.0 g, resin [B-5] 2 having the following structure
9.5g, resin particles [L-26] 3.8g, zinc oxide 2
00g, uranine 0.02g, rose bengal 0.04
g, bromophenol blue 0.03 g, phthalic anhydride 0.20 g and toluene 300 g in a homogenizer at a rotational speed of 6 x 103 r. p. m. Dispersion was carried out for 10 minutes to prepare a photosensitive layer-forming material, which was then spread on electrically conductive treated paper.
It was coated with a wire bar so that the dry coating weight was 22 g/m2, dried at 110°C for 20 seconds, and further heated at 120°C for 2 hours. Next, each electrophotographic light-sensitive material shown in Table 12 below was prepared by allowing the material to stand for 24 hours at 20 DEG C. and 65% RH in a dark place. Resin [B-5]

[Chemical formula 320]

Comparative Example C In Example 19, 4 g of resin [A-1] and resin [B
-5] Only resin [B-5] instead of 31.5g 35.
An electrophotographic light-sensitive material was produced in the same manner as in Example 19 except that 5 g was used. The characteristics of each photoreceptor were examined in the same manner as in Example 1, and the results are listed in Table 13.

[Table 20] In the above measurements, the electrostatic properties and imaging properties were performed in the same manner as in Example 1, except that the following operations were followed.

Note 6) Electrostatic characteristics E1/10 and E1
/100 measurement method: After charging the photoconductive layer surface to -400V by corona discharge, the photoconductive layer surface was charged with an illuminance of 2.
Irradiated with visible light of 0 lux, the surface potential (V10) was 1
/10 or E1/100, and calculate the exposure amount E1/10 or E1/100 (lux seconds) from this.

Note 7) Imageability 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 EPL-404V (manufactured by Fuji Photo Film Co., Ltd.) using EPL-T as a toner. The resulting copied images were visually evaluated for fog and image quality. The environmental conditions during imaging were 20°C, 65%RH (I), and 30°C.
It was carried out at 80% RH (II).

Note 8) Water retention and printing durability Notes 4) and 5) were carried out in the same manner as in Example 1, except that the following E-2 was used instead of the desensitizing liquid: E-1. carried out. Desensitizing treatment liquid: E-2 boric acid

55g Neo Soap (Matsumoto Yushi (
Co., Ltd.) 6
g Tetrahydrofuran
80
After dissolving g with distilled water and making the total volume 1.0 liters,
The pH was adjusted to 11.0 with potassium hydroxide.

[0188] In both the present invention and Comparative Example C, it was possible to obtain copied images with good electrostatic properties and clear image quality. Furthermore, when used as an offset master original plate, the present invention had good water retention and printing durability of up to 10,000 sheets. However, Comparative Example C, which did not contain resin [A], did not have sufficient water retention even though it was made hydrophilic under the forced conditions, and when it was actually desensitized and printed under normal conditions, Up to 4,000 prints had no visible stains. 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 20 to 27 In Example 19, 5 g of resin [A] shown in Table 14 below (
Each photosensitive material was prepared in the same manner as in Example 19, except that the resin particles [L] were 4 g (as a solid content), the resin [B] was 31 g (as a solid content), and the resin [B] was 31 g.

[Table 21]

All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and actual copied images can also be produced under high temperature and high humidity (
Even under harsh conditions (30°C, 80% RH), it provided clear images without background fog or skipped fine lines. Furthermore, when printed as an offset master master plate, 1
Printed matter with clear image quality and no background smearing was obtained even after printing 10,000 copies.

Examples 28 to 31 In Example 19, 5.5 g of resin [A-1], 5.5 g of resin [A-1],
B-5] Using 31.5 g, binder resin 3 in Table-15 below.
Each electrophotographic photoreceptor was produced in the same manner as in Example 19 except that 1.5 g was used.

[Table 22]

All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention rate, and photosensitivity, and actual copied images are also produced under high temperature and high humidity conditions (
Under severe conditions (30° C., 80% RH), it provided clear images without background fog or skipped fine lines. Furthermore, when printed as an offset master master plate, 1
Printed matter with clear image quality and no background smearing was obtained even after printing 10,000 copies.

Examples 32 to 35 ELP-
After desensitization by immersion in EX for 4 minutes, printing was performed in the same manner as in Example 1, and 10,000 prints with clear image quality and no background smudge were obtained.

[Table 23]

Examples 36 to 41 The original plate after making each photoreceptor shown in Table 17 below was subjected to ELP-
After passing through an etching machine using EX once, the resin particles were desensitized by being immersed in a desensitizing solution having the following formulation for 3 minutes. Resin particle desensitization liquid: diethanolamine
8
0g Nucol BSN (manufactured by Nippon Nyukazai Co., Ltd.) 6g
benzyl alcohol
Dissolve 100g in distilled water to make a total volume of 1 liter, then pip with potassium hydroxide.
Aqueous solution adjusted to H10.5.

[Table 24]

[0195] When this was printed in the same manner as in Example 1,
For each original plate, more than 10,000 prints with clear image quality and no background staining were obtained.

Examples 43 to 46 In Example 19, binder resin particles of the present invention [L-26
] Instead of 3.8g, use the particles shown in Table 18 below [L] 4g each
Each photosensitive material was prepared in the same manner as in Example 19, except that the following was used.

[Table 25]

After each photoreceptor was plate-made in the same manner as in Example 19, the plate-making sensitive materials were irradiated with light for 5 minutes at a distance of 10 cm from the light source using a 400 W high-pressure mercury lamp as a light source. Later ELP-FX (manufactured by Fuji Photo Film Co., Ltd.)
The film was desensitized by passing it through an etching processor once. When these printing original plates were printed in the same manner as in Example 19, they had good water retention and printing durability up to 10,000 sheets.

[0198]

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 photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin on a conductive support. At least one of the following resins [A] as adhesive resin
The photoconductive layer contains at least one of the following non-aqueous dispersion resin particles having a particle diameter that is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles. Characteristic original plate for electrophotographic planographic printing. 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. -PO3 H2, -SO3 H, -C at the end
OOH, [Chemical formula 1] [R1 represents a hydrocarbon group or -OR2 (R2 represents a hydrocarbon group)] and a resin containing at least one polar group selected from a cyclic acid anhydride-containing group . General formula (I) [Formula 2] [In the above formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group, and R3 represents a hydrocarbon group] Non-aqueous solvent System-dispersed resin particles: In a non-aqueous solvent, thiol group, phosphono group, amino group, which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, [Formula 3] [R1 is a hydrocarbon group or -OR2 group (R2 represents a hydrocarbon group)] Monofunctional monomer (A) containing at least one functional group selected from the functional groups that produce the group (R2 represents a hydrocarbon group)
Polymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. 2. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) or 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. General formula (Ia) [Chemical formula 4] General formula (Ib) [Chemical formula 5] [However, in the above formulas (Ia) and (Ib), T1
and T2 are each independently a hydrogen atom and a carbon number of 1 to 1
0 hydrocarbon group, chlorine atom, -COR4 or -COO
R5 (R4 and R5 each represent a hydrocarbon group having 1 to 10 carbon atoms), L1 and L2 each represent -C
Number of single bonds or connected atoms connecting OO- and benzene ring: 1
~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. An original plate for electrophotographic planographic printing according to items 3 to 3. General formula (II) [Formula (II)] [In the general formula (II), V0 is [Formula 7] (However, p represents an integer of 1 to 4, and R6 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ), a3,
a4 may be the same or different, and a4 may be a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-R7
or -COO-R7 (R7 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group]