JPH04296865A - Original plate for electrophotograhic lithography - Google Patents

Abstract

PURPOSE:To improve water holding performance by proper mutual action between zinc oxide, specific resin and dispersed resin particles, and obtain a superior printing image and high printing resistance even under severe conditions and secure effectiveness also in the scanning light exposure method utilizing the semiconductor laser beam. CONSTITUTION:An original plate for electronic photograph type lithography printing contains at least each one kind of the polymer component having the repetitive unit represented by the formula I and the nonaqueous solvent group dispersed resin particles having an average particle diameter of 0.8 or less and is obtained through the polymerization reaction between the resin (A) which has an average molecular weight of 1X10<3>-2X10<4> and is formed by joining the polar group at one terminal of the main chain of the polymer, and the monomer (C) containing a specific polar group at one terminal of the main chain of the polymer, under the presence of the dispersion stabilizing resin containing the substitution group containing silicon atoms and/or fluorine atoms.

Description

[Detailed description of the invention]

0001

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

0002

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

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

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

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

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

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

[0008]

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

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

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

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

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

[0013] A second object of the present invention is to provide a lithographic printing original plate that has a clear and high-quality image even when the environment during copy image formation varies from low temperature and low humidity to high temperature and high humidity. .

A third object of the present invention is to provide a lithographic printing original plate that is not easily affected by the types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even when used in a scanning exposure method using semiconductor laser light.

[0015]

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

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 -PO3H2,
-SO3H, -COOH, -P(=O)(OH)R
01 [R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group)] and a cyclic acid anhydride-containing group. [The above -P(=O)(OH)R01 is

[0017]

[C4] shows. ]

[0018]

embedded image [However, in the above formula (I), a 1 , a 2
each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R03 represents a hydrocarbon group]

Non-aqueous solvent-based dispersed resin particles: Carboxyl groups, sulfo groups, sulfino groups, phosphono groups, -P(= O)(OH)R0 [R0 represents a hydrocarbon group or -OR10 [R10 represents a hydrocarbon group]], hydroxyl group, formyl group, amide group,
A monofunctional monomer (C) containing at least one polar group selected from a cyano group, an amino group, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterocyclic group is combined with a silicon atom and/or Copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, which comprises at least one type of repeating unit containing a fluorine atom-containing substituent.

Further, the lithographic printing original plate of the present invention contains at least zinc oxide particles, a repeating unit polymer component, a low molecular weight resin [A] having a polar group bonded to one end of the polymer main chain, and Each of them is characterized by containing non-aqueous solvent-based dispersed resin particles (hereinafter sometimes abbreviated as resin particles).

[0021] 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.

As mentioned above, the technique of incorporating hydrophilic resin particles into the photoconductive layer and the binder resin of the electrophotographic photoreceptor,
Techniques using resins containing acidic groups in their side chains are known, but as in the present invention, as the resin particles and binder resin contained in the photoconductive layer, components containing polar groups and silicon atoms and/or fluorine are used. Low molecular weight resin [A
] Surprisingly, the above-mentioned problems that were unresolved using only these known techniques can be solved,
That is, it has been found that scumming and printing durability are dramatically improved.

[0023] In a printing original plate in which the non-image area of the photoconductive layer containing at least photoconductive zinc oxide and a binder resin is treated with a desensitizing liquid to make the surface hydrophilic and a lithographic printing original plate is obtained. Compared to known technologies that coexist with hydrophilic resin particles, the technology of the present invention achieves both faithful reproduction of copied images and excellent water retention in non-image areas even under harsh environmental conditions of high temperature and humidity. It is possible.

[0024] Although the details are unknown, this means that when dispersed in the presence of zinc oxide, resin [A], and resin particles, a specific polar group is bonded to a specific position. Each polar group of the low molecular weight resin [A] and the monodispersed, microscopic resin particles containing a specific polar group is adsorbed to the stoichiometric defects of the photoconductive zinc oxide, and the oxidation Appropriate surface coverage and adsorption conditions of zinc compensate for trapping of photoconductive zinc oxide and dramatically improve humidity characteristics, while sufficient dispersion of photoconductive zinc oxide is achieved. It is estimated that it suppresses aggregation.

Furthermore, the resin particles contain a polymer component containing fluorine atoms and/or silicon atoms, and as a result, the particles migrate and concentrate on the surface portion of the photoconductive layer, which is known in the art. It is also mentioned that an extremely small amount is required to produce the same effect as that of the technology, that is, to produce hydrophilicity. Furthermore, since sufficient hydrophilicity can be obtained with a small amount, adverse effects on electrophotographic properties can be suppressed.

In other words, due to these factors, the state of the film formed by the interaction of the above three factors changes depending on the hydrophilization reaction of zinc oxide by the desensitizing treatment liquid and the membrane surface portion of the hydrophilization product (chelate compound). This is considered to be a very suitable method for holding. Furthermore, since the resin particles are particles that inherently have hydrophilic properties, they play an important role in promoting the hydrophilization reaction during desensitization treatment and improving the water retention of the surface portion after hydrophilization. considered to be a thing. In other words, it is estimated that the water retention properties of the non-image areas of the printing original plate of the present invention are dramatically improved by the actions of the three parties mentioned above, especially the actions of the resin particles.

However, in general, in the electrophotographic method, if the electrophotographic method does not exhibit good water retention and excellent electrophotographic properties, background stains may occur in non-image areas during copy image formation, and document reproducibility in image areas may deteriorate. It is known that the image quality of printed matter deteriorates, and as a result, it becomes impossible to obtain printed matter with satisfactory image quality. In contrast, in the lithographic printing original plate of the present invention, even the microscopic state of photoconductive zinc oxide is dispersed only when both the resin particles and the resin [A] are appropriately present in the zinc oxide. Since the state is controlled,
Not only has water retention been improved, but electrophotographic properties (especially actual imaging performance) have also been improved, and good performance can now be stably maintained even under harsh conditions of high temperature and high humidity, or low temperature and low humidity.

[0028] The resin particles used in the present invention have an average particle diameter that is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and that the particle diameters are uniform compared to zinc oxide and resin. favorable for interaction.

On the other hand, in the resin particles of the present invention, if the resin particles have a particle size larger than the zinc oxide particle size, the electrophotographic properties deteriorate (particularly, uniform charging properties cannot be obtained), and as a result, In the copied image, density unevenness in the image area, broken or skipped characters and thin lines, and background fog in the non-image area occur.

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

[0031] In the present invention, if the resin particles form a high-order mesh structure, the dissolution in water is further suppressed,
On the other hand, water swelling properties are developed, and water retention properties are further improved.

[0032] Furthermore, as the above-mentioned dispersion stabilizing resin in the present invention, one containing at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain is particularly preferable. It is mentioned as a thing.

[0033]

[C6]

[In general formula (II), V 0 is -
O −, −COO −, −OCO −, −(CH 2
) pOCO-, -(CH2)pCOO-
, -SO2 -, -CONR1 -, -SO2 NR1
-, -C6H4-, -CONHCOO-, or -CONHCONH- (where p represents an integer of 1 to 4, and R1 is a hydrogen atom or a carbon number of 1 to 18
(represents a hydrocarbon group), a 1 and a 2 may be the same or different from each other, and represent a hydrogen atom, a halogen atom,
Represents a cyano group, a hydrocarbon group, -COO-R 2 or -COO-R 2 via a hydrocarbon group (R 2 represents a hydrogen atom or a hydrocarbon group which may be substituted)]

[0035] A polymerizable double bond represented by general formula (II) only at one end of the polymer main chain comprising at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom of the present invention. It is important that the dispersion stabilizing resin, which is characterized by bonding a group, copolymerizes with the monomer (C) and is solvated and soluble in the non-aqueous solvent, so that it is a so-called non-aqueous dispersion. It functions as a stabilizing resin.

