JPH04294359A - Electrophotographic planographic printing plate - Google Patents

Abstract

PURPOSE:To improve water-holding property and printing durability by incorporating a specified resin and nonwater solvent dispersion resin obtd. by polymn. in the presence of dispersion stabilizing resin. CONSTITUTION:The photoconductive layer contains such a resin having 1X10<3>-2X10<4> weight average mol.wt., a polymer component of recurring unit expressed by formula I by >30wt.%, and at least one of polar groups selected from -PO3H2, -SO3H, -COOH, -P(=O)(OH)R01, (wherein R01 represents a hydrocarbon group, etc.,) and cyclic acid anhydride-contg. groups at the one end of the polymer main chain. Further, the layer contains copolymer resin particles obtd. by the dispersion polymn. reaction of a one-functional monomer in the presence of a dispersion stabilizing resin which is soluble in the solvent and consists of a recurring unit containing substd. groups with silicon and fluorine atoms. The one functional monomer is soluble in nonwater solvent but becomes insoluble by polymn., and contains functional groups which produce hydroxyl groups by decomposition.

Description

[Detailed description of the invention]

0001

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

0002

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

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

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

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

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

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

[0008]

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

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

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

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

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

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

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

[0015]

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

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

[0017]

[C4]

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

[0019]

[C5]

[However, in the above formula (I), a1,
a2 each represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R03 represents a hydrocarbon group] The non-aqueous solvent-based dispersed resin particles are soluble in the non-aqueous solvent but become insolubilized by polymerization, and generate at least one hydroxyl group by decomposition. A monofunctional monomer containing at least one functional group (C
) in the presence of a dispersion stabilizing resin soluble in the solvent, the copolymer resin comprising at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom. It has the characteristics of particles.

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

[0022]

[C6]

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

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

[0025]

[C7]

[In general formula (II), V0 is -O
-, -COO-, -OCO-, -(CH2)p -O
CO-,-(CH2)p-COO-,SO2-,
-CONR1 -, -SO2 R1, -C6 H4
-, -CONHCOO-, or -CONHCONH-, (where p represents an integer of 1 to 4, and R1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms),
b1 and b2 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-R2 or -COO-R2 (
R2 represents a hydrogen atom or a hydrocarbon group which may be substituted].

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

As mentioned above, the technique of containing hydrophilic resin particles in the photoconductive layer and the binder resin of the electrophotographic photoreceptor,
Techniques using resins containing acidic groups in their side chains are known, but as in the present invention, components containing functional groups that generate hydroxyl groups upon decomposition are used as resin particles and binder resin to be included in the photoconductive layer. and non-aqueous solvent-based dispersed resin particles each containing a component containing a substituent containing a silicon atom and/or a fluorine atom, and a low molecular weight resin [A] containing an acidic group in the side chain of the polymer. According to
Surprisingly, it has been found that the above-mentioned problems that were unsolved using only these known techniques can be solved, that is, water retention, printing durability, etc. can be dramatically improved.

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

Furthermore, the resin particles [L] 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. They are all in one place. and the resin particles [L]
During desensitization treatment, the protected hydroxyl groups of the monomer (C) undergo a chemical reaction through hydrolysis, redox reactions, photolysis reactions, etc. to generate hydroxyl groups, which change the hydrophobic property. By combining a dispersion stabilizing resin containing at least a repeating unit that is converted into hydrophilic properties and contains a substituent containing at least one fluorine atom and/or silicon atom, the fluorine atom and/or This shows that the large lipophilicity of the silicon atom-containing substituent causes a migration/concentration phenomenon on the surface portion of the photoconductive layer.

Furthermore, the dispersion stabilizing resin containing fluorine atoms and/or silicon atoms, which stabilizes the dispersion of non-aqueous dispersed resin particles, is physicochemically adsorbed onto the copolymer portion to be insolubilized during the reaction process of polymerization granulation. and/or the above formula (II
) In the case of a dispersion stabilizing resin containing a polymerizable double bond group moiety, it is preferable that both polymer components are chemically bonded.

[0032] In the binder resin of the present invention, [A] contains a specific polymer component represented by formula (I) and has the specific polar group bonded to at least one end of the polymer main chain. It is characterized by being a low molecular weight polymer.

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

That is, when the photoconductive zinc oxide particles, the spectral sensitizing dye, the resin particles [L] and the resin [A] are dispersed,
A low molecular weight resin [A] formed by bonding a specific polar group to one end of the polymer main chain adsorbs to the stoichiometric defects of the photoconductive zinc oxide and interacts with the zinc oxide and the dye. Appropriate coating and adsorption conditions compensate for the trapping of photoconductive zinc oxide and dramatically improve humidity characteristics, while ensuring sufficient dispersion of photoconductive zinc oxide to prevent agglomeration. This is thought to be due to control.

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

Another important aspect of the original plate for electrophotographic lithographic printing systems is that the non-image areas are made sufficiently hydrophilic through desensitization treatment and have high water retention properties that prevent ink from adhering during printing. That's true. In the lithographic printing original plate of the present invention, the resin particles [L] concentrated on the surface portion of the photoconductive layer generate the above-mentioned specific hydrophilic groups by desensitization treatment, thereby expressing hydrophilicity. The non-image area is sufficiently modified to be hydrophilic and exhibits sufficient water retention without causing scumming. Furthermore, it is also possible to desensitize the zinc oxide particles uniformly dispersed in the resin [A] by a known method to make the non-image area hydrophilic.

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

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

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

[0040] The smaller the particle diameter of the resin particles, the larger the specific surface area, which brings about good effects on the above-mentioned electrophotographic properties, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, If it is too large, it will resemble the case of molecular dispersion, and the effect of particles on improving water retention capacity will be diminished, so it is preferable to use the particle size at 0.001 μm or more.

Further, in the present invention, the resin particles are made of a hydrophobic polymer component, that is, a dispersion stabilizing resin is bonded with a corresponding polymer component, and this hydrophobic portion is bonded to the binder resin of the photoconductive layer. Because of the interaction, the anchor effect of this part prevents it from being eluted by dampening water during printing, and good printing characteristics can be maintained even when printing a large number of sheets. Furthermore, when one of the polymer components as the dispersion stabilizing resin contains a heat-curable and/or photo-curable group, elution can be further suppressed by further chemically bonding with the binder resin. can.

Furthermore, in the present invention, resin particles forming a high-order network structure can further suppress dissolution in water, exhibit water swelling properties, and further improve water retention. In the present invention, the resin particles that do not form a higher-order network structure as described above or the resin particles that do form a higher-order network structure (hereinafter simply referred to as network resin particles) contain 100% by weight of photoconductive zinc oxide. It is preferably used in an amount of 0.05 to 30% by weight. If the resin particles or network resin particles are less than 0.05% by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 30% by weight, the hydrophilicity of the non-image area can be further improved, but it is difficult. The electrophotographic characteristics under these conditions deteriorate, resulting in a deteriorated copy image.

Furthermore, the resin particles contain a polymer component containing fluorine atoms and/or silicon atoms, and as a result, the particles migrate to the surface portion of the photoconductive layer and undergo concentration development. In order to produce the same effect (water retention) as the above effect, only a very small amount is required.

[0044] The binder resin [A
] will be explained in more detail. In resin [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 -30°C to 110°C, more preferably -20°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.

[0047] 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.

[0048] As the low molecular weight resin [A], those represented by the above general formula (Ia) and general formula (Ib),
Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring at the 2-position and/or the 2-position and the 6-position
(Hereinafter, this low molecular weight material will be referred to as resin [A']).

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

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

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

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

In formula (Ia), preferred T1 and T2 are, independently of each other, hydrogen, chlorine and bromine atoms, as well as hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), carbon number 7 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.

[0056]

[Chemical formula 8]

[0057]

[Chemical formula 9]

[0058]

[Chemical formula 10]

[0059]

[Chemical formula 11]

[0060]

[Chemical formula 12]

[0061]

[Chemical formula 13]

[0062]

[Chemical formula 14]

[0063]

[Chemical formula 15]

[0064]

[Chemical formula 16]

[0065]

[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.

[0071] These polar groups may be bonded directly to the terminal end of the polymer main chain, or may be bonded via a linking group. The linking group may be any bonding group, but specific examples include -[C(d1)(d2
)] - (d1 and d2 may be the same or different, and each represents a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.),
OH group, cyano group, alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl (representing a group, etc.),
-(CH(d3)-CH(d4))]-(d3, d
4 represents the same content as d1 and d2), -C6 H
10-, -C6 H5, -O-, -S-, -N(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 0.05 to 10% by weight of a copolymerization component containing at least one polar group selected from O3H, -COOH, -P(=O)(OH)R01, and a cyclic acid anhydride-containing group. is preferable in terms of further improving electrostatic properties.

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

Copolymerization 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.

[0076]

[Chemical formula 18]

[0077]

[Chemical formula 19]

[0078]

[C20]

[0079]

[C21]

[0080]

[C22]

[0081]

[C23]

[0082]

[C24]

[0083]

[C25]

[0084]

[C26]

[0085]

[C27]

[0086]

[C28]

[0087]

[C29]

[0088]

[C30]

[0089]

[Chemical formula 31]

[0090]

[C32]

[0091]

[Chemical formula 33]

[0092]

[C34]

[0093]

[C35]

[0094]

[C36]

[0095]

[C37]

[0096]

[C38]

[0097]

[C39]

[0098]

[C40]

0099

[C41]

[0100]

[C42]

[0101]

[C43]

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

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

It is desirable that the amount of these other monomers in the resin [A] does not exceed 30% by weight. 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.).

[0107] 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 each of these chain transfer agents or polymerization initiators is 0.5 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers. The low molecular weight resins [A] (including [A']) as described above are preferably used in combination with known resins for conventional photoconductive zinc. The ratio of the low molecular weight resin [A] to other resins is preferably 5-50/95-50 (weight ratio).

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

[0110] Other resins to be used in combination have a weight average molecular weight of 3 x 104 to 1 to 106, preferably 5 x 104.
It is a medium to high molecular weight substance of ~5x105. Further, the glass transition point of the resin used in combination is -10°C to 120°C, preferably 0°C to 90°C.

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

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

Further, a medium to high molecular weight resin to be used in combination satisfies the above-mentioned physical properties and is preferably a resin 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).

[0114]

[C44]

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

R07 represents the same content as R03 in formula (I). As the medium to high molecular weight binder resin (hereinafter referred to as resin [B]) containing the polymer component represented by the general formula (III), for example, a random binder resin containing the polymer component represented by the formula (III) can be used. Polymer resin (Japanese Patent Application Laid-open No. 63-49
817, 63-220149, 63-220148
various publications, etc.), combination resins of the random copolymer and crosslinkable resin (JP-A-1-102573, etc.), graft-type copolymers (JP-A-2-53064, JP-A-2-56558, etc.), etc. Examples include medium to high molecular weight substances described in each specification.

[0117] The non-aqueous solvent-based dispersed resin particles used in the present invention will be explained in 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 contain a monofunctional monomer (C ) consisting of a polymer component [polymer component (
C)] and a polymer component consisting of 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

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

[0122] The molecular weight of the dispersed resin particles is 104 to 106
, preferably 104 to 5×105. As a polymerization component in the resin particles, the proportion of monomer (C) present is 30% by weight or more, preferably 50% by weight or more,
Particularly preferably, the resin is composed only of monomer (C) and a 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, which improves water retention while satisfying electrophotographic properties when added to the surface layer, will be diminished.

[0126] In the total number of repeating units in the dispersion stabilizing resin of the present invention, repeating units having a substituent containing a fluorine atom and/or a silicon atom account for 30% by weight of the total.
It is preferable that the content is 5 or more, more preferably 5
It is 0% by weight or more.

[0127] If the above-mentioned components of the present invention are less than 30% by weight of the total, the effect of concentrating the resin particles on the surface layer when dispersed in the surface layer decreases, and as a result, the effect of improving water retention as a printing original plate decreases. fades away.

The dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the monomer (C) to be insolubilized as described above. The resin particles [L] of the present invention dispersed in the photoconductive layer will be explained in more detail below.

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

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

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

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

[0133]

[Image Omitted] However, R1 ′, R2 ′, R3 ′, R4
', R5', R6' may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, or -O-R'(R'
represents a hydrocarbon group), Y1 and Y2 represent a hydrocarbon group, and Z represents an oxygen atom, a sulfur atom, or -NH
- group, and X represents a sulfur atom or an oxygen atom.

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

[0135] When L represents -CO-Y1, Y1 is preferably an optionally substituted straight or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group, a trichloromethyl group, a trifluoromethyl group). , methoxymethyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-i-propyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.), optionally substituted with 6 to 1 carbon atoms
2 aryl group (eg, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, trifluoromethylphenyl group, etc.).