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

[0037] Furthermore, a film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent has a contact angle with distilled water (measured with a goniometer) of 50 degrees or less, preferably 40 degrees. A hydrophilic polymer component having the following values and consisting of a specific polar group that is insoluble in the non-aqueous solvent and a dispersion stabilizing resin that is soluble in the non-aqueous solvent. In the case of a dispersion stabilizing resin formed by physicochemically adsorbing a polymer component or containing a polymerizable double bond group moiety represented by the above formula (II), both polymer components are chemically bonded. It is preferable that

Furthermore, the resin [A] contains at least one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). A resin [A] (hereinafter, this low molecular weight product will be referred to as a resin [A']) containing 1 is preferable.

[0039]

[C7]

[However, in the above formulas (Ia) and (Ib), T 1 and T 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -CO
R 04 or -COOR05 (R 04 and R 05 each represent a hydrocarbon group having 1 to 10 carbon atoms), and L
1 and L 2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring]

When resin [A'] is used, the electrophotographic properties (especially V10, D.R.
R, E1/10) improvement can be achieved.

The reason for this is unknown, but one reason is that due to the planarity effect of the benzene ring or naphthalene ring, which is the ester component of methacrylate, the alignment of these polymer molecular chains at the zinc oxide interface in the film is This is thought to be due to proper implementation.

[0043] The binder resin [A
] will be explained in more detail. In weight [A],
The weight average molecular weight is 1 x 103 to 2 x 104, preferably 3 x 103 to 1 x 104, and the glass transition point of the resin [A] is preferably -20°C to 110°C, more preferably -10°C to 90°C. It is ℃.

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

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

[0046] The polar group content in resin [A] is 0.5
If it is less than % by weight, the initial potential will be low and sufficient image density will not be obtained. On the other hand, if the polar group content is more than 15% by weight, the dispersibility decreases no matter how low the molecular weight is, and furthermore, background smudge increases when used as an offset master.

[0047] As the low molecular weight resin [A], resins having specific substituents at the 2-position and/or at the 2- and 6-positions as shown in the general formulas (Ia) and (Ib) above are used. Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring
] (hereinafter, this low molecular weight material will be referred to as resin [A']).

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

Next, the repeating unit represented by the general formula (I), which is contained in the resin [A] in an amount of 30% by weight or more, will be further explained. In general formula (I), a1 and a2 are
Preferably -C via a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), -COO-R06 or a hydrocarbon group
OO-R06 (R06 is a hydrogen atom or a carbon number of 1 to 18
represents an alkyl group, alkenyl group, aralkyl group, alicyclic group, or aryl group, which may be substituted, and specifically represents the same content as described for R03 below.

Hydrocarbons in the -COO-R06 group via the hydrocarbon include methylene group, ethylene group,
Examples include propylene group. R03 has 1 or more carbon atoms
18 optionally substituted alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc.), optionally substituted alkenyl group having 2 to 18 carbon atoms (e.g. vinyl group,
allyl group, isopropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7-12
optionally substituted aralkyl group (benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.) having 5 to 8 carbon atoms; optionally substituted cycloalkyl groups (e.g. cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, (ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.).

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

In formula (Ia), preferred T1 and T2 are independently hydrogen, chlorine and bromine atoms, respectively, and hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), carbon number 7 or more
9 aralkyl groups (e.g. benzyl group, phenethyl group,
3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group) , methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR04
and -COOR05 (preferred examples of R04 and R05 include those described above as preferred hydrocarbon groups having 1 to 10 carbon atoms).

In formulas (Ia) and (Ib), L1
and L2 are each a direct bond connecting -COO- and a benzene ring, or -(CH2)n1- (n1 represents an integer of 1 to 3), -CH2 OCO-, -CH2 CH2 O
A linking group having 1 to 4 linking atoms such as CO-, -(CH2O)m1- (m1 represents an integer of 1 or 2), -CH2CH2O-, and more preferably a direct bond or bond. A linking group having 1 to 2 atoms can be mentioned.

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

[0055]

[Chemical formula 8]

[0056]

[Chemical formula 9]

[0057]

[Chemical formula 10]

[0058]

[Chemical formula 11]

[0059]

[Chemical formula 12]

[0060]

[Chemical formula 13]

[0061]

[Chemical formula 14]

[0062]

[Chemical formula 15]

[0063]

[Chemical formula 16]

[0064]

[Chemical formula 17]

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

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

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

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

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

[0070] These polar groups may be bonded directly to the terminal of the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but specific examples include -[C(d1)(d2
)] - (d1 and d2 may be the same or different, and each represents a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.),
OH group, cyano group, alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl (representing a group, etc.),
-(CH(d3)-CH(d4))]-(d3, d
4 represents the same content as d1 and d2), -C6 H
10-, -C6 H5, -O-, -S-, -N(d5
)-[d5 represents a hydrogen atom or a hydrocarbon group (the hydrocarbon group specifically includes a hydrocarbon group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, Octyl group, decyl group, dodecyl group, 2
-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorofer group, methoxyphenyl group, butylphenyl group)],
-CO-, -COO-, -OCO-, -(d5)CO
N-, -SO2 N(d5)-, -SO2 -, -N
HCONH-, -NHCOO-, -NHSO2 -, -
CONHCOO-, -CONHCONH-, heterocycle (any 5- to 6-membered ring containing at least one type of O, S, N, etc. as a hetero atom, or a condensed ring thereof; for example, a thiophene ring, a pyridine ring, (furan ring, imidazole ring, piperidine ring, morpholine ring, etc.) or -Si(d6)(d7)-(d6, d7
may be the same or different, and may be a hydrocarbon group or -Od8
(d8 is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones listed for d5) alone or in combination.

Furthermore, preferably, the binder resin [A] is a copolymer component represented by the above general formula (I) [general formula (Ia)
or (Ib)], and as polymer components copolymerized therewith, -PO3 H2, -S
Contains 0.5 to 10% by weight of a copolymerization component containing at least one polar group selected from O3H, -COOH, -P(=O)(OH)R01, and a cyclic acid anhydride-containing group. is preferable in terms of further improving electrostatic properties.

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

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

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

[0075]

[Chemical formula 18]

[0076]

[Chemical formula 19]

[0077]

[C20]

[0078]

[C21]

[0079]

[C22]

[0080]

[C23]

[0081]

[C24]

[0082]

[C25]

[0083]

[C26]

[0084]

[C27]

[0085]

[C28]

[0086]

[C29]

[0087]

[C30]

[0088]

[Chemical formula 31]

[0089]

[C32]

[0090]

[Chemical formula 33]

[0091]

[C34]

[0092]

[C35]

[0093]

[C36]

[0094]

[C37]

[0095]

[C38]

[0096]

[C39]

[0097]

[C40]

[0098]

[C41]

0099

[C42]

[0100]

[C43]

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

Such other copolymerization components include, for example, methacrylic esters, acrylic esters, and crotonic esters containing substituents other than those explained in general formula (I), as well as α-olefins. vinyl carboxylates or acrylic esters (e.g. carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic esters (e.g. dimethyl ester, diethyl ester, etc.)
, acrylamides, methacrylamides, styrenes (e.g. styrene, vinyltoluene, chlorostyrene,
hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

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

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

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

[0106] Specific examples of the polymerization initiator containing the polar group or a specific reactive group include 4,4'-azobis(4-cyanovaleric acid) and 4,4'-azobis(4-cyanovaleric acid).
cyanovaleric acid chloride), 2,2'-azobis(2-
cyanopropanol), 2,2'-azobis(2-cyanopentanol), 2,2'-azobis[2-methyl-
N-(2-hydroxyethyl)-propioamide], 2
, 2'-azobis{2-methyl-N-1,1-bis(hydroxymethyl)-2-hydroxyethyl]propioamide}, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2 -imidazolin-2-yl]propane}, 2,2'-azobis[2-(2-imidazoline-2
-yl)propane], 2,2'-azobis[2-(4,
5,6,7-tetrahydro-1H-1,3-diazopin-2-yl)propane] and the like.

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

[0108] Other resins used in combination have a weight average molecular weight of 3 x 104 to 1 to 106, preferably 5 x 104.
It is a medium to high molecular weight substance of ~5x105. Further, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C.

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

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

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

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).

[0113]

[C44]

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

R07 represents the same content as R03 in formula (I). As the medium to high molecular weight binder resin (hereinafter referred to as resin [B]) containing the polymer component represented by the general formula (III), for example, a random binder resin containing the polymer component represented by the formula (III) can be used. Polymer resin (JP-A-63-4
9817, 63-220149, 63-22014
8 publications, etc.), combined resins of the random copolymer and crosslinkable resin (JP-A-1-102573, etc.), graft copolymers (JP-A-2-53064, JP-A-2-56558, etc.), etc. Examples include medium to high molecular weight substances described in each specification.

[0116] The non-aqueous solvent-based dispersed resin particles used in the present invention will be explained in more detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization.

The non-aqueous solvent-based dispersed resin particles of the present invention are polymers comprising a monofunctional monomer (C) that contains at least one of the above-mentioned specific polar groups and becomes insoluble in the non-aqueous solvent after polymerization. A polymer consisting of a component [abbreviated as polymer component (C)] and a dispersion stabilizing resin that contains a repeating unit containing at least a fluorine atom and/or a silicon atom as a substituent and is soluble in the non-aqueous solvent even after polymerization. It is characterized by a combination of components.

[0118] The resin particles used in the present invention have an average particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles, and have a narrow particle size distribution and uniform particle size. It is.

Specifically, the resin particles of the present invention have a maximum particle 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.

[0120] The smaller the particle diameter of the resin particles, the larger the specific surface area, which brings about good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, If it is too large, it will resemble the case of molecular dispersion, and the effect of particles on improving water retention capacity will be diminished, so it is preferable to use the particle size at 0.001 μm or more.

[0121] In the present invention, resin particles that do not form a higher-order mesh structure as described above or resin particles that do form a higher-order mesh structure (hereinafter simply referred to as "wire resin particles") are photoconductive oxidized resin particles. It is preferably used in an amount of 0.01 to 10% by weight based on 100 parts by weight of zinc. If the resin particles or mesh resin particles are less than 0.01% by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 10% by weight, the hydrophilicity of the non-image area can be further improved, but it is difficult. The electrophotographic characteristics under these conditions deteriorate, resulting in a deteriorated copy image.

Monomer (C) as a polymerization component in the resin
The presence ratio of the resin is 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the resin is composed only of the monomer (C) and the dispersion stabilizing resin.

[0123] Specifically, the solubility of the dispersion stabilizing resin of the present invention in the nonaqueous solvent is such that it dissolves at least 5% by weight in 100 parts by weight of the solvent at a temperature of 25°C.

[0124] The weight average molecular weight of the dispersion stabilizing resin is 1 x 103 to 1 x 105, preferably 2 x 1
03 to 5×104, particularly preferably 3×103 to
It is 2×104.

[0125] The weight average molecular weight of the dispersion stabilizing resin is 1×1
If it is less than 0.03, the produced dispersed resin particles will aggregate, making it impossible to obtain fine particles with a uniform average particle size.

On the other hand, if it exceeds 1×10 5 , the effect of the present invention of improving water retention while satisfying electrophotographic properties when added to the surface layer will be diminished.

[0127] In the total number of repeating units in the dispersion stabilizing resin of the present invention, repeating units having a substituent containing a fluorine atom and/or a silicon atom account for 30% by weight of the total.
It is preferable that the content is 5 or more, more preferably 5
It is 0% by weight.

[0128] When the above-mentioned components of the present invention are less than 40% by weight of the total, the effect of concentrating the resin particles on the surface layer when dispersed in the surface layer decreases, and as a result, the effect of improving water retention as a printing original plate decreases. fades away.

The dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the monomer (C) to be insolubilized as described above.

First, to explain the monofunctional monomer (C) which is soluble in non-aqueous solvents but becomes insolubilized by polymerization, the monomer (C) has - in its molecular structure.
CO2H, -SO3H, -PO3H2,
-SO2H, -OH, -CN, -CHO, -CO
NH2, -SO2 NH2, -P(=O)(OH)
It contains at least one polar group selected from R0, -N(R11)(R12), a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterocyclic group.

Here, -P(=O)(OH)(R 0 )
and the cyclic acid anhydride-containing group are the same as explained in the section of the resin [A] above.

R11 and R12 may each be the same or different, and each represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (specifically, a hydrocarbon group having the same content as R 0 ). ). However, the total number of carbon atoms in R11 and R12 is 8 or less. More preferably, the total number of carbon atoms in R11 and R12 is 4 or less.

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

[0134] Moreover, the above -COOH group, -SO2 H group,
-SO3 H group, -PO3 H2 group, -P(=O)(
The OH)R0 groups each represent a metal salt of an alkali metal (e.g., lithium, sodium, potassium, etc.), an alkaline earth metal (e.g., calcium, magnesium, etc.), zinc, aluminum, or an organic base (e.g., triethylamine, pyridine, etc.). morpholine, piperazine, etc.).

The monomer (C) constituting the main component of the resin particles of the present invention contains at least one of the above polar groups and has a polymerizable double bond group in one molecule. Any item is fine. More specifically, an example of the monomer (C) is shown by the general formula (V).

[0136]

[C45]

[0137] In the formula, X1 is a direct bond or -CO
O-, -OCO-, -O-, -SO2 -, -CO-,
-SO2 NR15-, -CONR15-, -CONH
COO-,-CONHCONH-,-[C(R16)(
R17)]i -, -C6 H4 - or -C6 H1
Represents 0-.

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

R16 and R17 may be the same or different and are hydrogen atoms, halogen atoms (preferably, for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) or aliphatic groups having 1 to 4 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, etc.),

[0140] i represents an integer from 1 to 6. ]

0141
] W represents a polar group of the monomer (C) described above.

[0142] L3 is -[C(l1)(l2)]
-, -C6 H10-, -C6 H4 -, -[C(l
3)=C(l4)], -COO-, -OCO-, -
O-, -S-, -SO2 -, -N(l5), -CO
N(l6)-,-SO2 N(l7)-,-NHC
OO-,-Si(l8)(l9)-,-NHCON
Represents a linking group selected from H- or -CO- or a linking group formed by a combination of these linking groups. [Here, l1 to l4 may be the same or different,
Hydrogen atom, halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2 -chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, etc.) or the formula (V
) represents a -[L3-W] group,

l5 to l9 represent the same contents as R15 above. ]

[0144] e1 and e2 may be the same or different, and are hydrogen atoms, halogen atoms (preferably, for example,
fluorine atom, chlorine atom, bromine atom, etc.), -COOH group,
-COOR18 groups, -CH2 COOR18 groups (R18
represents a hydrocarbon group having 1 to 7 carbon atoms, and specifically includes the same content as the hydrocarbon group of R15 above) or an alkyl group having 1 to 4 carbon atoms (preferably, for example, a methyl group, (ethyl group, propyl group, butyl group, etc.).