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

[0137]

In the case of formula, X represents an oxygen atom or a sulfur atom. R4', R5', and R6' may be the same or different from each other, and specifically R1 to R3 described above
represents the same content as .

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

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

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

[0141]

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

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

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

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

[0145]

[C48]

[0146]

[C49]

[0147]

[C50]

[0148]

[C51]

[0149]

[C52]

[0150]

[C53]

[0151]

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

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

[0153]

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

[0154]

[C56]

[0155]

[C57]

[0156]

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

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

[0158] U represents a carbon-carbon bond which may be via a heteroatom, and the number of atoms between oxygen atoms is 5 or less. At least two hydroxyl groups as described above
Monomer (C) protected with two protecting groups can be synthesized by the method described in the same known technical documents cited in the synthesis method of [-O-L].

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

[0160]

[C59]

[0161]

[C60]

[0162]

[C61]

[0163]

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

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

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

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

[0167] These repeating units having a substituent containing a fluorine atom and/or a silicon atom will be explained. Examples of the chemical structure of the repeating unit include those obtained from radical addition polymerizable monomers, those consisting of a polyester structure, or those consisting of a polyether structure, and the side chains in the repeating units of these polymer structures, Any material may be used as long as it contains a fluorine atom and/or a silicon atom.

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

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.

[0170] However, R 3 , R 4 , R 5
represent a hydrocarbon group or an -OR9 group (R9 represents the same content as the hydrocarbon group of R3), which may be the same or different and may be substituted.

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

In the -OR9 group, R 9 represents the same content as the hydrocarbon group of R 3 above. R 6
, R 7 , R 8 may be the same or different,
Represents the same symbol content as R 3 , R 4 , R 5 .

Next, specific examples of repeating units having a substituent containing a fluorine atom and/or a silicon atom as described above are shown below. Here, 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.

[0174]

[C63]

[0175]

[C64]

[0176]

[C65]

[0177]

[C66]

[0178]

[C67]

[0179]

[C68]

[0180]

[C69]

[0181]

[C70]

[0182]

[C71]

[0183]

[C72]

[0184]

[C73]

[0185]

[C74]

[0186]

[C75]

[0187]

[C76]

[0188]

[C77]

In addition, 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 amount of the polymer component containing fluorine atoms and/or silicon atoms is 30 parts by weight or more, preferably 50 parts by weight or more, based on 100 parts by weight of the total polymer of the resin.

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

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

[0193]

[C78]

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 R 1 above.

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

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

[0200] 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-
, -Nq1 -, -SO-, -SO2 -, -COO
-, -OCO-, -CONHCO-, -NHCONH
-, -CONq2 -, -SO2 Nq3 - and -S
composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues, which may include a bonding group selected from i(q4)(q5)- Represents an organic residue. Here, q1 to q5 are expressed by the formula (II
) represents the same content as R 1 in ).

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

[0202]

[C79]

{q6 and q7 may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 12 carbon atoms (for example, a methyl group, ethyl group, propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.). Q represents -O-, -S- or -NR10-, R10 is an alkyl group having 1 to 4 carbon atoms, -CH2
Cl or -CH2Br}.

[0204] Examples of divalent aromatic groups include benzene ring groups, naphthalene ring groups, and 5- or 6-membered heterocyclic groups (the hetero atoms constituting the heterocycle are selected from oxygen atoms, sulfur atoms, and nitrogen atoms). containing at least one type of heteroatom). These aromatic groups may have a substituent, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, propyl group). , butyl group, hexyl group, octyl group, etc.), and an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) as examples of the substituent.

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

[0206] Specifically, the polymerizable double bond group-containing moiety as described above is a moiety that 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.

[0207]

[C80]

[0208]

[Chemical formula 81]

[0209]

[C82]

[0210]

[Chemical formula 83]

[0211]

[Chemical formula 84]

[0212]

[Chemical formula 85]

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

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

[0215] As the method (2) above, for example, Japanese Patent Application Laid-Open No. 1986-
Examples include the method described in Japanese Patent No. 185962. As for the above method (■), specifically, Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (published in 1977), Ryohei Oda "Polymer Fine Chemicals" Kodansha (published in 1976), JP-A-6
It is described in detail in Japanese Patent Application No. 1-43757 and the specification filed as Japanese Patent Application No. 1-149305.

[0216] For example, a polymer reaction using a combination of a functional group of group A and a functional group of group B shown in Table 1 below is a commonly known method. In addition, R21, R in Table-1
22 is a hydrocarbon group and has the same content as l8 and l9 in L3 of the above formula (IV).

[0217]

[Table 1]

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

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

[0220] More specifically, as a method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radically polymerizable monomer is synthesized according to Japanese Patent Application Laid-Open No.
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application No. 1-206989, No. 1-69011, etc., and contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] is disclosed in Japanese Patent Application No. 1-56379, No. 1-58989,
It can be obtained in the same manner as the methods described in the specifications of the applications as No. 1-56380.

As explained above, the dispersed resin particles of the present invention combine the polar group-containing monofunctional monomer (C) with the above monomer containing at least a repeating unit containing a silicon atom-containing and/or fluorine atom-containing substituent. These are copolymer resin particles obtained by dispersion polymerization in the presence of a dispersion stabilizing resin.

Furthermore, when the dispersed resin particles of the present invention have a network structure, the above polar group-containing monofunctional monomer (C
) as a polymerizable component [abbreviated as polymer component (C)], the polymers are bridged to form a high-order network structure.

[0223] That is, the dispersed resin particles of the present invention are non-aqueous latex composed of a portion insoluble in a non-aqueous dispersion solvent composed of the polymer component (C) and a polymer that is soluble in the solvent. When the polymer component has a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged.

[0224] As a result, the network resin particles become poorly soluble or insoluble in water. in particular,
The solubility of the resin in water is 80% by weight or less, preferably 5% by weight or less.
It is 0% by weight or less.

[0225] The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (a) the polymer component (C
) A method of crosslinking a polymer containing (b) with various crosslinking agents or curing agents, (b) carrying out a polymerization reaction by containing at least a monomer corresponding to the polymer component (C),
A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, and (c) the polymer component (C
) and a polymer containing a component containing a reactive group through a polymerization reaction or a polymer reaction.

[0226] As the crosslinking agent in the above method (a), compounds that are commonly used as crosslinking agents can be mentioned. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. Can be used.

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

[0228] Furthermore, in the method (b) above, a polyfunctional monomer containing two or more polymerizable functional groups (also referred to as polyfunctional monomer (E)) or a polyfunctional oligomer can be polymerized. Specifically, the sexual functional group is CH2=CH-C
H2-, CH2=CH-CO-O-, CH2=C
H-, CH2=C(CH3)-CO-O-, CH(
CH3)=CH-CO-O-, CH2=CH-CO
NH-, CH2=C(CH3)-CONH-, CH
(CH3)=CH-CONH-, CH2=CH-O
-CO-, CH2=C(CH3)-O-CO-, C
H2=CH-CH2-O-CO-, CH2=CH
-NHCO-, CH2 = CH-CH2 -NHCO-
, CH2=CH-SO2-, CH2=CH-CO
-, CH2 = CH-O-, CH2 = CH-S-, and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

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

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

[0231] The monomer or oligomer having two or more polymerizable functional groups used in the present invention is monomer (C)
and 10 relative to the total amount of other monomers coexisting with (C)
Polymerization is performed using mol % or less, preferably 5 mol % or less, to form a resin.

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

[0233] In dispersion polymerization, monodisperse particles with a uniform particle size can be obtained, and microparticles of 0.5 μm or less can be easily obtained, so polyfunctional polymerization is recommended as a method for forming a network structure. Method (b) using monomers is preferred.

As described above, the network-dispersed resin particles of the present invention contain a repeating unit containing a functional group that decomposes to produce a hydroxyl group, and have a structure in which the molecular chains are highly cross-linked. It is composed of a polymer component insoluble in an aqueous solvent and a polymer component soluble in the non-aqueous solvent, which contains at least a repeating unit having a fluorine atom and/or a silicon atom-containing substituent.

[0235] 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.

[0237] By synthesizing dispersed resin particles in these nonaqueous solvent systems by dispersion polymerization, the average particle size of the resin particles can easily be 0.8 μm or less, and the particle size distribution is extremely narrow and monodisperse. particles.

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

[0239] The dispersed resin particles of the present invention consist of at least one of each of the monomer (C) and a dispersion stabilizing resin,
When forming a network structure, a polyfunctional monomer (D) may be coexisting as necessary; in any case, the important thing is that the resin particles synthesized from these monomers do not contain the non-aqueous solvent. If the resin is insoluble in the resin, desired dispersed resin particles can be obtained. More specifically, for the monomer (C) to be insolubilized,
It is preferable to use the dispersion stabilizing resin in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight. Further, the molecular weight of the dispersed resin particles of the present invention is 104 to 106,
Preferably it is 104 to 5×105.

[0240] In order to produce the dispersed resin particles used in the present invention as described above, the monomer (C), the dispersion stabilizing resin, and the polyfunctional monomer (D) are generally mixed in a non-aqueous solvent. The polymerization may be carried out by heating in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of monomer (C), a dispersion stabilizing resin, and a polyfunctional monomer (D), (ii) a method of adding a polymerization initiator to a nonaqueous solvent , a method in which a mixture of the above-mentioned polymerizable compound and a polymerization initiator is added dropwise or arbitrarily, and the method is not limited to these methods, and any method can be used for production.

[0241] The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the nonaqueous solvent.
~50 parts by weight.

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

[0243] The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles with a uniform particle size distribution.

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

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

[0246] 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.

[0247] In the lithographic printing original plate of the present invention, the total amount of binder resin used for photoconductive zinc oxide is such that the ratio of binder resin to 100 parts by weight of photoconductive zinc oxide is 10 to 100 parts by weight. , particularly preferably in a proportion of 15 to 50 parts by weight.

[0248] In the binder resin provided to the photoconductive layer,
The proportion of resin [A] and other binder resins is 5 to 90/95 to 5 by weight based on 100 parts by weight of the total binder resin.
Preferably the weight ratio is 10-60/90-40.

If the proportion of resin [A] used is less than 5 parts by weight, the electrophotographic properties will deteriorate, and especially when combined with a spectral sensitizing dye for semiconductor laser light, the effect will be significantly reduced.

[0250] If the amount exceeds 90 parts by weight, the film strength of the photoconductive layer deteriorates, resulting in a decrease in printing durability when used as an original plate for offset printing. The amount of resin particles [L] used in the present invention is 0.1 parts by weight based on 100 parts by weight of all binder resins.
~30 parts by weight is preferred.

[0251] If the proportion of resin particles [L] used is less than 0.1 part by weight, the effect of improving water retention will be diminished. If it exceeds 30 parts by weight, electrophotographic properties may deteriorate;
This is particularly a concern when used for semiconductor laser light.

The spectral sensitizing dye used in the photoconductive layer of the present invention may be any conventionally known dye, and these may be used alone or in combination. for example,
Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8)
) page 12, C. J. Young et al.: RCA Rev
iew 15, 469 pages (1954), Wataru Kiyota:
Transactions of the Institute of Electrical Communication Engineers J63-C (No. 2) p. 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal p. 66, 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35
, p. 208 (1972), carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (e.g., oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, cytylyl dyes). etc.), phthalocyanine dyes (which may contain metal), and the like.

More specifically, carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are mainly used in Japanese Patent Publication No. 51-4.
52, JP-A No. 50-90334, No. 50-114227
, 53-39130, 53-82353 publications,
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

0255 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.

[0256] Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region, JP-A-47-840, JP-A-47-44180, and JP-A-51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 361954, U.S. Patent No. 4175956
Specifications of each issue, “Research Disclosure
re'', 1982, 216, pp. 117-118. The photoreceptor of the present invention is also excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together.

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

[0258] The amount of these various additives added is not particularly limited, but is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0μ, especially 10-50μ is suitable.

[0259] 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.

[0261] 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.

[0263] 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.

[0264] In order to produce printed matter using the electrophotographic printing original plate of the present invention, a copy image is formed on the electrophotographic printing original plate having the above-described structure by a conventional method, and then the non-image area is desensitized. Created.

[0265] The desensitization treatment provided in the present invention includes a method in which the resin particles of the present invention are hydrolyzed by passing through a treatment liquid;
Examples include a method in which hydroxyl groups are generated by decomposition by redox reaction or light irradiation, or a method in which resin particles are hydrophilized and zinc oxide is desensitized with a desensitization treatment liquid. .