[0145] More specifically, the above monomer (C) will be described below.
are illustrated, but the present invention is not limited thereto.

[0146] Here, a is -H, -CH3, -Cl,
-CH2COOH or -CH2COOCH3, b is -CH3, -COOH, -CONH2, -
CONHC2 H5 or -COOCH3, c
represents -CH3 or -H, d represents -CH3, -H or -Cl, e represents -H, -CH3, -CH2C
OOH or -CH2COOCH3, f is -H
, -CH3 or -CH2COOCH3, R
19 represents -H, -CH3 or -C2H5, Y
1 is -SO3H, -COOH, -CH2OH, -
O-P(=O)(OH)2,-SO2H,-CON
H2 , -SO2 NH2 or -OH, Y2
represents -OH or -NH2, n1 represents an integer of 1 to 12, n2 represents an integer of 1 to 4, and n3 represents an integer of 2 to 4.
represents an integer of 12, n4 represents an integer of 1 to 11, n
5 represents a positive number from 1 to 10, n6 represents an integer from 2 to 10, n7 represents an integer from 1 to 3, and m1 represents an integer from 1 to 1.
represents an integer of 0, and m2 represents an integer of 1 to 4.

[0147]

[C46]

[0148]

[C47]

[0149]

[C48]

[0150]

[C49]

[0151]

[C50]

[0152]

[C51]

[0153]

[C52]

[0154]

[C53]

[0155]

[C54]

[0156]

[C55]

[0157]

[C56]

[0158]

[C57]

[0159] Along with the polar group-containing monomer (C) as described above, other copolymerizable monomers may be contained as a polymer component. Examples of other monomers include α-olefins, vinyl alkanoates or allyl esters, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls [for example, nonmetallic atoms other than nitrogen atoms] It is a 5- to 7-membered heterocycle containing 1 to 3 oxygen atoms, sulfur atoms, etc., and specific examples include vinylthiophene, vinyl dioxane, vinylfuran, etc. As a preferable example, for example,
Vinyl alkanoates or allyl esters having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives (e.g. vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, ethoxystyrene, etc.), etc. Can be mentioned. However, it is not limited to these.

Next, in the non-aqueous solvent-based dispersed resin particles of the present invention, a soluble dispersion-stabilizing resin that stabilizes the dispersion of the resin particles in the non-aqueous solvent will be described.

The dispersion stabilizing resin used in the present invention is characterized by containing a substituent containing a fluorine atom and/or a silicon atom in the polymer.

[0162] These repeating units having a substituent containing a fluorine atom and/or a silicon atom will be explained.

[0163] Examples of the chemical structure of the repeating unit include those obtained from radical addition polymerizable monomers, those consisting of a polyester structure, and those consisting of a polyether structure. Any chain containing a fluorine atom and/or a silicon atom may be used.

Examples of the fluorine atom-containing substituent include -C h F 2h+1 (h represents an integer of 1 to 12), -(CF 2 ) j CF2 H (j is 1 to 1)
), -C 6 Hl F l' [(l
, l' are each an integer of 1 to 5, provided that l+l'=5) or (l=5-l', l' is an integer of 1 to 5).

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

[0166] However, R 3 , R 4 , R 5
represent a hydrocarbon group or an -OR9 group (R9 represents the same content as the hydrocarbon group of R3), which may be the same or different and may be substituted.

R 3 is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group,
Dodecyl group, hexadecyl group, 2-chloroethyl group, 2
-bromoethyl group, 2,2,2-trifluoroethyl group,
2-cyanoethyl group, 3,3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2
-methoxycarbonylethyl group, 2,2,2,2',2
',2'-hexafluoroisopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group,
phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl group, 2-cyclopentylethyl group, etc.), or carbon Number 6
~12 optionally substituted aromatic groups (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group,
Dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxy (carbonylphenyl group, acetamidophenyl group, propylamidophenyl group, dodecoylamidophenyl group, etc.).

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

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

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

[0171]

[C58]

[0172]

[C59]

[0173]

[C60]

[0174]

[C61]

[0175]

[C62]

[0176]

[C63]

[0177]

[C64]

[0178]

[C65]

Further, the dispersion stabilizing resin may contain other components together with the fluorine atom- and/or silicon atom-containing component. Other copolymerized components may be any components that copolymerize with the corresponding polymer, and examples of the corresponding monomers include α-olefins, styrenes, acrylonitrile, methacrylonitrile, Vinyl-containing heterocycles (heterocycles include, for example, pyran ring, pyradoline ring, imidazole ring, pyridine ring, etc.), vinyl group-containing carboxylic acids and their esters (for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
(maleic acid and its esters, etc.), vinyl group-containing carboxamides (eg, acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.). In the dispersion stabilizing resin of the present invention, the fluorine atom and/or silicon atom-containing polymer component is the total polymer component of the resin.
00 parts by weight or more, preferably 50 parts by weight or more.

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

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

[0182]

[C66]

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

In addition to a hydrogen atom, R 1 is preferably a hydrocarbon group such as an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). , hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-methoxycarbonylethyl group, 2
-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g. 2-bromopropyl group, etc.),
-Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-
methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro benzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (for example, cyclohexyl group) , 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
Or, an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group) , ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group,
acetamidophenyl group, propioamidophenyl group,
dodecoylamidophenyl group, etc.).

When V0 represents -C 6 H 4 -, the benzene ring may have a substituent. Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, etc.),
Alkyl groups (e.g. methyl, ethyl, propyl, butyl, chloromethyl, methoxymethyl, etc.)
, alkoxy groups (eg, methoxy group, ethoxy group, propioxy group, butoxy group, etc.).

b 1 and b 2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, (methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R 2 or COOR2 via a hydrocarbon (R 2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group) represents a formula group or an aryl group, which may be substituted, and specifically represents the same content as described for R1 above.

-COO-R 2 via the above hydrocarbon
Examples of the hydrocarbon group include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in general formula (II), V 0 is -COO-, -OCO-, -CH2
OCO -, -CH2 COO -, -O -, -C
represents ONH-, -SO2NH- or -C6H4-, b1 and b2 may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COOR2 or -CH2COOR2, (R2 is hydrogen Represents an atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). Still more preferably b 1 , b 2
One of these always represents a hydrogen atom.

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

The polymerizable double bond group moiety represented by the general formula (II) described above is located at one end of the main chain of a polymer containing at least a repeating unit having a substituent containing a fluorine atom and/or a silicon atom. and are bonded directly or via any linking group. Specifically, the connecting group is a divalent organic residue, -O-, -S-
, -Nd1 -, -SO-, -SO2 -, -COO
-, -OCO-, -CONHCO-, -NHCONH
-, -CONd2 -, -SO2 Nd3 - and -S
composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from i(d4)(d5)- Represents an organic residue. Here, d 1 to d5 are expressed by the formula (I
It represents the same content as R 1 in I).

As a divalent aliphatic group, for example, -C(e
8 ) (e 9) −, − C(e8 ) = C(e
9) -, -(C≡C)-, -C6H10-,

[0192]

[C67]

{e 8 and e 9 are
They may be the same or different from each other, and each contains a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a chloromethyl group, Bromomethyl group,
butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q is -O-, -S- or -NR20-
, R20 is an alkyl group having 1 to 4 carbon atoms, -C
H2Cl or -CH2Br}.

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

Examples of the heterocyclic group include a furan ring, a thiophene ring, a pyridine ring, a pyrazine ring, a piperazine ring, a tetrahydrofuran ring, a pyrrole ring, a tetrahydropyran ring, and a 1,3-oxazoline ring.

[0196] Specifically, the polymerizable double bond group-containing moiety as described above is bonded only in the polymer chain, or has a polymerizable double bond group only at one end of the main chain of the polymer chain. A polymer to which a containing moiety is bonded (hereinafter abbreviated as a monofunctional polymer [M]) can be mentioned. Specific examples of the portion composed of the polymerizable double bond group component represented by the general formula (II) of the monofunctional polymer [M] and an organic residue linked thereto include the following. However, it is not limited to these. However, in each example below, P 1 is -H
, -CH3, -CH2COOCH3, -Cl,
-Br or -CN, P2 is -H or -CH3
, X represents -Cl or -Br, and n is 2 to 12
represents an integer of 1 to 4, and m represents an integer of 1 to 4.

[0197]

[C68]

[0198]

[C69]

[0199]

[C70]

[0200]

[C71]

[0201]

[C72]

[0202]

[C73]

[0203]

[C74]

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. for example,
■ A method using an ionic polymerization method in which a monofunctional polymer [M] is obtained by reacting various reagents with the ends of a living polymer obtained by anionic or cationic polymerization, ■
Polymers with terminal reactive groups bonded by radical polymerization using a polymerization initiator and/or chain transfer agent containing reactive groups such as carboxyl groups, hydroxyl groups, and amino groups in the molecule and various A monofunctional polymer [M
], and (2) a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into a polymer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. It will be done.

Specifically, P. Dreyfuss &
R. P. Quirk, Encycle. Polym. S
ci. Eng. , 7, 551 (1987), P. F. R
empp, E. Franta, Adv. Polym
．． Sci. , 58, 1 (1984), V. Perce
c, Appl. Poly. Sci. , 285, 9
5 (1984), R. Asami, M. Takar
i, Makromol. Chem. Suppl. ,1
2, 163 (1985), P. Rempp. et
al, Makromol. Chem. Suppl. ，
8, 3 (1984), Yuji Kawakami, Chemical Industry, 38, 5
6 (1987), Yuya Yamashita, Kobunshi, 31,988 (1
982), Shiro Kobayashi, Polymers, 30,625 (198
1), Toshinobu Higashimura, Japan Adhesive Association Journal, 18,536 (1)
982), Koichi Ito, Polymer Processing, 35,262 (1
986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987
, No. It can be synthesized according to the methods described in reviews such as 10, 5 and the literature/patents cited therein.

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

[0207] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (1) a method of crosslinking a polymer containing the polymer component (C) with various crosslinking agents or curing agents; (2) a method of carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (C); a method of forming a wire structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and This can be carried out by a method such as a method in which a polymer containing a component containing a reactive group is crosslinked by a polymerization reaction or a polymer reaction.

[0208] As the crosslinking agent in the above method (2), compounds which are commonly used as crosslinking agents can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
Compounds described in "Polymer Data Handbook Basic Edition" edited by the Society of Polymer Science, Baifukan (1986), published by Taiseisha (1981), etc. can be used.

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

[0210] In addition, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (D)) or a polymerizable functional group of a polyfunctional oligomer that is made to coexist in the method (2) above can be used. Specifically, the group is CH2=CH-CH2
-, CH2 = CO-O, CH2 = CH -, C
H2 = C(CH3)-CO-O-, C(CH3
)H=CH-CO-O-, CH2=CH-CONH-
, CH2=C(CH3)-CONH-, CH(CH
3)=CH-CONH-, CH2=CH-O-
CO-, CH2=C(CH3)-O-CO-, C
H2=CH-CH2-O-CO-, CH2=C
H-NHCO-, CH2=CH-CH2-NHCO
-, CH2 = CH-SO2 -, CH2 = CH-
CO-, CH2=CH-O-, CH2=CH-S
- and so on. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

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

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

[0214] Furthermore, in the case of forming chemical bonds and bridging between polymers by the reaction of the reactive groups between the polymers in the above method It can be carried out. Specifically, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (published in 1976)
It is described in detail in books such as . For example, polymer reactions involving combinations of functional groups in Group A (hydrophilic group polymer components) and Group B (polymers containing components containing reactive groups) in the table below are usually well known. This is one of the methods. Note that R21 and R22 in Table 1 are hydrocarbon groups, and are represented by the above formula (
Represents the same content as l 8 and l 9 in L 3 of V).

[0215]

[Table 1]

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

[0217] In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can easily be obtained, so polyfunctional polymerization is a method for forming a wire structure. Method (2) using a monomer is preferred.

[0218] As the non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles, any organic solvent with a boiling point of 200°C or less may be used, and it may be used alone or in a mixture of two or more. good.

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

[0220] 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
“Dispersion Polymerizati
on in Organic Media”John
Wiley (1975), Koichiro Murata, Polymer Processing,
23, 20 (1974), Tsunetaka Matsumoto and Toyokichi Tange, Journal of Japan Adhesive Association 9, 183 (1973), Toyokichi Tange, Journal of Japan Adhesive Association 23, 26 (1987), D. J. Walbr
idge, NATO. Adv. study. Inst
．． Ser. E. No. 67, 40 (1983), British Patent Nos. 893429 and 934038, U.S. Patent Nos. 1122397, 3900412, and 4606
989 specifications, JP-A-60-179751, JP-A-60
The method is disclosed in publications such as No.-185963.

[0222] The dispersion resin of the present invention is composed of at least one each of monomer (C) and monofunctional polymer [M],
When forming a wire structure, polyfunctional monomers (D) are allowed to coexist as necessary; in any case, the important thing is that the resin synthesized from these monomers does not dissolve in the non-aqueous solvent. If it is insoluble, a desired dispersed resin can be obtained.

[0223] In order to produce the dispersed resin particles used in the present invention as described above, the monomer (C), the monofunctional polymer [M], and the polyfunctional monomer (D) are generally used. benzoyl peroxide, azobisisobutyronitrile, in a non-aqueous solvent,
The polymerization may be carried out by heating in the presence of a polymerization initiator such as butyllithium. Specifically, the methods include: (1) adding a polymerization initiator to a mixed solution of monomer (C), monofunctional polymer [M], and polyfunctional monomer (D); (2) adding a polymerization initiator to a nonaqueous solvent; , a method in which a mixture of the above-mentioned polymerizable compound and a polymerization initiator is added dropwise or arbitrarily, and the method is not limited to these methods, and any method can be used for production.

[0224] The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the nonaqueous solvent.
~50 parts by weight.

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

[0226] The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

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

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Furthermore, other inorganic photoconductors such as titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, etc. may be used in combination.

However, these other photoconductive materials account for less than 40% by weight of the photoconductive zinc oxide, preferably less than 20% by weight.

[0230] When the amount of other photoconductive materials exceeds 40% by weight,
The effect of improving the hydrophilicity of the non-image area as a lithographic printing original plate is weakened. As the photoconductive zinc oxide according to the present invention, those conventionally known in this type of technical field may be used, including not only so-called zinc oxide, but also zinc oxide treated with an acid, zinc oxide pretreated with a dye, etc. It may be kneaded and then ground again (so-called press treatment), and there is no particular limitation.

[0231] In the lithographic printing original plate of the present invention, the total amount of binder resin used for photoconductive zinc oxide is 10 to 100 parts by weight based on 100 parts by weight of photoconductive zinc oxide. , preferably in a proportion of 15 to 50 parts by weight.

The spectral sensitizing dye used in the photoconductive layer of the present invention may be any conventionally known dye and these may be used alone or in combination. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8)
Page 12, C. J. Young et al.: RCA Revi
ew 15, 469 pages (1954), Wataru Kiyota: Journal of the Institute of Electrical Communication, J63-C (No. 2), 97 pages (
1980), Yuji Harasaki et al., Industrial Chemistry Journal pp. 66, 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35,
Carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, cited in reviews such as p. 208 (1972),
Examples include xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, sityryl dyes, etc.), phthalocyanine dyes (which may contain metals), and the like.