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

[0267] As a method for desensitizing zinc oxide, any conventionally known treatment liquid can be used. for example,
Using a ferrocyanic compound as the main desensitizing agent,
JP 62-239158, JP 62-292492, JP 63-99993, JP 63-9994, JP 40-7
334, 45-33683, JP-A-57-10788
9, Special Publication No. 46-21244, No. 44-9045, No. 4
7-32681, 55-9315, Japanese Patent Application Publication No. 52-10
1102 publications, etc. However, from the viewpoint of the safety of the treatment liquid, the following treatment liquids are preferred.

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

[0269] The method for desensitizing the resin particles, ie, the method for decomposing the protected hydroxyl groups, is arbitrarily selected depending on the decomposition reactivity of the protected hydroxyl groups. One such method is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 or alkaline conditions of pH 8 to 12. These pH values can be easily adjusted using known compounds. Alternatively, a method using a redox reaction using a reducing or oxidizing water-soluble compound is also possible, and known compounds can be used as these compounds, such as hydrazine hydrate, zincate, lipoic acid, hydroquinones, formic acid, etc. , thiosulfate, hydrogen peroxide,
Examples include persulfates and quinones.

[0270] The processing solution may contain other compounds in order to promote the reaction or improve the storage stability of the processing solution. For example, add 1 part by weight of a water-soluble organic solvent to 100 parts by weight of water.
It may contain up to 50 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol,
ethanol, propanol, propargyl alcohol,
benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.), and these may be used alone or in combination of two or more.

[0271] In addition, 0 parts of surfactant was added to 100 parts by weight of water.
．． It may be contained in an amount of 1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic, and nonionic surfactants. For example, Hiroshi Horiguchi, “New Surfactants,” Sankyo Publishing Co., Ltd. (published in 1975), Ryohei Oda, Kazuhiro Teramura, “Synthesis of Surfactants and Their Applications,” Maki Shoten (
(1980), etc. can be used.

[0272] The scope of the present invention is not limited to the above-mentioned specific compound examples. The processing conditions are a temperature of 15°C.
The immersion time is preferably 10 seconds to 5 minutes at ~60°C.

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

[0274] The "chemically active light" used in the present invention includes visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays,
Any radiation such as γ rays or α rays may be used, but ultraviolet rays are preferred. More preferably wavelength 310 nm to wavelength 5
It is preferable to use one that can emit light in the 00 nm range, and generally a high-pressure or ultra-high pressure mercury lamp or the like is used. Light irradiation treatment is usually performed from a distance of 5cm to 50cm.
Irradiation for 1 to 10 seconds is sufficient.

0275]

[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.

0276]

[C86]

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.

[0278]

[Table 2]

0279]

[Table 3]

0280]

[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.

0282]

[Table 5]

0283

[Table 6]

0284

[Table 7]

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

0286]

[Chemical formula 87]

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.

0288

[Chemical formula 88]

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.

0291

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

0293

[C90]

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

0295]

[Chemical formula 91]

0296

[C92]

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

0298

[C93]

0299]

[C94]

Production Examples 4 to 22 of dispersion stabilizing resin (monofunctional polymer): [M-4] to [M-22] In Production Example 2, other monomers were used instead of monomer (MA-1). mer (monomer corresponding to the polymer component listed in Table 3).
Each dispersion stabilizing resin [M] was produced in the same manner as in Production Example 2. Each weight average molecular weight is 4 x 103 ~ 6 x 108
Met.

0301]

[Table 8]

0302]

[Table 9]

0303]

[Table 10]

0304]

[Table 11]

[0305] Production examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [M-23] to [M-30] In production example 2 of dispersion stabilizing resin, monomer (MA-1) and 2-
Each dispersion stabilizing resin [M] was produced in the same manner except that hydroxyethyl methacrylate was replaced with a compound corresponding to each of the polymers in Table 4 below. Each weight average molecular weight was 5 x 103 to 6 x 103.

0306]

[Table 12]

0307]

[Table 13]

0308

[Table 14]

[0309] Production example 31 of resin for dispersion stabilization: [M-31
] 30 g of octyl methacrylate, a monomer with the following structure (M
A-3) A mixed solution of 70 g of 3 g of glycidyl methacrylate and 200 g of benzotrifluoride was heated to a temperature of 75° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (A.I.B.N.) was added and reacted for 4 hours, and then A.I.B.N. I. B. N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N,N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110° C. for 8 hours. After cooling, it was reprecipitated into 2 liters of methanol, and a slightly brownish oil was collected and dried. The yield was 73 g, and the weight average molecular weight was 3.6 x 104.

0310]

[C95]

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

0312]

[C96]

[0313] Production examples 33 to 39 of dispersion stabilizing resin: M-
33-M39 By performing the reaction shown in Production Example 32, the following Table-5
Each of these dispersion stabilizing resins was synthesized. The weight average molecular weight of each resin was in the range of 6 x 103 to 9 x 103.

0314

[Table 15]

0315]

[Table 16]

0316

[Table 17]

Production example 40 of dispersion stabilizing resin: A mixed solution of 95 g of M-40 monomer [MA-2], 5 g of methacrylic acid, and 200 g of benzotrifluoride was heated to 75° C. with stirring under a nitrogen stream. It was warm. To this A. I.
B. N. 1.0g was added and reacted for 4 hours, and then A. I. B
．． N. 0.5 g was added and reacted for 4 hours. The weight average molecular weight of the obtained polymer was 3.3 x 104.

0318

[Chemical formula 97] Production example 1 of resin particles: [L-1] 10 g of dispersion stabilizing resin [M-32] and 2 n-octane
00g of mixed solution was heated to 60°C while stirring under nitrogen flow.
It was heated to To this, 50 g of the following monomer [C-1], 5 g of ethylene glycol dimethacrylate, A. I. V.
N. A mixed solution of 0.5 g and 240 g of n-octane was added dropwise over 2 hours, and the reaction was continued for 2 hours. Furthermore, A
．． I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a white dispersion was obtained through a 200 mesh nylon cloth. The latex had an average particle size of 0.20 μm. {: Particle size measurement with CAPA-500 [manufactured by Horiba, Ltd.]}

0319]

[Chemical formula 98] Production examples 2 to 11 of resin particles: [L-2]-[L-11]
In Production Example 1 of Resin Particles, the resin was produced in the same manner as in Production Example 1, except that the monomer [C-1] and the dispersion stabilizing resin [M-32] were replaced with each compound in Table 6 below. Particles were produced.

[0320] The average particle diameter of each particle was within the range of 0.15 to 0.30.

0321]

[Table 18]

0322]

[Table 19] Resin particle production example 12: [L-12] Dispersion stabilizing resin AK-5 [manufactured by Toagosei Co., Ltd. Macromonomer: Macromonomer having a dimethylsiloxane structure as a repeating unit: Weight average molecular weight 1.5 ×104〕7.5
A mixed solution of 133 g of methyl ethyl ketone and 133 g of methyl ethyl ketone was heated to 60° C. with stirring under a nitrogen stream. To this, 50 g of the following monomer [C-12], 5 g of diethylene glycol dimethacrylate, A. I. V. N. A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour. I. V. N. 0.25g was added and reacted for 2 hours.

After cooling, the resulting dispersion was passed through a 200 mesh nylon cloth and the average particle size was 0.18 μm.

0324]

[Chemical Formula 99] Production Example 13 of Resin Particles: [L-13] A mixed solution of 7.5 g of dispersion stabilizing resin M-35 and 230 g of methyl ethyl ketone was stirred under a nitrogen stream for 6 hours.
Warmed to 0°C. To this, 35 g of monomer [C-13],
Acrylamide 15g A. I. V. N. 0.5
A mixed solution of g and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. Furthermore, A. I
．． V. N. After adding 0.25 g and reacting for 2 hours, the resulting dispersion was cooled and passed through a 200 mesh nylon cloth, and the average particle size of the obtained dispersion was 0.20 μm.

0325]

[Chemical formula 100] Production example 14 of resin particles: [L-14] 50 g of monomer [C-14], 2 g of ethylene glycol diacrylate, 8 g of dispersion stabilizing resin M-33, and 230 g of dipropyl ketone were added under a nitrogen stream. 2 into a solution of 200 g of dipropyl ketone heated to 60°C while stirring.
It dripped in time. After reacting for 1 hour, A. I.
V. N. 0.3 g was added and reacted for 2 hours. After cooling 2
The average particle size of the dispersion obtained through a 00 mesh nylon cloth was 0.28 μm.

0326]

[Chemical formula 101] Production examples 15 to 25 of resin particles: [L-15] to [L-2
5] Resin particles [L-
15] to [L-25] were produced. The polymerization rate of each particle was 95 to 98%, and the average particle size was 0.15 to 0.25 μm.

0327]

[Table 20] Production examples 26 to 31 of resin particles: [L-26] to [L-3
1] In Production Example 12 of resin particles, dispersion stabilizing resin AK-
Particles were produced in the same manner as in Production Example 12, except that each dispersion stabilizing resin shown in Table 8 below was used instead of Sample 6. The average particle size of each particle was in the range of 0.20 to 0.25.

0328

[Table 21] Production examples 32 to 35 of resin particles: [L-32]-[L-3
5] Production Example 13 of resin particles except that each compound in Table 9 below was used instead of the monomer [C-13] acrylamide and the reaction solvent: methyl ethyl ketone.
Each particle was produced in the same manner.

[0329] The average particle size of each particle was in the range of 0.15 to 0.30.

0330]

[Table 22] Production Example 36 of Resin Particles: [L-36] In Production Example 12 of Resin Particles, dispersion stabilizing resin [AK
-5] Instead of 7.5g, dispersion stabilizing resin [M-40
] was synthesized in the same manner as in Resin Particle Production Example 12, except that 12.5 g of the resin particles were used. The average particle size of the obtained dispersion was 0.26
It was μm. Example 1 and Comparative Examples A to B Example 1 Resin [A-7] 6 g (as solid content), resin [B-1] with the following structure 32 g (as solid content), photoconductive zinc oxide 200 g, the following structure Methine dye [I] 0.018
g, salicylic acid 0.15 g, and toluene 300 g in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) 7×
103 r. p. m. Dispersion was carried out for 10 minutes at a rotation speed of . To this, dispersed resin particles [L-1] 2g (as solid content) phthalic anhydride 0.05g, o-chlorophenol 0.00
5g was added and the rotational speed was increased to 1×103 r. p. m. de1
Dispersed for minutes. This dispersion for forming a photosensitive layer was applied to conductively treated paper using a wire bar so that the dry adhesion amount was 25 g/m2, dried at 100°C for 30 seconds, and further heated to 120°C.
It was heated for 1 hour. Next, an electrophotographic light-sensitive material was prepared by allowing the mixture to stand in a dark place at 20° C. and 65% RH for 24 hours.

0331]

[Chemical formula 102]

0332]

Comparative Example A An electrophotographic material was produced in the same manner as in Example 1 except that 2 g of resin particles [L-1] were removed. Comparative Example B In Example 1, 6 g of resin [A-7] and resin [B-
1] An electrophotographic light-sensitive material was prepared in the same manner as in Example 1, except that 38 g of resin [B-1] was used instead of 32 g.

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. (After printing, we used Hamadastar 800SX model manufactured by Hamadastar Co., Ltd.)
The above results are summarized in Table-11.

0334

[Table 23] The implementation aspects of the evaluation items listed in Table-11 are as follows. Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) with an air volume of 1
The smoothness (sec/cc) was measured under cc conditions. Note 2) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH.
-6 using a paper analyzer (Paper Analyzer SP-428 model manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material.
After corona discharge for 20 seconds at kV, leave it for 10 seconds,
The surface potential V10 at this time was measured. Next, the potential V120 was measured after being allowed to stand still in the dark for 120 seconds, and the retention of the potential after dark decay for 120 seconds, that is, the dark decay retention rate [DRR (%)] was determined as [(V120 /V
10)×100(%)].

[0335] Furthermore, the surface of the photoconductive layer is -
After charging to 500V, irradiate 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/cm).
2) Calculate. The environmental conditions during imaging were I (20℃, 6
5% RH) and II (30°C, 80% RH). Note 3) Imaging properties: Each photosensitive material was left for one day and night under environmental conditions I or II. Next, it is charged with -5kV and used as a light source with 2.8
Using a mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm), the surface of the photosensitive material was exposed at a dose of 50 erg/cm3, at a pitch of 25 μm, and at a scanning speed of 330 m/sec.
ELP-T (Fuji Photo Film Co., Ltd.) as a liquid developer
Copied images obtained by developing and fixing the images were visually evaluated for fogging and image quality. Note 4) Water retention of raw plate: The degree of hydrophilization due to desensitization treatment when a photosensitive material is used as a printing original plate was investigated under the following forced conditions.