More specifically, 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,
Examples include those described in U.S. Pat. No. 3,052,540, U.S. Pat.

Polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes, and rhodacyanine dyes include F. M. Hammer “The Cya”
nine

[0235] Dyes and Related
It is possible to use pigments described in U.S. Pat.
, 3128179, 3132942, 36223
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.

[0236] Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region, JP-A-47-840, JP-A-47-44180, and JP-A-51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 361954, U.S. Patent No. 4175956
Specifications of each issue, “Research Disclosure
re'', 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

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

[0238] 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 1 μm.
0 to 50μ is suitable.

[0240] When a photoconductive layer is used as the charge generation layer of a photoconductor 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 1μ. 0
．． 5μ is suitable.

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

[0242] As the resin used for forming the charge transport layer,
Typical examples are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride acid copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, and epoxy. Thermoplastic resins and curable resins such as resins, melamine resins, and silicone resins are used as appropriate.

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

[0244] Specifically, as an example of a conductive substrate or a conductive material, see Yukio Sakamoto, Electrophotography, 14, (No. 1
), p2-11 (1975), Hiroyuki Moriga, "Introduction to the Science of Special Paper", Kobunshi Publishing Association (1975), M. F. Hoov
er, J. Macromol. Sci. Chem. A-
4(6), pp. 1327-1417 (1970), etc. are used.

[0245] In order to actually produce the original plate for lithographic printing of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives, etc. are placed on a conductive support by volatile carbonization with a boiling point of 200°C or less. An electrophotographic photosensitive layer (photoconductive layer) can be produced by dissolving or dispersing it in a hydrogen solvent, coating it, and drying it. The organic solvent used is
Specifically, dichloromethane, chloroform, 1,2
- 1 to 3 carbon atoms, such as dichloroethane, tetrachloroethane, dichloropropane or trichloroethane;
Preferred are halogenated hydrocarbons. Other various solvents used in coating compositions, such as aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran, and methylene chloride, and the above-mentioned solvents. Mixtures of can also be used.

[0246] A printing plate using the lithographic printing original plate of the present invention is produced by forming a copy image on the electrophotographic original plate having the above-mentioned structure by a conventional method, and then subjecting the non-image area to a desensitization treatment. be done. The desensitizing treatment used in the present invention may be carried out by desensitizing zinc oxide according to a conventionally known method.

[0247] As a method for desensitizing zinc oxide, any conventionally known treatment liquid can be used. for example,
Using a ferrocyanic compound as the main desensitizing agent,
JP 62-239158, JP 62-292492, JP 63-99993, JP 63-9994, JP 40-7
334, 45-33683, JP-A-57-10788
9, Special Publication No. 46-21244, No. 44-9045, No. 4
7-32681, 55-9315, Japanese Patent Application Publication No. 52-10
1102 publications, etc.

[0248] Furthermore, Japanese Patent Publications No. 43-28408, No. 45-24609,
JP 51-103501, JP 54-10003, JP 53-83805, JP 53-83806, JP 53-12
7002, 54-44901, 56-2189, 57-2796, 57-20394, 59-207
A water-soluble polymer capable of forming a metal chelate as described in each publication of No. 290 was used as the main ingredient. Special Public Service 1977-1996
65, 39-22263, 40-763, 43-
28404, 47-29642, JP-A-52-126
302, 52-134501, 53-49506,
Those described in Publications No. 53-59502 and No. 53-104302, etc., using metal complex compounds as the main ingredient,
JP-A-53-104301, JP-A-55-15313,
54-41924, etc., or those using inorganic and organic acid compounds as the main ingredient,
9-13702, 40-10308, 46-261
24, JP-A-51-118501, JP-A No. 56-11169
Examples include those described in each No. 5 publication.

[0249] The treatment conditions are preferably a temperature of 15°C to 60°C and an immersion time of 10 seconds to 5 minutes.

0250]

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

[0251]

[C75]

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

0253]

[Table 2]

0254]

[Table 3]

0255]

[Table 4]

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

0257]

[Table 5]

[0258]

[Table 6]

0259]

[Table 7]

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

[0261]

[C76]

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

0263

[C77]

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

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

0266]

[C78]

[0267] Next, specific examples of production of a dispersion stabilizing resin (monofunctional polymer) for resin particles and resin particles will be illustrated. Production example 1 of dispersion stabilizing resin (monofunctional polymer): [M-
1]

[0268] A mixed solution of 95 g of 2,2,2,2',2',2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to 70°C while stirring under a nitrogen stream. . 1.0 g of azobisisobutyronitrile (abbreviated as A.I.B.N.) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate and 1 g of N,N-dimethyldodecylamine were added to this reaction solution.
．． Add 0g and 0.5g of t-butylhydroquinone,
The mixture was stirred at a temperature of 100°C for 12 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol to obtain 8 liters of white powder.
I got 2g. The weight average molecular weight of polymer [M-1] is 400
It was 0.

0269]

[C79]

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

0271]

[C80]

0272]

[Chemical formula 81]

Production example 3 of dispersion stabilizing resin (monofunctional polymer): [M-3] A mixed solution of 95 g of monomer (W-2) having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated with nitrogen. The mixture was heated to a temperature of 75° C. with stirring under a stream of air. 2 g of 4,4'-azobis(4-cyanovaleric acid) (abbreviated as A.C.V.) was added and reacted for 8 hours. After cooling, the resulting polymer was reprecipitated into 1 liter of methanol and dried. Next, this polymer 50
g, 11 g of 2-hydroxyethyl methacrylate, and 150 g of benzotrifluoride, and the temperature was set at 25°C. Add D. to this mixture under stirring. C. C. 15g, 4-(N
, N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. After that, 3 g of formic acid was added and stirred for 1 hour. The precipitated insoluble matter was filtered off, and the filtrate was diluted with methanol 800 g.
It was reprecipitated in ml. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to form a viscous substance 3.
Obtained 0g. The weight average molecular weight of polymer [M-3] is 3.
It was 3×104.

0274]

[C82]

0275]

[Chemical formula 83]

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

0277]

[Table 8]

[0278]

[Table 9]

0279]

[Table 10]

0280]

[Table 11]

Production Examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [M-23] to [M-30] In Production Example 2 of macromonomer, monomers (W-1) and 2 Macromonomers [M] were produced in the same manner except that -hydroxyethyl methacrylate was replaced with a compound corresponding to each of the polymers in Table 5 below. Each weight average molecular weight was 5 x 103 to 6 x 103.

0282]

[Table 12]

0283

[Table 13]

0284

[Table 14]

[0285] Production example 1 of resin for dispersion stabilization: [M-31]
37 g of octyl methacrylate, 60 monomers with the following structure
g A mixed solution of 3 g of glycidyl methacrylate and 200 g of benzotrifluoride was stirred under a nitrogen stream,
It was heated to a temperature of 75°C. 1.0 g of 2,2'-azobisisobutyronitrile (2,2'-A.I.B.N) was added and reacted for 4 hours. I. B. N. 0.5g
The mixture was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N,N-dimethyldodecylamine, t
-Add 0.5g of butylhydroquinone, temperature 110℃
The mixture was stirred 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 was 3.6 x 104.