[0336] Each photosensitive material itself (original plate without plate making:
That is, an aqueous solution prepared by diluting a desensitizing treatment liquid ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) five times with distilled water was passed through an etching machine once. Further, this was immersed for 3 minutes in a solution [:E-1] prepared by diluting 0.5 mol monoethanolamine in 1 liter of distilled water.

Next, these plates were printed using Hamadastar Model 8005X manufactured by Hamadastar Co., Ltd., and the presence or absence of scumming on the 50th printed matter after printing was visually evaluated. Note 5) Scratching of printed matter: After each photosensitive material was plate-made in the same manner as in Note 3) above, it was passed through an etching machine once using ELP-EX, and then the monoethanolamine-containing aqueous solution of Note 4) was applied. After soaking for 3 minutes, it was washed with water. Use these offset master plates as dampening water in ELP-
Printing was performed using FX (dampening water manufactured by Fuji Photo Film Co., Ltd.), and the number of prints until background stains on the printed matter could be visually determined was determined.

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

[0339] Next, when used as an offset master original plate, a photosensitive material that was not made into a plate was desensitized by diluting the desensitization treatment solution under severe conditions, and the water retention properties were examined by actually printing. The product of the present invention exhibited good water retention without scumming from the start of printing, and even when an original plate actually made was used, 10,000 clear prints without scumming were obtained. On the other hand, Comparative Example A, in which no resin particles for promoting hydrophilicity were added, had insufficient water retention, and background stains on printed matter occurred from the beginning of printing and were not resolved even after printing.

[0340] In Comparative Example B, the electrostatic properties were significantly deteriorated, and a satisfactory copy image could not be obtained in terms of actual imaging performance. On the other hand, regarding water retention as an offset original plate, ink adhesion was significant and staining was significant. This is due to the fact that the hydrophilicity is not sufficiently made; in fact, even when printing with an original plate that has been made hydrophilic under normal desensitization conditions, the background smearing of the printed matter is significant, and the copied image cannot be reproduced on the original plate after plate making. It had deteriorated and prints of satisfactory print quality could not be obtained from the press run.

From the above, it can be seen that an electrophotographic photoreceptor that satisfies the electrostatic properties and printing properties can be obtained only when both the resin [A] and the resin particles [L] of the present invention are used. Example 2 Resin [A-25] 5.5 g (as solid content), resin [B-2] with the following structure 30 g, resin particles [L-12] 3 g
(as solid content), methine dye [II] with the following structure 0
．． An electrophotographic light-sensitive material was prepared in the same manner as in Example 1 except for 02g.

0342]

[Chemical formula 104]

0343]

embedded image The electrophotographic properties and printability of the obtained photosensitive material were measured in the same manner as in Example 1, and the following results were obtained.

[0344] Electrostatic characteristics (30°C, 80%RH) V10
:-620V DRR: 82% E1/10: 28erg/cm2 Imaging performance I(
20℃, 65%RH): Good II (30℃, 80%RH
): Good water retention: ◎ Good stamp resistance: Both electrostatic properties and printability were good, as seen on 10,000 sheets or more. Examples 3 to 18 5 g each (as solid content) of resin [A] shown in Table 12 below,
Resin particles [L] 2.5 g (as solid content) Resin [B-3] 32.5 g with the following structure and methine dye [III] 0
．． Each photosensitive material was prepared in the same manner as in Example 1 except for 018 g.

0345]

[Chemical formula 106]

0346]

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

0347]

[Table 24] The electrostatic properties are as shown in Table 12, at 30°C and 80% RH.
It showed very good results even under the harshest conditions. The actual imaging performance was also good, the water retention as an original plate for offset masters was also good, and the printing durability was up to 10,000 sheets. Examples 19 to 22 Each light-sensitive material was produced in the same manner as in Example 1, except that the dyes shown in Table 13 below were used in place of the spectral sensitizing dye [I].

0348

[Table 25]

0349]

[Table 26] When the electrostatic properties and printing properties of each photosensitive material were measured in the same manner as in Example 1, all of them had excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images were also high temperature. High humidity (
Even under severe conditions (30° C., 80% RH), it provided clear images without background fog or skipped fine lines.

[0350] In addition, when the performance of the offset lithographic plate precursors was evaluated by desensitization treatment in the same manner as in Example 1, the water retention properties of the raw plates were good, and even in the actual printing results after plate making, 10,000 sheets could be printed. Ta.

[0351] However, in the desensitization treatment, desensitization treatment liquid E-1 with the following formulation was used instead of E-1 used in Example 1.
2 was used. Desensitization treatment liquid: E-2 Diethanolamine 80g Newcol B4SN 8g (manufactured by Nippon Nyukazai Co., Ltd.) Methyl ethyl ketone 100g was dissolved in distilled water to make a total volume of 1.0 liters, and the pH was adjusted to 10.0 with potassium hydroxide. Example 23 and Comparative Example C Example 23 6 g of resin [A-1], 32 g of resin [B-4] with the following structure
, a mixture of 2 g of resin particles [L-33], 200 g of zinc oxide, 0.02 g of uranine, 0.04 g of rose bengal, 0.03 g of bromophenol blue, 0.20 g of phthalic anhydride, and 300 g of toluene was heated in a homogenizer at the rotation speed. 1×104 r. p. m. Disperse for 5 minutes, then
To this dispersion, 0.03 g of 1,2,4,5-benzenetetracarboxylic dianhydride and 0.001 g of phenol were added, and the rotation speed was further increased to 1×103 r.p.m. p. m. Dispersion was performed for 1 minute. The dry adhesion amount is 25g on conductive treated paper.
/m2 with a wire bar and dried at 110°C for 1 minute. Next, each electrophotographic photoreceptor shown in Table 14 below was prepared by leaving it in a dark place under conditions of 20° C. and 65% RH for 24 hours.

0352]

Comparative Example C In Example 23, 6 g of resin [A-1] and resin [B
-4] Only 35.5g of resin [B-4] instead of 32g
An electrophotographic photoreceptor was produced in the same manner as in Example 23 except that . The characteristics of each photoreceptor were examined in the same manner as in Example 1, and the results are listed in Table 14.

0353]

[Table 27] In the above measurements, the electrostatic properties and imaging properties were performed in the same manner as in Example 1, except that the following operations were followed. Note 6) Method for measuring E1/10 of electrostatic properties: After the surface of the photoconductive layer is charged to -400V by corona discharge, the surface of the photoconductive layer is irradiated with visible light at an illuminance of 2.0 lux to determine the surface potential. The time required for (V10) to attenuate to 1/10 is determined, and the exposure amount E1/10 (lux/second) is calculated from this. Note 7) Imaging properties After each photosensitive material was left for one day and night under the following environmental conditions, it was obtained by making a plate using a fully automatic plate making machine ELP-404V (manufactured by Fuji Photo Film Co., Ltd.) using ELP-T as a toner. The copied images were visually evaluated for fog and image quality. The environmental conditions during imaging were 20°C, 65% RH (I), and 30°C.
It was carried out at 80% RH (II). Note 8) Water retention and printing durability Same as Note 4) and Note 5) except that the following desensitizing liquid E-3 was used instead of desensitizing liquid E-1 used in Example 1. carried out.

[0354] Desensitizing treatment liquid: E-3 Monoethanolamine 8
0g Neo Soap (manufactured by Matsumoto Yushi Co., Ltd.) 6g
benzyl alcohol 10
After dissolving 0 g in distilled water to make a total volume of 1 liter, the pH was adjusted to 10.5 with potassium hydroxide.

[0355] In both the present invention and Comparative Example C, it was possible to obtain copied images with good electrostatic properties and clear image quality. Furthermore, when used as an offset master original plate, the present invention had good water retention and printing durability of up to 10,000 sheets. However, Comparative Example C, which did not contain resin particles, did not have sufficient water retention under forced hydrophilic conditions, and when it was actually desensitized and printed under normal conditions, there was background smearing in non-image areas. Up to 5,000 pieces of printed matter could not be seen.

From the above, only the photosensitive material of the present invention was able to maintain excellent performance in both electrostatic properties and printing properties. Examples 24 to 31 In Example 23, 6 g of resin [A] shown in Table 15 below (
Each photosensitive material was prepared in the same manner as in Example 23, except that the resin particles [L] were 2 g (as a solid content), the resin [B] was 32 g (as a solid content).

0357]

[Table 28] All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images are also good at high temperature and high humidity (30°C, 80°C).
%RH), it provided clear images without background fog or skipped fine lines.

[0358] Further, when printing was performed as an offset master original plate, printed matter with clear image quality and no scumming was obtained even after printing 10,000 sheets. Examples 32 to 35 Each electrophotographic photoreceptor was prepared in the same manner as in Example 23, except that 31.5 g of the binder resin shown in Table 16 below was used instead of 32 g of resin [B-4]. Created.

0359]

[Table 29] All of the photosensitive materials of the present invention have excellent chargeability, dark charge retention, and photosensitivity, and the actual copied images are also produced at high temperatures and high humidity (30°C, 80°C).
%RH), it provided clear images without background fog or fine line skipping.

[0360] Further, when printing was performed as an offset master original plate, printed matter with clear image quality and no scumming was obtained even after printing 10,000 sheets. Examples 36-39 ELP-
After desensitization by immersion in EX for 4 minutes, printing was performed in the same manner as in Example 1, and 10,000 prints with clear image quality and no background smudge were obtained.

0361]

[Table 30] Examples 40 to 45 The original plate after making each photoreceptor in Table 18 below was subjected to ELP
After passing through an etching machine using -EX once, the resin particles were immersed in a desensitizing solution having the following formulation for 3 minutes to desensitize them. Dissolve in distilled water to make a total volume of 1 liter, and then adjust the pH to 10.5 with potassium hydroxide.

0362]

[Table 31] When these were printed in the same manner as in Example 1, more than 10,000 prints with clear image quality and no scumming were obtained for each original plate.

0363]

According to the present invention, it is possible to obtain an original plate for electrophotographic lithographic printing which has excellent printed images and high printing durability even under severe conditions. Further, the lithographic printing original plate of the present invention is effective in a scanning exposure method using semiconductor laser light.

Claims (4)

[Claims] 1. An original plate for electrophotographic lithography, comprising at least one photoconductive layer containing at least photoconductive zinc oxide, a spectral sensitizing dye, and a binder resin on a conductive support. The photoconductive layer contains at least one of the following resins [A] as the binder resin, and the photoconductive layer further contains at least one of the following resins [A] with a maximum particle diameter of the photoconductive zinc oxide particles or larger. An original plate for electrophotographic lithographic printing, characterized in that it contains at least one type of non-aqueous solvent-based dispersed resin particles having a small particle size as described below. Resin [A]: has a weight average molecular weight of 1 x 103 to 2 x 104, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and has a polymer main chain fragment. At the end, -PO3 H2, -SO3 H, -
At least one polar group selected from COOH, -P(=O)(OH)R01 [R01 represents a hydrocarbon group or -OR02 (R02 represents a hydrocarbon group]] and a cyclic acid anhydride-containing group A resin made by combining [In formula (I) above, a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R03 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles: in a non-aqueous solvent, they are soluble in the non-aqueous solvent but become insolubilized by polymerization;
Monofunctional monomer (C) containing at least one functional group that generates at least one hydroxyl group upon decomposition
Copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the solvent, which comprises at least a repeating unit containing a substituent containing a silicon atom and/or a fluorine atom. . 2. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). The electrophotographic lithographic printing original plate according to claim 1, characterized in that it contains at least one of the following. [Formula (Ia) and (Ib) above, T1
and T2 are each independently a hydrogen atom and a carbon number of 1 to 1
0 hydrocarbon group, chlorine atom, -COR04 or -COO
R05 (R04 and R05 each represent a hydrocarbon group having 1 to 10 carbon atoms), and L1 and L2 each represent -CO
The number of single bonds or connected atoms connecting O- and the benzene ring is 1 or more
Represents 4 linking groups] 3. The electrophotographic lithographic printing original plate according to claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 4. Claim 1, wherein the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. The original plate for electrophotographic planographic printing according to any one of items 1 to 3. [In general formula (II), V0 is -O-, -COO
-, -OCO-, -(CH2)p -OCO-, -(
CH2 ) p -COO-, -SO2 -, -CONR
1 -, -SO2 NR1 -, -C6 H4 -, -
CONHCOO-, or -CONHCONH- (where p represents an integer of 1 to 4, R1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b1,
b2 may be the same or different, and may be a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-R2
or -COO-R2 (R2 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon group]