0286]

[Chemical formula 84]

0287]

[Chemical formula 85]

Production Example 1 of Resin Particles: [L-1] 20 g of acrylic acid, polymer of Production Example 1 of Dispersion Stabilizing Resin [M-1]
] 5g and 110g of methyl ethyl ketone,
It was heated to a temperature of 60° C. under a nitrogen stream. 2,2'-azobis(isovaleronitrile) (abbreviation A.B.V.N.) 0
．． 2g was added and reacted for 2 hours, and then A. B. V. N. 0.
1 g was added and reacted for 2 hours. The obtained dispersion was
Resin particles obtained by filtering with mesh nylon cloth [L-1]
is the average particle size (manufactured by Horiba, Ltd.: C) at a polymerization rate of 100%.
(measured with APA500) was 0.20 μm.

Production example 2 of resin particles: [L-2] 20 g of acrylic acid, macromonomer AK-5 (commercial product as a monofunctional polymer with a polysiloxane structure manufactured by Toagosei Co., Ltd.)
5g, divinylbenzene 2g and methyl ethyl ketone 1
A 20 g mixed solution was prepared, and the reaction was carried out in the same manner as in Production Example 1 of Resin Particles, except that the mixture was prepared in an amount of 20 g. The polymerization rate of the obtained dispersion [L-2] was 100%, and the average particle size was 0.28 μm.

[0290] Production examples 3 to 26 of resin particles: [L-3] to
[L-26] Prepare a mixed solution of 20 g of monomer (C) listed in Table 6 below, 4 g of dispersion stabilizing resin [M], and 150 g of organic solvent, and prepare each dispersion resin in the same manner as in Production Example 1. Particles were produced. The polymerization rate of each dispersion was 95 to 100%. Further, the average particle diameter of each particle was in the range of 0.15 to 0.30 μm, and the monodispersity was also good.

0291

[Table 15]

0292

[Table 16]

[0293] Production examples 27 to 37 of resin particles: [L-27
] to [L-37] Resin particles were produced in the same manner as in Production Example 2, except that the polyfunctional compound shown in Table 7 below was used in place of 2 g of divinylbenzene. The polymerization rate of each particle is 100
% and the average particle size was 0.25-0.35 μm.

0294

[Table 17]

Example 1 and Comparative Examples A to B

Example 1 Resin [A-6] 6g (as solid content) Binder resin [B-1] having the following structure 33.2g, Photoconductive zinc oxide 200g
, 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene were mixed in a homogenizer at 6×10 3 r.p. p. m. 1 at the rotation speed of
Dispersed for 0 minutes. Dispersed resin particles [L-2] 0.8
g (as solid content), and further, the number of rotations was 1×10
3 r. p. m. Dispersion was performed for 1 minute. The dry adhesion amount of this dispersion for forming a photosensitive layer on conductive-treated paper was 25 g/m2.
It was coated with a wire bar so that Then, an electrophotographic light-sensitive material was prepared by leaving it in a dark place for 24 hours at 20° C. and 65% RH.

0297]

[C86]

Comparative Example A An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 0.8 g of dispersed resin particles [L-2] was not added.

Comparative Example B In Example 1, 6 g of resin [A-6] and resin [B-
1] Instead of 33.2g, resin with the following structure [R-1]
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that 39.2 g was used.

0300]

[Chemical formula 87]

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

[0302] The above results are summarized in Table 8.

0303]

[Table 18]

[0304] The implementation of the evaluation items listed in Table 8 is as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested for smoothness (sec
/cc) 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 V70 after leaving it for 60 seconds in the dark
is measured, and the potential retention property after dark decaying for 60 seconds, that is, the dark decay retention rate [D. R. R. (%)] to [(V70
/V10)×100(%)]. After the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was then irradiated with visible light at an illuminance of 2.0 lux.
The time required for the surface potential V10 to attenuate to 1/10 is determined, and the exposure amount E1/10 (lux/second) is calculated from this time. Similarly, find the time until V10 attenuates to 1/100, and from this calculate the exposure amount E1/100 (lux・sec)
Calculate.

Note 3) Imaging properties: After leaving each photosensitive material and a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) at room temperature and humidity (20°C, 65%) for one day and night, plate making and copying were performed. An image is formed, and the image (fog, image quality) of the obtained original copy plate is visually observed (this is designated as I). Image quality II of the copied image is determined by making the plate at high temperature and high humidity (30℃).
, 80%), but the same method as in I above is used.

[0308] Water retention of raw plate: Each photosensitive material itself (original plate without plate making: ie, abbreviated as raw plate) is treated by diluting the desensitizing treatment liquid ELP-EX manufactured by Fuji Photo Film Co., Ltd. by 5 times with distilled water. The diluted aqueous solution was used for one pass through the etching machine. 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.

Note 5) Background stains on printed matter: After each photosensitive material was plate-made in the same manner as in Note 3) above, it was passed through an etching machine once using ELP-EX as dampening water. An original plate for offset mastering was printed, and the number of prints until background stains on the printed matter could be visually determined was determined. The electrostatic properties of the present invention and Comparative Example A were good, and both of the actual image pickup properties and the copied images had clear image quality. but,
In Comparative Example B, the photosensitivity is decreased and the imaging performance is also poor.
Characters and small dots with low density were missing and blurred.

[0310] When each of these photoreceptors was desensitized and the degree of hydrophilization of the non-image area (raw plate water retention) was evaluated, Comparative Examples A and B both showed significant scumming due to printing ink adhesion. , the non-image area was not sufficiently hydrophilized.

[0311] Furthermore, when the lithographic plate of the present invention was desensitized and printed after plate making, 10,000 prints with clear images and print quality were obtained without any occurrence of scumming.

On the other hand, in Comparative Example A, which uses resin [A] but does not contain resin particles, scumming occurred on the printed surface after about 5,000 sheets. In Comparative Example B, which uses a known resin and resin particles, but uses a reduced amount of resin particles similar to that of the photoreceptor of the present invention, scumming occurred after about 3,000 sheets.

[0313] As described above, the electrophotographic lithographic printing original plate in which the hydrophilicity of the non-image area has sufficiently progressed and does not cause background fog, is
It was only the one of the present invention.

Example 2 In Example 1, 6 g of resin [A-6], 6 g of resin [B-1]
] 33.2 g and resin particles [L-2] 0.8 g, resin [A-9] 4 g, resin [B-2] 3 having the following structure
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 5.0 g of resin particles [L-24] and 0.8 g of resin particles [L-24] were used.

0315]

[Chemical formula 88]

[0316] Each characteristic was measured in the same manner as in Example 1. The following are particularly harsh environmental conditions (30℃, 80%RH).
) shows the measurement results below. Electrostatic characteristics V10
: -630V
D. R. R. : 92%
E1/10:
8.2 lux・sec
E1/100: 15.6
lux・sec Imaging performance
: Very good (◎)
Fresh version water retention:
〃 (◎) Background stains on printed matter: No background stains up to 10,000 sheets

03
17] Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention rate, and photosensitivity, and the actual copy images and printed materials are durable even under harsh conditions of high temperature and high humidity (30°C, 80% RH). , clear images without background fog were obtained.

Examples 3 to 14 Resin particles [L], resin [A], and resin particles used in Example 1
Instead of resin [B], 0.9 g (as solid content) of the resin particles [L] of the present invention shown in Table 9 below and 5 g of resin [A]
Further, each photosensitive material was produced in the same manner as in Example 1, except that 34 g of resin [B-3] having the following structure was used.

[0319] The electrostatic properties and printing properties were evaluated in the same manner as in Example 2.

0320]

[Chemical formula 89]

0321]

[Table 19]

[0322] When the electrostatic properties and printing properties of each photosensitive material were measured in the same manner as in Example 2, they all had excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images were also stable at high temperatures. Even under harsh humid conditions (30°C, 80% RH), clear images were produced without background fog or skipped fine lines.

[0323] Furthermore, when the performance of the offset lithographic plate precursors was evaluated after being desensitized, the water retention properties of the raw plates were good and 10,000 sheets could be printed even after actual plate making.

Example 15 and Comparative Examples C to D Resin [A-1
9] 6.0 g, resin with the following structure [B-4] 34 g, zinc oxide 200 g, cyanine dye with the following structure [I] 0.01
A mixture of 8 g and 300 g of toluene was heated to 6 x 103 r.p. in a homogenizer. p. m. After dispersing for 10 minutes at a rotational speed of 1.0 g (solid content) of resin particles [L-24], the mixture was further dispersed at a rotational speed of 1 x 103 r.p.m. p. m.
Dispersion was performed for 1 minute. This was applied to conductive-treated paper using a wire bar so that the dry adhesion amount was 22 g/m2, dried at 100°C for 3 minutes, and then heated at 20°C in the dark at 65°C.
An electrophotographic light-sensitive material was produced by leaving it for 24 hours under conditions of %RH.

0325]

[C90]

0326]

[Chemical formula 91]

Comparative Example C An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except that 1.0 g of resin particles [L-24] in Example 15 was not added.

Comparative Example D In Example 15, 6 g of resin [A-19] and resin [B
-4] Instead of 34g, use resin [R-2]3 with the following structure.
An electrophotographic light-sensitive material was produced in the same manner as in Example 15, except that 9 g was used.

0329]

[C92]

[0330] The film properties (surface smoothness), film strength, electrostatic properties, imaging properties, and environmental conditions of these photosensitive materials were measured at 30°C,
The electrostatic characteristics of the image pickup body at 80% RH were investigated. Furthermore,
When these photosensitive materials are used as original plates for offset masters, the photoconductive desensitization (water retention) and printability (
Background stains, printing durability, etc.) were investigated.

[0331] The above results are summarized in Table 10.

0332]

[Table 20]

[0333] Among the evaluation items shown in Table 10, the smoothness of the photoconductive layer and the scumming of printed matter were evaluated in the same manner as in Example 1.

[0334] Electrostatic properties and imaging properties were tested in the following manner.

Note 6) Electrostatic properties: Temperature 20°C, 65%
A paper analyzer (
After corona discharge was performed for 20 seconds at -6 kV using Paper Analyzer SP-428 (manufactured by Kawaguchi Electric Co., Ltd.),
It was left to stand for 10 seconds, and the surface potential V10 at this time was measured. Then, the potential V after leaving it in the dark for 120 seconds
190 and the potential after dark decaying for 120 seconds is the retention property, that is, the dark decay retention rate [D. R. R. (%)] was calculated as (V130/V10)×100(%).

[0336] Furthermore, the surface of the photoconductive layer was heated to -4 by corona discharge.
After charging to 00V, irradiate it with monochromatic light with a wavelength of 780nm, calculate the time until the surface potential (V10) attenuates to 1/10, and calculate the exposure amount E1/10 (erg/cm2).
) is calculated.

[0337] Also, find the time until the surface electron (V10) attenuates to 1/100, and from this, calculate the exposure amount E1/100.
(erg/cm2) is calculated.

Note 7) Imaging properties: Each photosensitive material was left for one day and night under the following environmental conditions. Next, a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) charged at -5 kV and having an output of 2.0 mW was used as a light source to illuminate the surface of the photosensitive material with an irradiation dose of 45 erg/cm2, a pitch of 25 μm, and a scanning speed of 330 m. After exposure at a speed of /sec, ELP-T (manufactured by Fuji Photo Film Co., Ltd.) was used as a liquid developer to develop and fix the resulting copied image (fogging, image quality), which was visually evaluated. .

The photoreceptors of Example 15 of the present invention and Comparative Example C had good electrostatic properties and good imaging properties.

On the other hand, in Comparative Example D, the electrostatic properties were deteriorated and were significantly affected by this, especially when the environmental conditions changed, and even in actual copied images, background fog and breaks in characters and thin lines occurred.

On the other hand, among the desensitized original plates, only the one of the present invention had sufficient hydrophilicity in the non-image areas and could print up to 10,000 sheets without any adhesion of printing ink or the like.

[0342] In Comparative Example C, the hydrophilization was insufficient, and in Comparative Example D, the copied image was actually deteriorated in the original plate after plate making, so the printed matter was unsatisfactory from the beginning of printing due to this effect. I could only get it.

Examples 16 to 29 In Example 15, 5 g (as solid content) of each resin [A] and 0.0 g of resin particles [L] shown in Table 11 below were used instead of resin [A] and resin particles [L]. 9g (as solid content)
Also, as resin [B], resin [B-5] with the following structure
An electrophotographic light-sensitive material was produced in the same manner as in Example 15, except that 33.5 g was used.

0344

[C93]

0345]

[Table 21]

[0346] Each photosensitive material was exposed to high temperature and high humidity (30°C,
Even under conditions of 80% RH), excellent electrostatic properties were obtained in the present invention.

[0347] Both the imaging performance and the water retention property were good, and when printing was performed using it as an offset master original plate, more than 10,000 prints with clear image quality and no background smudge were obtained.

0348

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

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

Claims (4)

[Claims] 1. An original plate for electrophotographic lithographic printing comprising at least one photoconductive layer containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin on a conductive support. The photoconductive layer contains at least one of the following resins [A] as the binder resin, and the photoconductive layer further contains at least one of the following resins [A] with a maximum particle diameter of the photoconductive zinc oxide particles or larger. An original plate for electrophotographic lithographic printing, characterized in that it contains at least one type of non-aqueous solvent-based dispersed resin particles having a small particle size as described below. Resin [A]: has a weight average molecular weight of 1 x 103 to 2 x 104, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and -PO3H 2 , -SO3H at one end
, -COOH, -P(=O)(OH)R01 [R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group]] and a cyclic acid anhydride-containing group. A resin made by bonding polar groups. [Formula (I) above, a 1 , a 2
each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R03 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles: in a non-aqueous solvent, they are soluble in the non-aqueous solvent but become insolubilized by polymerization;
carboxyl group, sulfo group, sulfino group, phosphono group, -P(=O)(OH)R0 [R0 represents a hydrocarbon group or -OR10 [R10 represents a hydrocarbon group]],
A monofunctional monomer containing at least one polar group selected from a hydroxyl group, a formyl group, an amide group, a cyano group, an amino group, a cyclic acid anhydride-containing group, and a nitrogen atom-containing heterocyclic group ( A copolymer obtained by subjecting C) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, which comprises at least one type of repeating unit containing a substituent containing a silicon atom and/or a fluorine atom. Polymer resin particles. 2. The electrophotographic lithographic printing original plate according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order mesh structure. 3. Claim 1, wherein the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. or the original plate for electrophotographic planographic printing described in 2. [In general formula (II), V 0 is -O -, -C
OO-, -OCO-, -(CH2)pOCO
−, −(CH 2 ) p COO −, −SO2 −
, -CONR1 -, -SO2 NR1 -, -C 6
H4-, -CONHCOO-, or -CONH
CONH- (where p represents an integer of 1 to 4, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b1 and b2 may be the same or different from each other, and hydrogen through an atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R 2 or a hydrocarbon group -
COO-R 2 (R 2 represents a hydrogen atom or an optionally substituted hydrocarbon group)] 4. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). The original plate for electrophotographic lithographic printing according to any one of claims 1 to 3, characterized in that it contains at least one. embedded image [However, in the above formulas (Ia) and (Ib), T 1
and T 2 are each independently a hydrogen atom and a carbon number of 1
~10 hydrocarbon groups, chlorine atoms, -COR04 or -COOR05 (R04 and R05 each have 1 to 1 carbon atoms)
10 hydrocarbon groups), L 1 and L 2
each represents a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring]