JPH02250065A - Planographic original plate - Google Patents

Abstract

PURPOSE:To enhance desensitization performance to fatty change by incorporating hydrophilic resin particles having an average particle diameter same as the maximum particle diameter of photoconductive zinc oxide particles or smaller in a photoconductive layer and adding 2 kinds of specified resins to a binder resin. CONSTITUTION:The photoconductive layer contains the hydrophilic resin particles having an average particle diameter same as the maximum particle diameter of photoconductive zinc oxide particles or smaller than this, and the binder resin contains at least one kind of resin A having a weight average molecular weight of 10<3> - 2X10<4> and copolymerized structural units each having at least one kind of polar group, such as -PO3H2, in an amount of 0.5 - 20wt.%, and at least one kind of resin B having a weight average molecular weight of >=5X10<4>, and a cross-linking structure, and at least one kind of repeating units of copolymerized components each represented by formula I in which T is -COO- or the like; V is a 1 - 22 C hydrocarbon group; and each of a1 and a2 is H or the like, each optionally same or different; thus permitting desensitization for fatty change performance to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an electrophotographic lithographic printing original plate made by an electrophotographic method, and in particular to a composition for forming a photoconductive layer of the lithographic printing original plate. Concerning the improvement of things.

(Prior art and its problems) Currently, various types of offset original plates for direct plate making have been proposed and put into practical use. A photoreceptor with a photoconductive layer mainly composed of resin is subjected to a normal electrophotographic process to form a highly hydrophilic toner image on the surface of the photoreceptor, and then the surface is desensitized with an etchant. A widely used technique is to obtain an offset original plate by selectively making non-image areas hydrophilic by treatment with a liquid.

In order to obtain good printed matter, first, the original image is faithfully copied onto the offset master plate, the surface of the photoreceptor is easily compatible with the desensitizing treatment liquid, and the non-image area is made sufficiently hydrophilic, while at the same time it is water resistant. In addition, during printing, the photoconductive layer with the image does not separate and is compatible with dampening water,
It is necessary to have performance such as sufficient hydrophilicity of non-image areas to prevent staining even if the number of printed sheets increases.

It is already known that these performances are affected by the ratio of zinc oxide to binder resin in the photoconductive layer.For example, it is possible to reduce the ratio of binder resin to zinc oxide particles in the photoconductive layer. For example, the desensitization property of the surface of the photoconductive layer is improved and scumming is reduced, but on the other hand, the internal cohesive force of the photoconductive layer itself is decreased, and the printing durability is decreased due to a lack of mechanical strength. arise. Conversely, if the ratio of the binder resin is increased, the printing durability will be improved, but the scumming will increase. In particular, it goes without saying that scumming is a phenomenon related to the desensitization property of the surface of the photoconductive layer. It has become clear that it is not only influenced by the ratio of , but also largely influenced by the type of binder resin.

In particular, for offset master plates, as mentioned above, scumming due to insufficient desensitization is a major problem. Various developments have been considered. for example,
In Japanese Patent Publication No. 50-31011, a (meth)acrylate-based monomer is copolymerized with other monomers in the presence of fumaric acid, and a (meth)acrylate-based resin is copolymerized with [1,8 to 10XIO' at 7810 to 80°C]. A combination of a monomer and a copolymer consisting of a monomer other than fumaric acid,
Furthermore, JP-A No. 53-54027 discloses a method using a terpolymer containing a (meth)acrylic acid ester having a substituent having a carboxylic acid group separated by at least 7 atoms from the ester bond; No. 54-20735, Japanese Unexamined Patent Publication No. 1973
No. 7-202544 uses a quaternary or penta-component copolymer containing acrylic acid and hydroxyethyl (meth)acrylate, and JP-A-58-68046 uses an alkyl group having 6 to 12 carbon atoms as a substituent. It is described that a method using a ternary co-assembly containing a (meth)acrylic acid ester and a carboxylic acid-containing vinyl monomer is effective in improving the desensitization property of the photoconductive layer.

However, even if the resin is said to be effective in the above-mentioned desensitization property (2), when it is actually evaluated, it is still unsatisfactory in terms of scumming and printing durability.

Furthermore, as a binder resin, resins containing functional groups that generate hydrophilic groups upon decomposition are being considered.
For example, those containing functional groups that generate hydroxyl groups upon decomposition (JP-A No. 62-195684, No. 62-2)
No. 10475, No. 62-210476) and those containing a functional group that generates a carboxyl group upon decomposition (Japanese Patent Application Laid-Open No. 62-212669).

These resins are resins that are hydrolyzed or hydrolyzed by desensitizing liquid or dampening water used during printing to generate hydrophilic groups, and when used as binder resins for lithographic printing original plates, hydrophilic groups can be generated. When a resin containing the group itself is used, various problems (deterioration of smoothness, dark charge retention, The deterioration of electrophotographic properties such as photosensitivity) can be avoided, and the hydrophilicity of the non-image area, which is made hydrophilic by the desensitizing liquid, is generated by decomposition in the resin. As the oleophilicity of the image area and the hydrophilicity of the non-image area become clearer, it prevents ink from adhering to the non-image area during printing, resulting in clear image quality without background smearing. It is stated that it is possible to print a large number of printed materials.

Nowadays, there is a demand for even greater efficiency in planographic printing using electrophotography. Specifically, improvements in plate-making speed, etching processing speed, and clear image quality from the start of printing are required. Obtaining printed matter (particularly without background smudges) (reducing waste paper) has become an important issue.

In order to meet these required performances, hydrophilic groups are generated by the above decomposition. Offset master plates using binder resins have not yet achieved sufficient performance in terms of improving etching processing speed and reducing paper waste.

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

In other words, the first object 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, as an offset original plate, has uniform background smudges on the entire surface. An object of the present invention is to provide a lithographic printing original plate which does not cause even dotted background stains and has excellent desensitization properties.

A second object of the present invention is to provide a lithographic printing original plate that produces clear and high-quality images even when the environment during copy image formation fluctuates, such as low temperature and low humidity, or high temperature and high humidity.

The third object of the present invention is to provide a lithographic printing original plate that retains sufficient hydrophilicity in non-image areas even when the process from etching to printing is sped up, does not cause scumming, and has high printing durability. The goal is to provide the following.

A fourth object of the present invention is to provide a CPC photoreceptor with excellent electrostatic properties and low environmental dependence.

A fifth object of the present invention is to provide a lithographic printing original plate that is not easily influenced by the types of sensitizing dyes that can be used in combination.

(Means for Solving the Problems) The present invention achieves the above-mentioned object by providing an electrophotographic photoconductive layer comprising at least one photoconductive layer containing photoconductive zinc oxide and a binder resin on a conductive support. In the type lithographic printing original plate, the photoconductive layer contains hydrophilic resin particles having an average particle diameter that is the same as or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is as follows: This is achieved by a lithographic printing original plate characterized by containing at least one resin [A] and at least one resin CB below.

Resin [A]: has a weight average molecular weight of 103 to 2 x 104, and -P
03H2 group, -3O,ll group, -COO11 group, -0
1l group, -3N group.

Resin resin [B] containing 0.5 to 20% by weight of a copolymer component containing at least one polar group selected from
: It has a weight average molecular weight of 5X103 or more and has the following general formula [
A resin containing at least a repeating unit represented by [I] as a polymer component and having a crosslinked structure.

General formula [I]; There may be.

(i): 30% by weight or more of one repeating unit represented by formula [■] or formula [I11] Formula [11] % Formula % [In the formula, T is -COD-, -11Cn--CIl□0C
Represents O-C112COD-, -0- or -3O,-.

(2) represents a hydrocarbon group having 1 to 22 carbon atoms.

al and a2 may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano atom, a hydrocarbon group having 1 to 8 carbon atoms, -coo-z, or a hydrogen atom via a hydrocarbon group having 1 to 8 carbon atoms. COO-Z (Z represents a hydrocarbon group having 1 to 18 carbon atoms). ] The above resin [A] contains the following repeating units (i) and (ii) as copolymerization components, and has the formula [111] [In the formula, X and x2 are each independently a hydrogen atom, It represents a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COY, or C00Y2 (Y, and Y2 each represent a hydrocarbon group having 1 to 10 carbon atoms). however,
Both x1 and x2 do not represent hydrogen atoms.

W and W2 each represent a direct bond or a linking group having 1 to 4 linking atoms that connects -000- to the benzene ring.

] (ii): -PO,82 group, -3O,)I group, -C00I+ group, -
P-OH group [R is a hydrocarbon group having 1 to 10 carbon atoms or -O
R'(R' represents a hydrocarbon group having 1 to 10 carbon atoms). ], 0.5 to 15% by weight of at least one repeating unit among the polar groups of the -511 group and the phenolic -011 group and the cyclic acid anhydride-containing group The above resin [B) further contains at least one polymer -110,11,, -3O,ll only at one end of the main chain,
-COOI+.

-II+, -3l+, -P-011 (R' represents a hydrocarbon)'nR cyclic acid anhydride, -CHO, -CONI+□, -3
A resin that binds at least one polar group selected from O, NH, and each of which represents a hydrogen atom or a hydrocarbon group [
B'] may be used.

Moreover, the above-mentioned resin [B] may be a resin that does not contain, as a polymer component, a repeating unit containing a polar group or a cyclic acid anhydride-containing group as shown in resin [A].

Furthermore, the above-mentioned hydrophilic resin particles may form a high-order network structure.

In addition, the above-mentioned hydrophilic resin particles in the present invention have the above-mentioned average particle diameter, and a film of the resin formed by coating the resin particles dissolved in an arbitrary soluble solvent is dissolved in distilled water. A contact angle (measured with a goniometer) of 50 degrees or less, preferably 30 degrees or less.

(Function) In the present invention, it is important that the hydrophilic resin is dispersed as particles in the photoconductive layer, and that the average particle diameter is the same as or smaller than the largest particle of the photoconductive zinc oxide particles. It is. Such hydrophilic resin particles have a smaller specific surface area than those existing in the molecular state, eliminate interaction with the zinc oxide surface, do not inhibit electrophotographic properties, and have good printing properties. It is possible to obtain a lithographic printing plate that expresses. If the resin particles have a particle size larger than the zinc oxide particle size, the electrophotographic properties will deteriorate (in particular, uniform charging properties will not be obtained), resulting in uneven density in the image area, characters, etc. in the copied image. Breakage or skipping of thin lines, or blurring of the non-image area may occur.

Specifically, the resin particles of the present invention have a maximum particle diameter of 1
It is 0 μm or less, preferably 5 μm or less. The average particle diameter of the particles is 1.0 μm or less, preferably 0.5 μm or less.

In addition, the smaller the particle diameter of the hydrophilic resin particles, the larger the specific surface area, which gives good effects on the electrophotographic properties mentioned above, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, If the thickness is too large, the same disadvantages as in the case of molecular dispersion will occur, so it is preferable to use the thickness at 0.001 μm or more.

Furthermore, in the present invention, if the hydrophilic resin particles form a high-order network structure, they will not be eluted by dampening water during printing, and will maintain good printing characteristics even when printing a large number of sheets. can be maintained.

In accordance with the present invention, hydrophilic resin particles that do not form a high-order network structure as described above (hereinafter simply referred to as hydrophilic resin particles)
Alternatively, hydrophilic resin particles forming a high-order network structure (hereinafter simply referred to as network hydrophilic resin particles) are photoconductive zinc oxide 1
It is preferable to use it in an amount of 0.1 to 5% by weight based on 0.00 weight parts.

0.1% by weight of hydrophilic resin particles or mesh hydrophilic resin particles
If the amount is less than 0, the hydrophilicity of the non-image area will not be sufficient;
．． When the amount is more than 5% by weight, the hydrophilicity of the non-image area can be further improved, but the electrophotographic properties deteriorate and the copied image deteriorates.

The hydrophilic resin particles of the present invention include synthetic hydrophilic resins and natural hydrophilic resins, and both can be preferably used in the present invention.

Furthermore, as the network hydrophilic resin particles, those obtained by modifying these are preferably used.

For example, P,1Jolyneax rWater-5
olable 5ynthetic Polymer
s: Properties and Be
havior JVol I and Vol II
CRC Press, Inc. (1982) C1^
, Pinch chemistry and Te
Chnology of Water-3olable
PolymersJPlenam Press (19
1973), Nobuo Nakamura “Water-Soluble Polymer” Kagaku Kogyosha (19
1968), Surface Chemistry Study Group, “Latest processing/modification technology and application development of water-soluble polymer water-dispersed resins” Management Development Center Publishing Department (1981), Dav+d-son rWa
ter 5olable Re5in JReinho
ld (1968) and other review articles.

Among these, synthetic hydrophilic resins include ether groups, ethylene oxide groups, -Go, -811 groups, -C0011 groups, -3O,l+ groups, -303H groups, J
selected from O-R2 group, -CN group, -CONIl, group, -CI group, -3O,R, group, 4- to 6-membered heterocyclic ring containing at least one nitrogen atom, or organosilane group Examples include those containing at least one type of hydrophilic group.

In the above hydrophilic group, R8 is an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroenyl group, 2-bromoethyl group, 2-fluoroethyl group). group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group, benzyl group, phenyl group, propenyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl μ, etc.).

R3 is an optionally substituted aliphatic group having 1 to 6 carbon atoms (specifically, represents the same substituent as R1) or =OR'
(R' represents the same content as R1).

R3 and R1 may be the same or different, and represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 6 carbon atoms (specifically, the same content as R1). however,
The total number of carbon atoms in R5 and R1 is 8 or less.

Rs, Rs and R7 may each be the same or different and represent the same content as Ra and R4.

xe represents an anion, for example, a halogen ion (
For example, chloride ions, bromide ions, iodine ions, etc.)
barchlorate ion, tetrafluoroborate ion,
Examples include hydroxyl ions, carboxylate ions (eg, acetonate ions, propionate ions, etc.), and sulfonate ions (eg, methanesulfonate ions, benzenesulfonate ions, p-toluenesulfonate ions, etc.).

r represents 1 or 2, and when r=1, -R3-,
at least one acidic group (-3O,H.

-PO, l+2. -COOII) is contained as a substituent.

Ru.

In addition, the -COOII group, -3O2H group, -3O,H group, -Po, 112 group, and -P-R group each represent an alkali metal (e.g., lithium, sodium, potassium, etc.), an alkaline earth metal ( For example, salts with metal salts such as calcium, magnesium, etc.), zinc, aluminum, etc., or salts with organic bases (eg, triethylamine, pyridine, morpholine, piperazine, etc.) may be formed.

Also, a 4- to 6-membered compound containing at least 61 of the above nitrogen atoms.
Examples of membered heterocycles include pyridine rings, piperidine rings, pyrrole rings, imidazole rings, pyrazine rings,
Examples include a pyrrolidine ring, viroline ring, imidacilline ring, imidacilline ring, pyrazolidine ring, piperazine ring, morpholine ring, and pyrrolidone ring. These heterocycles may contain substituents, such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), optionally substituted hydrocarbons having 1 to 8 carbon atoms. groups (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2
-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-carboxyethyl group, carboxymethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-methoxycarbonylethyl group, 2-
Ethoxycarbonylethyl group, 2-methanesulfonylethyl group, benzyl group, carboxybenzyl group, carboxymethylbenzyl group, phenyl group, carboxyphenyl group, sulfophenyl group, methanesulfonylphenyl group,
ethanesulfonylphenyl group, carboxymethylphenyl group, methoxyphenyl group, chlorophenyl group, etc.), 0
11'(R' represents the same content as the above-mentioned optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or -0001~ group (R" represents the same content as R'), etc. Can be mentioned.

In addition, as an organosilane group, for example, the following general formula (
Examples include repeating units represented by IV).

In formula (rV), A is an optionally substituted alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-methoxyethyl group, 2- cyanoethyl group, etc.) -OR- (R~ represents the same content as the optionally substituted alkyl group having 1 to 4 carbon atoms in A), or "Z" group [z is trimethylsiloxy, pentamethylsiloxy, Siloxanyl, heptamethyl) IJ
Siloxanyl, nonamethyltetracyclate: tosanyl, bis(trimethylsiloxy)methylsiloxanyl, tris(
(trimethylsiloxy)siloxanyl, etc.].

Wl is an optionally substituted alkyl group having 1 to 6 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
Hexyl group, 2-methoxyethyl group, 2-ethoxypropyl group, 2-cyanoethyl group, 2-hydroxyethyl group, 2-hydroxy-3-chloro-propyl group, 2-chloroethyl M "IF", -〇R''' (R″″ represents the same content as R#) or vinyl, methacryloxy, acryloxy, methacrylamide, acrylamide, styryl, allyl, etc. via a divalent hydrocarbon group having 1 to 6 carbon atoms. Represents a group in which an unsaturated bond selected from the group is polymerized and linked to other repeating units.

a is 0 or an integer from 1 to 10, and represents that the sum of the values of a is at least 2.

The hydrophilic resin of the present invention is a homopolymer or copolymer containing a polymeric component containing at least one of the above hydrophilic groups in the polymer side chain, and the polymeric component is a polymeric component in the resin. 20% to 100% by weight, preferably 3
It is contained in an amount of 0% to 100% by weight.

More specifically, an example of this hydrophilic group-containing polymerization component is shown by general formula (V).

'FchiC7　　　(V) -W-Y In formula (V), X is -coo-, -coc-, -o-.

o　　　　　z, 　　　　z, 　　　　z.

So 2. ．． 22 is each a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-hydroxyethyl group, 3-bromo-2- hydroxypropyl group,
2-carboxyethyl group, 3-carboxypropyl group,
4-carboxybutyl group, 3-sulfopropyl group, benzyl group, sulfobenzyl group, methoxybenzyl group, carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2-methoxyethyl group, 3- Methoxypropyl group, 2-methanesulfonylethyl group, 2-cyanoethyl group, N,N(dichloroethyl)aminobenzyl group, N,N(dihydroxyethyl)aminobenzyl group, chlorobenzyl group, methylbenzyl group, N,N( dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc. may be the same or different, and may be a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an aliphatic group having 1 to 4 carbon atoms (preferably, for example, a methyl group, an ethyl group, a propyl group, etc.). group, butyl group, etc.), and n represents an integer of 1 to 6. ] h.

(-c=c→ , -coo-, -oco-, -o--5
bs b,, b.

Represents a linking group selected from -NHCONH- or -C- or a linking group formed by a combination of these linking groups.

[Here, b1 to b4 may be the same or different,
Hydrogen atom, halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.) or a hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2 -chloroethyl group, 2-methoxyethyl group, 2-methoxycarbonylethyl group, benzyl group, methoxybenzyl group, phenyl group, metonide diphenyl group, methoxycarbonylphenyl group) or formula (
V) represents the -[tY] group, and bs-b7 represents the above 21. Represents the same content as L. ] Y represents the above-mentioned hydrophilic group, -OH group, -311
group, -CI-10 group, -CN group, -COO11 group, -3
It represents a 4- to 6-membered heterocycle containing one O2H group or an organosilano group.

[Here, R1-R1 represents the same contents as R, -R, above. ] In formula (V), Y may be directly bonded to the main chain of the polymer, or X may be directly bonded to one row X.

al*as may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a ~C00II group, -CDO
R3 group, -['H, [''00R1 group (Rs has 1 carbon number
-7 hydrocarbon group, specifically, the above-mentioned 2. ,
2. ) or an alkyl group having 1 to 4 carbon atoms (preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

More specifically, hydrophilic group-containing polymerization components indicated by "-" are illustrated below, but the present invention is not limited thereto.

Z.

a a: -C113.

CD D H -(CIl□-CH-) [:0NII2゜C0NHC2H5゜0OH COOCI+3 1l -CONII,l -SO□N]12 -(CH2-C-) -C)13゜I C0NH(CIl□7old 1 n; integer from 1 to 12 L: U U (L: II 2t S U s If
Integer M: Li, Na, K.

H-N(C2H5) 3 a: ■.

C.L. -(CHz -C+ [:0NH2 a ni -H.

CH.

-(CII, -C1l-) Y: -Nl+2 1h-ULIJ (1,:112) rlt: Old 111 Integer -(CIl□-C+ CD (CI+2)28IICO(C112) l, C
Mouth OHa Knee II.

-CH.

Mouth: Integer from 1 to 10 -(CH.

CD-C00 (C112), OC1] (C112), COO
1+11°-CI+,.

-C) I2COOCH.

n: An integer from 2 to 1O - (CH2-C-) m: An integer from 1 to 10 (however, n+m is less than or equal to 1O) COD (C112) 2(1(:11 (Cllz)
nCO[]ll-H1-CI+.

-(C11, -C-) Con(C112C11211-hOcl(+:112
), C00I+a: -If.

C11,.

I -(CH2-C+ [Integer from 11 to 4 0mouth0(CH□)20COC)I=CHC0011 m: integer from l to 4 a2 -11, -C)! ,.

CH2C00CH3 -(CH.

C± a ni -CH,.

H COD(CtL)2-3O2CH3 -(CH2-C-) COD (CH2) 2N (C113) 2a:
it, -CL-(Ctl x-咋■-CH.

C0D(CH2)2N (C112CII□O11)2
a: C11s -(CL-C-) Cfln (C112) 2NII[':n (C7)
acfl[INa a: =11°Cll3°CIl□C0DCI+.

-(C11, -CI+-) COOC! (2C112Sl+ CH3 -(CH, -C-) CODCII□CIICLDCD(CI42)2COO
)1CH3-(C')1. -C-)-C=0 Together with the above hydrophilic group-containing polymer component, C11,
C00+1 Examples of other polymer components that can be copolymerized include those represented by the general formula. You can make it heavier.

-(N-CII2CIIr)- COCll.

formula P is the formula (V) Same content as the X inside represents.

Q is an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, probyl group, butyl group, octyl group, decyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 4-methoxycarbonylbutyl group, 4
-methoxybutyl group, 3-chloro-2-methoxypropyl group, 3-chloro-2-ethoxycarbonylpropyl group, 2-glycidylpropyl group, 3-bromo-2-acetyloxylpropyl group, etc.), carbon number 2- 20 optionally substituted alkenyl groups (e.g. vinyl group, allyl group, etc.), optionally substituted alicyclic groups having 5 to 12 carbon atoms (e.g. cyclopentyl group, cyclohexyl group, cyclopentyl group, chlorocyclohexyl group, bromo cyclohexyl group, 2-cyclohexylethyl group, cyclohexylmethyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, ethyl-2-phenylethyl group) , naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
(dichlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, dimethoxybenzyl group, trimethoxybenzyl group, methoxycarbonylbenzyl group, acetamidobenzyl group, etc.), carbon atoms of 6 to 12 Aryl groups that may be substituted (e.g. phenyl group, tolyl group, xylyl group, mesitylene group, naphthyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, fluorophenyl group, methoxyphenyl group, chloro-methyl - phenyl group, methyl-methoxy-phenyl group, nitrophenyl group, methoxycarbonylphenyl group, acetamidophenyl group, ethoxyphenyl group, chloronaphthyl group, ethoxycarbonylnaphthyl group, propylphenyl group, butylphenyl group, chloromethylphenyl group, methoxymethylphenyl group, N-methylaminosulfenyl group, etc.), or a 4- to 7-membered heterocycle (any heterocycle other than the nitrogen atom-containing heterocycle exhibiting hydrophilicity described above may be used, for example, Examples include a thiophene ring, a furan ring, a pyran ring, a benzopyran ring, a virol ring, an indole ring, a quinoline ring, a thiazole ring, an oxazole ring, a benzothiazole ring, and these rings may contain a substituent. As a substituent, the above-mentioned formula (V
1) represents the same content as Q in).

As natural hydrophilic resins, in particular, the above-mentioned comprehensive technical data collection of water-soluble polymer water-dispersible resins (Management Development Center Publishing f.
f1s), for example, everignin,
Examples include starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigeran, and derivatives thereof.

As the derivative, particularly preferred are sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated derivatives, and salts thereof.

In the present invention, two or more natural hydrophilic resins may be used in combination.

Among natural hydrophilic resins, glucose polymers and derivatives thereof are preferred, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, nigeran, etc. are preferred, and dextran and its derivatives are preferred. Derivatives are preferred.

In order to form the above synthetic/natural hydrophilic resin into fine particles having a specific particle size as described above, conventionally known dry and wet methods can be employed. That is, the hydrophilic resin powder is directly pulverized with a conventionally known pulverizer to form fine particles (for example, a ball mill, a paint shaker, a jet mill,
A method using a hammer mill etc.) and a method of forming polymer latex particles can be used. As a method for producing the latter polymer latex particles, a conventionally known method for producing latex particles for paints or liquid developing materials for electrostatic photography can be used. That is, in a method of dispersing the hydrophilic resin in combination with a dispersing polymer, the hydrophilic resin and the dispersion-assisting polymer (or coating polymer) are kneaded in advance to form a kneaded product, which is then pulverized, and then the dispersed polymer is This is a method of coexisting and dispersing.

Specifically, for example, translated by Kenji Ueki [Paint Flow and Pigment Dispersion] Kyoritsu Shuppan (1971), "Solomon, Chemistry of Paint", rPaint and SurfaceCoa
ting theory and practice
”, Yuji Harasaki “Coating Engineering” Breakfast Bookstore (1971
), Yuji Harasaki “Basic Science of Coatings” Maki Shoten (1)
977), JP-A-62-96954, JP-A No. 62-11
No. 5171, No. 62-75651, and the like.

Alternatively, a method for easily obtaining latex particles of the hydrophilic resin by a conventionally known polymerization reaction such as a suspension polymerization method or a dispersion polymerization method can also be used.

Specifically, So Muroi - "Chemistry of polymer latex" Kobunshi Publishing (1970), Taira Okuda, Hiroshi Inagaki [Synthetic Resin Emulsion] Kobunshi Publishing (1978), So Muroi - "
It is described in the bottom of ``Introduction to Polymer Latex'', Kobunsha (1983), etc.

In the present invention, a method of forming polymer latex particles is preferred, and by this method, it is possible to easily obtain particles with an average particle diameter of 1.0 μm.
The following resin particles can be used.

By the way, in the electrophotographic lithographic printing original plate of the present invention, when forming a photoconductive layer, a method of dispersing photoconductive zinc oxide in an aqueous system (for example, Japanese Patent Publication No. 51-450, No. 4) is used.
No. 7-18599, No. 46-41350, etc.) and methods of dispersing in non-aqueous solvents (for example,
No. 31011, JP-A No. 53-54027, JP-A No. 54-2
No. 0735, No. 57-202544, No. 58-680
No. 46, etc.), but if water remains in the photoconductive layer, the electrophotographic properties will be impaired, so a method of dispersing in a non-aqueous solvent is preferred. Therefore, in order to sufficiently disperse the latex particles of the hydrophilic resin of the present invention in the non-aqueous dispersed photoconductive layer, it is preferable that the latex particles are also non-aqueous latex.

The non-aqueous solvent used in the non-aqueous latex may be any organic solvent as long as it has a boiling point of 200° C. or less, and it may be used alone or in combination of two or more.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propatool, butanol, alcohol fluoride, and hexylsilkol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, diethyl ether, tetrahydrofuran, and dioxane. ethers such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc., hexane, octane, decane, tridecane, tridecane, etc.
Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, Examples include halogenated hydrocarbons such as chloropropane and trichloroethane.

If polymer latex is synthesized using dispersion polymerization in these non-aqueous solvent systems, the average particle diameter of latex particles can easily be reduced to 1 μm.
m or less, and the particle size distribution is very narrow and monodisperse particles can be obtained.

Specifically, B, J., Barrett r Di
spersion Polymerization i
n Organic Media J John
n Wiley (1975), Koichi Murata, Polymer Processing, 23.20 (1974), Tsunetaka Matsumoto and Toyokichi Tange, Japan Adhesive Association Journal 9.183 (1973), Toyokichi Tange,
Japan Adhesive Association Journal 23.26 (1987), Kuchi, J.
WaIbridge, NAT port, Adv,
5tudy,rnst,Ser,B,Na67
．． 40 (1983), B, P, No. 893429, B,
P, No. 93403H, No. ll5P1122397, US
P 3900412, tlsP 4606989,
The method is disclosed in JP-A-60-179751 and JP-A-60-185963.

In addition, the network hydrophilic resin particles specifically include -H,
-311, -C port 011. -3O211, -5O4H,
-CN.

-CONIl, -CIIO, -5O,R,.

Examples include those containing at least 11:1 hydrophilic groups selected from ether groups, ethylene oxide groups, 4- to 6-membered heterocycles, and organosilane groups.

In the above hydrophilic group, R6 is an optionally substituted alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group) , 3-chloropropyl group, 3-methoxypropyl group, methoxyethyl group, ethoxymethyl group, 2-methoxyethyl group, etc.).

R3 is an optionally substituted alkyl group having 1 to 4 carbon atoms (
Specifically, it represents the same substituent as R5) or -OR
'(R' represents the same content as L).

R3 and R4 may be the same or different, and represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms (specifically, the same content as R3). However, the total number of carbon atoms in R3 and R1 is 6 or less.

Rs, Rs and R1 may be the same or different, and represent the same content as Ra and R4.

Xe and r are the same as those of the hydrophilic resin particles described above.

In addition, examples of the heterocycle forming a 4- to 6-membered ring include:
Furan ring, pyran ring, tetrahydrofuran ring, pyridine ring, piperidine ring, virol ring, imidazole ring, pyrazine ring, pyrrolidine ring, pyrroline ring, imidazolidine ring, imidacilline ring, pyrazolidine ring, piperazine ring, morpholine ring, pyrrolidone ring, dioxane ring, dioxolane ring, oxazoline ring, 1.3-year old xazin-2one ring, morpholinedione ring, morpholine ring and the like.

These heterocycles may contain substituents, such as halogen atoms (fluorine atoms, chlorine atoms,
bromine atom, etc.), an optionally substituted alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, 2-
Chloroethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl M, etc.>, -OR
' group (R' represents the same content as the above-mentioned optionally substituted alkyl group having 1 to 3 carbon atoms), and the like.

Further, examples of the organosilane group include the same organosilane groups as those of the hydrophilic resin particles described above.

The network hydrophilic resin of the present invention is a homopolymer or copolymer containing a polymeric component containing at least one of the above-mentioned hydrophilic groups in the polymer side chain, and as in the case of the hydrophilic resin described above. , the polymerization component is 2 as a polymerization component in the resin.
0% to 100% by weight, preferably 30% to 10% by weight
It contains 0% by weight.

The specific general formula and specific component examples of this network hydrophilic resin are the general formula (V) of the hydrophilic resin described above, component examples (1) to
It is the same as (57).

In addition, as a natural network hydrophilic resin, specifically, Interface Chemistry Research Group, "Latest processing/modification technology and application development of water-soluble polymers and water-dispersed resins" Management Development Center Publishing Department (1
(published in 1981), Yoshio Nakamura, "Water-soluble polymer" Kagaku Kogyosha (published in 1973), R, L, Kuchi avidson,
r Handbook of Water-3o
lubleGums and Re5ius J
&lcGraw-11i11 ro00R['o
mpany (published in 1980), r [1ncyclo
pedia of Polymerscience
and Bnginearing J VOI
3, p. 69-270, John
Wiley and 5ons (published in 1985)
etc. are described in detail.

Specifically, the same derivatives as the above-mentioned natural hydrophilic resins and the same derivatives as the above-mentioned natural hydrophilic resin derivatives can be mentioned.

The network hydrophilic resin particles of the present invention have a high-order network structure in which the polymer molecular chains of the polymer made of the above hydrophilic polymer components are bridged.

As a result, the network hydrophilic resin particles become releasable or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The crosslinking of the present invention can be carried out by conventionally known crosslinking methods. That is, (1) a method of crosslinking a polymer containing the hydrophilic polymerization component with various crosslinking agents or curing agents, (2) a method of containing at least a monomer corresponding to the hydrophilic polymerization component and carrying out the polymerization reaction. A method of forming a network +11FF structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups during the process, and [3] the hydrophilic polymerization component and This can be carried out by a method such as a method in which a polymer sequence containing a component containing a reactive group is crosslinked by a polymerization reaction or a polymer reaction.

Examples of the crosslinking agent used in method (1) above include compounds commonly used as crosslinking agents. ), Compounds described in Polymer Science Yoshin "Polymer Data Handbook Basic Edition" Baifukan (1986), etc. can be used.

For example, silane coupling of organic silane compounds (e.g., vinyltrimethoxysilane, vinylolibutoxysilane, T-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, T-aminopropyltriethoxysilane, etc.) agents), polyisocyanate compounds (e.g. toluylene diisocyanate, 0-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, inholon) diisocyanate, polymeric polyisocyanate, etc.), polyol compounds (e.g. 1,4-butanediol, polyoxypropylene glycol, polyoxylene alkylene glycol, 1°1.1-)limethylolpropane, etc.), polyamine-based compounds (for example, ethylenediamine, T-hydroxypropylated ethylenediamine, phenylenediaminehexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds, and epoxy resins (for example, Compounds described in "Evo Toshi Resin" by Shokodo (published in 1985), "Epoxy Resin" edited by Yuki Hashimoto, Nikkan Kogyo Shimbun (published in 1969), melamine resin (for example, some Miwa resins,
Compounds described in "Area Melamine Resin" edited by Hideo Matsunaga, Nikkan Kogyo Shimbun (published in 1969), poly(
Meta) cyfrylate compounds (for example, compounds described in Shin Okawara, Takeo Saegusa, and Toshinobu Higashimura, eds. "Oligomer" Kodansha (1976), Eizo Omori "Functional Acrylic Resin" Technosystem (1985), etc. are mentioned,
Specifically, polyethylene glycol diacrylate,
Neopentyl glycol cyacrylate, ■, 6-hexanethiol diacrylate, trimethylolpropane triallylate, pentaerythritol polyacrylate, bisphenol A diglycidyl ether diacrylate, oligoester acrylate: these methacrylates etc.

Among the hardening agents used in the method (1) above, examples of hardening agents for natural hydrophilic resins such as gelatin include those described in US Patent No. 3.
No. 057.723, No. 3,671% No. 256, No. 3.3
96°029, 4.161.407, 4.20
7.109, British Patent No. 1.322.971, Japanese Patent Publication No. 17112-1972, Japanese Patent Publication No. 94817-1987, Japanese Patent Publication No. 56-66841, British Patent No. 57-207243, Japanese Patent Publication No. 59
-121327, ``The Theory of the Photographic Process,'' intaglio (T, I+, James et al.), page 94, and ``Polymeric Amines and Ammonium Salts J (B, J, Goetalsura), page 321. You can use whatever you have.

Moreover, as the polymerizable functional group of the polyfunctional monomer or polyfunctional oligomer containing two or more polymerizable functional groups in the method (2) above, specifically, CH2=CH-C1lz-
, Cll2=CII-C-0-, C112=C11-C
H,=C-C0NH CH=[: II-C(IN IICH,=[:
1I-CH, -0-C- C112= CH-N It CO- CH2=CH-CH2-NHCO-CH2=CH-8O
, -CH2=CHl-CO-CH2=CI+-0-CH
2=CH-3-, etc. can be mentioned. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of monomers having two or more polymerizable functional groups include, for example, monomers or oligomers having the same polymerizable functional groups, such as sularen derivatives such as divinylbenzene and trivinylbenzene: Polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #4
Fl 0, #600.1.3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol nato), or polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and esters of methacrylic acid, acrylic acid or crotonic acid (derivatives thereof), vinyl ethers or allyl ethers; Phthalic acid, itaconic acid, etc.) vinyl esters, allyl esters, vinylamide neck or esteramides: polyamines (e.g. ethylenediamine, 1,3-pylene diamine, 1,4-butylene diamine, etc.) and vinyl Examples include condensates with group-containing carboxylic acids (eg, 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 (e.g., methacrylic acid, allylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, allyloylprobion) reactants of alcohols or amines (e.g. allyloxyeruponylpropionic acid, allyloxycarbonyl acetic acid, allyloxycarbonyl acetic acid,
- Ester derivatives or amide derivatives containing vinyl groups such as 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate) , allyl itaconate,
Vinyl methacryloyl acetate, vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl acrylate methyloxyerbonylcartylene ester, N-allyl cyclylamide, N-allyl methacrylamide, N- allyl itaconic acid amide,
methacryloylpropionic acid orylamide, etc.) or amino alcohols (e.g., aminoethanol, -aminopropanol, 1-aminobutanol, l-aminohexanol, 2-aminobutanol, etc.) and carboxylic acids containing vinyl groups. Examples include condensates.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is used in an amount of 10 mol % or less, preferably 5 mol % or less of the total monomers, and is polymerized to form a resin.

Further, in the present invention, a polymer containing a polymerizable double bond group can also be used, and examples of the double bond group in this polymer include the same groups as described above. In the polymerization reaction between the polymers, it is also a commonly known method to carry out the reaction in combination with the above-mentioned polymerizable polyfunctional monomer.

Furthermore, in the case of forming a chemical bond and bridging the polymers by the reaction of the reactive groups between the polymers in the method (3) above, it is carried out in the same manner as the reaction of ordinary organic low-molecular compounds. be able to. Specifically, it is described in detail in the apparatuses of Yoshiyu Iwakura, Keisuke Kurita, "Reactive Polymers", Kodansha (published in 1977), Ryohei Oda, "Polymer Fine Chemicals", Kodansha (published in 1978), etc. For example, polymer reactions involving combinations of functional groups in Group A (hydrophilic group polymer components) and Group B (polymers containing components containing reactive groups) in the table below are usually well known. This is one of the methods.

Table 1 As described above, the network hydrophilic resin particles of the present invention are particles of a polymer containing a polymer component containing a hydrophilic group and having a structure in which molecular chains are highly cross-linked. Yes, e.g. L, Il, Sperling, rlntre-p
eneLrating Polymer Nature
ks and Re1ated Ma-terials
J P1enu+n Press (published in 1981)
, rBncyc-1opedia of Polym
e'r 5science and Bngneerin
g” vol 8 P 279 ~ 340 (
(1985) 1.1. Mouth, Anclrade.

rHyclyogels for medical
oandRe1atedApplic-ati
on J, ^C3, Symposium
5eries No.31. ^mer-ican
Chemical 5ociety, Washi
ngton Ro, C. (1976), Eizo Omori, “
``Development trends of super absorbent resins and their application development'', Technoforum Co., Ltd. Publishing Department (published in 1987), Masarai Irie, ``Manufacture and application of functional polymer gels'', CMC Co., Ltd. (1987).
(published in 1987), Kenji Tanaka, Petrotech, 1
025 (1987), N1kkei New Ma
terials June 1, 1987 issue, p57. Kushi Taguchi, Kunio Ishii, “Science and Industry” 59°188 (19
85), Fusayoshi Masuda, Functional Materials April 1982 issue p36
．． Mon @ Yoshinori, Chemical Industry 3H゜602 (1987)
Hydrogels or super absorbent resins described in et al. can be used. Examples of commercially available superabsorbent resins include Arasorb (manufactured by Arayo Kagaku Kogyo Co., Ltd.), Wonder Gel (manufactured by Kao Corporation), KI Gel (manufactured by Kuraray Soprene Co., Ltd.), Sunwet (manufactured by Sanyo Kasei Kogyo Co., Ltd.!1), and Sumikagel (manufactured by Kuraray Soprene Co., Ltd.). Aqua Keep (manufactured by Seitetsu Kagaku Kogyo Co., Ltd.), Lanseal (manufactured by Japan Exlan Kogyo Co., Ltd.), Lion Polymer (manufactured by Nippon Exlan Kogyo Co., Ltd.)
(manufactured by Lion Co., Ltd.), GP (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.),
Aqualic (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.), Aquabrene (Meisei Kagaku Kogyo Co., Ltd.!1II), CL D (Buck
eye (manufactured by Cellulose), 0. W.

^, L (mouth ow Chemical company!!!
> , G, P, f':, (Graim Proc
Made by essing>, Aqualon (Ile
rcules), Magic Water Get
(manufactured by Super Absorbent), Ce
cagum (manufactured by CBCA), Spon Zygnus (manufactured by Kanebo Synthetic Chemical Co., Ltd.), Super Love (manufactured by Asahi Kasei Industries, Ltd.)
etc.

Further, the granulation of the network hydrophilic resin in the present invention is the same as the granulation of the hydrophilic resin described above.

Next, the binding sesame used in combination with the above hydrophilic resin particles or mesh hydrophilic resin particles will be explained.

The binder resin used in the present invention is a resin CA) containing the polar group and having a weight average molecular weight of 20,000 or less.

Preferably, the weight average molecular weight of the resin [A] is 3X10
3 to 1x104, and the proportion of the copolymer component containing the polar group is preferably 1 to 10% by weight.

Conventional acidic group-containing binder resins as described above are mainly used for offset masters, and their molecular weights are large (for example, 5.
XlO' 2).

On the other hand, in the present invention, since the polar group contained in the binder resin [A] is adsorbed to the stoichiometric defects of the photoconductive zinc oxide and is a low molecular weight substance, Improving the surface coverage of photoconductive zinc oxide compensates for trapping of photoconductive zinc oxide and improves humidity characteristics, while ensuring sufficient dispersion of photoconductive zinc oxide and suppressing agglomeration. I found out something.

Therefore, the surface smoothness of the photoconductive zinc oxide becomes smooth.

On the other hand, when a photoreceptor with a rough surface of the photoconductive layer is used as an original plate for electrophotographic planographic printing, the dispersion state of the photoconductive zinc oxide particles, the above-mentioned hydrophilic resin particles, and the binder resin may not be appropriate. Since the photoconductive layer is formed in the presence of aggregates, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image area cannot be made uniformly and sufficiently hydrophilic, and the printing ink may not be sufficiently hydrophilized during printing. This causes adhesion, resulting in background smudges in non-image areas of printed matter.

On the other hand, due to the lower molecular weight of the binder resin [A] according to the present invention, there was a concern that the strength of the film would become weaker. It was found that sufficient film strength was maintained.

When the molecular weight of the binder resin [A] is less than 103, the film forming ability decreases and sufficient film strength cannot be maintained. On the other hand, if the molecular weight is greater than 2×10 4 , electrophotographic properties (especially initial potential and dark decay retention) deteriorate, which is not preferable. Particularly in the case of such a polymer, if the content of polar groups exceeds 3%, the electrophotographic properties deteriorate significantly, and when used as an offset master, background smudge becomes noticeable.

If the amount of the polar group-containing component in the binder resin [A] is less than 0.5% by weight, the initial ii position will be low and sufficient image density will not be obtained. On the other hand, if the amount of the polar group-containing component is more than 20% by weight, the dispersibility will be lowered, the film smoothness and high-humidity electrophotographic properties will be lowered, and furthermore, background smear will occur when used as an offset master. increase

The glass transition point of the resin (A) is preferably in the range of -10°C to 100°C, more preferably in the range of -5°C to 80°C.
It is.

Further, among the polar groups of the resin [A], in the -P-OR group, R is more specifically, for example, an optionally substituted alkyl group having 1 to 12 carbon atoms (for example, 1 to 12 carbon atoms).
f-methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, etc.) , an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group, chloropentyl group, methoxybenzyl group, methylbenzyl group, etc.), a substituted aralkyl group having 5 to 8 carbon atoms alicyclic groups (e.g. cyclopentyl group,
cyclohexyl group, etc.) or an optionally substituted aryl group (eg, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, clophenyl group, methoxyphenyl group).

In the present invention, the resin [A] may be any conventionally known resin as long as it has the physical properties described above, such as polyester resin, modified epoxy resin, silicone resin, olefin copolymer, polycarbonate resin, vinyl alkanoate resin. , allyl alkanoate resin, modified polyamide resin, phenol resin, fatty acid modified silkyto resin, acrylic resin and the like.

More specifically, as an example of the resin of the present invention, a (meth)acrylic copolymer containing a total amount of 30% by weight or more of a monomer represented by the following general formula (VIT) as a copolymer component can be mentioned.

General formula (■) CIl□-C COO-R' In the general formula (■), X represents a hydrogen atom, a halogen atom (e.g. chloro atom, bromo atom), a cyano group, or an alkyl group having 1 to 4 carbon atoms. .

R' is an optionally substituted alkyl group having 1 to 18 carbon atoms,
dodecyl group, tridecyl group, tetradecyl group, 2-methoxyethyl group, 2-ethoxyethyl group, etc.), carbon number 2~
18 optionally substituted alkenyl groups (e.g. vinyl group, allyl group, impropenyl group, butenyl group, hexenyl group, heptenyl group, octenyl group, etc.), carbon number 7 to 1
2 optionally substituted aralkyl groups (e.g. benzyl group, phenethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), optionally substituted cycloalkyl groups having 5 to 8 carbon atoms (e.g. cyclopentyl group,
cyclohenidosyl group, cycloheptyl group, etc.), aryl group (e.g. phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, me)-1-diphenyl group, ethoxyphenyl group, clophenyl group, dichlorophenyl M, etc.)
fit)t.

The [copolymer component containing a polar group] of the present invention may be any vinyl compound containing a polar group that can be copolymerized with the general formula (■). Molecular Data Handbook [Basic Edition]” Baifukan (
(1986) and others. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-amino)methyl form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α
, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-monopendenoic acid, 2-methyl-2-hexenoic acid) , 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid , vinyl sulfonic acid, vinylphosphonic acid, half ester derivatives of vinyl or allyl groups of dicarboxylic acids, and compounds containing the polar group in the substituent of Nisder derivatives and amide derivatives of these carboxylic acids or sulfonic acids. It will be done.

Furthermore, the resin [A] of the present invention contains the monomer of the general formula (■) described above and the monomer containing the polar No. 1 (), as well as other TV sliders other than these as copolymerization components. You may.

Examples: Eva, α-olefins, vinyl alkanoates or allyl esters n1, acrylonitrile, methacrylnitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g. vinylpyrrolidone, vinylpyridine, vinylimidacillin) le,
vinylthiophene, vinylimidacillin, vinylpyrazole, vinyldioxane, vinylkyrin, vinylthiazol, vinyloxazine, etc.). In particular, vinyl acetate, allyl acetate, acrylonitrile, methacrylonitrile, styrenes, etc. are preferred components from the viewpoint of film strength.

In addition, the previous resin [CB] does not impede the high performance of electrophotographic properties obtained by using the above resin [A], and improves the mechanical strength of the photoconductive layer, which is insufficient with resin [A] alone. It is sufficient.

The resin (B) is moderately crosslinked, and since the resin [B'] is a copolymer with a polar group bonded only to one end of the main chain, the interaction between the polymer chains and the polar group It is thought that the weak interaction between the photoconductive particles and the photoconductive particles acts synergistically, resulting in significantly improved performance in terms of electrophotographic properties and film strength.

On the other hand, if the resin [B] contains acidic groups similar to those shown in the resin [A], the dispersion of the photoconductor is destroyed, and aggregates or precipitates are formed, or even if a coating film is formed. This is also undesirable because the electrostatic properties of the resulting photoconductor are significantly reduced, the surface smoothness of the photoreceptor becomes rough, and the strength against mechanical abrasion is deteriorated.

Resin [B] is a polymer containing at least one type of repeating unit represented by general formula [1], and a part of the polymer is crosslinked ff [average molecular weight is 5 × 104 or more, and more Preferably weight average molecular weight 8X103 to 6Xl
It is O'.

The glass transition point of the resin CB is preferably 0°C to 120°C.
, more preferably from lO<0>C to 95<0>C.

When the weight average molecular weight of the resin [B] is less than 5×10 3 , the film strength becomes insufficient. Furthermore, if the weight average molecular weight of the resin [B] exceeds the above-mentioned preferred upper limit, it is not preferable because it has almost no solubility in organic solvents and cannot be used in practice.

The resin [B] of the present invention satisfies the above-mentioned physical properties, a part of the polymer is crosslinked, and the polymer component selected from the reversible units represented by the general formula [■] is a homopolymer. A polymer or copolymer contained as a component or as a copolymer component obtained by copolymerizing with another monomer that can be copolymerized with a monomer corresponding to a repeating unit represented by the general formula [111] described below. It is a polymer.

The hydrocarbon group on the repeating unit represented by the general formula [■] may be substituted.

In general 2N), T is preferably -C00--oc
o-, -C) 1.0CO-1-CIl, C00- or -
represents low, more preferably -COD-, -[:11
．． Represents C00- or -0-.

(2) preferably represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. The substituent may be any substituent other than the polar group bonded to one end of the polymer main chain as described below, such as halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -〇- v, -coo
-v2, -11cO-V, , (V.

~V represents an alkyl group having 6 to 22 carbon atoms, and includes substituents such as hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, etc. A preferable hydrocarbon group has 1 to 1 carbon atoms.
18 optionally substituted alkyl groups (e.g. methyl group,
Ethyl group, propyl group, butyl group, 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 -bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (e.g., 2-methyl-l-propenyl group, 2-butenyl group, 2-pentenyl group, 3≧methyl-2-pentenyl group, -pentenyl group, 1-hexenyl group, 2-h-4-t==l 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, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group), An optionally substituted alicyclic group having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexyl ethyl group, 2-cyclopentylethyl M, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms ( For example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butylphenyl group, decyloxyphenyl group, chlorophenyl group, Dichlorophenyl group, bromophenyl group, cyanophenyl group,
acetylphenyl group, methoxycarbonylphenyl group,
(ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

at and a2 may be the same or different, and are preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, -coo-z or -C112COOZ (Z preferably represents an aliphatic group having 1 to 22 carbon atoms). More preferably, al+12 may be the same or different from each other, and are hydrogen atoms, alkyl groups having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), -cn
oz or -C112COD-Z (Z is more preferably a C1-18 ゛f alkyl group represents an alkenyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, Decyl group, dodecyl group,
Examples include tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups may have the same substituents as shown in V above. good).

In resin [B], a commonly known method can be used to introduce a crosslinked structure into the polymer. That is, there are two methods: a method in which a polyfunctional monomer is coexisting in the polymerization reaction of monomers, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction.

The resin [B] of the present invention has a simple manufacturing method (for example, it requires a long reaction time, the reaction is not quantitative, and there are few problems such as contamination of impurities due to the use of reaction accelerators, etc.). , the functional group that undergoes a self-crosslinking reaction N+
Cross-linking reactions using 1 CH20R0 (Re represents a hydrogen atom or an alkyl group) or polymerization are effective.

In the case of a polymerization-reactive group, the polymerizable functional group is preferably 2
A method of bridging the polymer matrix by polymerizing a monomer having at least 1 or more monomers together with the monomer of formula [1] described above is preferred.

Specifically, the polymerizable functional group is CH□=CH-CL=CLCL-C)+2=CIl-CH-C-0-C
112-C) 1-CH2-N11CO-1C112=l
l? 1l-3O2-, CI+2=CH-CD-1C11
,=CI+-0-, CH2=Cll-3~, etc., but monomers having two or more of the above polymerizable functional groups may have the same or different polymerizable functional groups. Any monomer having two or more of these may be used.

Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene Glyfur, diethylene glycol, triethylene glycol, polyethylene glycol #200, #400, #600.1.3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives):
Vinyl Nisdels, allyl esters, vinylamides or allylamides of dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.): polyamines (e.g. ethylenediamine, .3-propylene diamine, 1.4
-butylenediamine, etc.) and a carboxylic acid containing a vinyl group (eg, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

In addition, as monomers having different polymerizable functional groups, for example, carboxylic acids containing vinyl groups (such as methacrylic acid,
Acrylic acid, methacryloyl acetic acid, acryloyl acetic acid,
Methacryloylpropionic acid, acryloylpropionic acid, itaconyloyl acetic acid, itaconyloylpropionic acid, reactant of carboxylic acid anhydride and alcohol or amine (
For example, vinyl group-containing ester derivatives or amide derivatives (such as allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminoerbonylpropionic acid, etc.)
For example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate,
Allyl itaconate, Vinyl methacryloyl acetate, Vinyl methacryloyl propionate, Allyl methacryloyl propionate, Vinyloxycarbonyl methyl methacrylate, Vinyloxyerbonyl acrylate methyloxycarbonyl ethylene ester, N-allyl acrylamide, N-allyl methacrylamide, N - allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.) or amino alcohols (e.g. aminoethanol, 1-aminopropanol, l-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.)
and a condensate of carboxylic acid containing a vinyl group.

In the present invention, the partially crosslinked resin [B] of the present invention is obtained by polymerizing a monomer having two or more of these polymerizable functional groups in an amount of 20% by weight or less of the total monomers. Jl
can be achieved. More preferably, the monomer is not more than 15% by weight in the case of resin [B'] synthesized by the method of introducing a polar group at the terminal with a chain transfer agent described below, and not more than 5% by weight in other cases. It is preferable that

On the other hand, if the resin [B] does not contain a terminal polar group (not the resin [B'] described below), a resin containing a crosslinkable functional group that causes a curing reaction with heat and/or light is used. CB] may form a crosslinked structure.

The functional group may be any functional group as long as it can cause a chemical reaction between molecules and form a chemical bond. That is, it is possible to use a reaction mode in which bonding between molecules by condensation reaction, addition reaction, etc. or crosslinking by polymerization reaction is caused by heat and/or light.

Specifically, a functional group having a dissociable hydrogen atom (for example, -COH group, -PO3112 group, -P-OR, (R1 is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms)
alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl groups having 7 to 11 carbon atoms (e.g. benzyl group, phenethyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group, etc.) ) or an aryl group having 6 to 12 carbon atoms (e.g. phenyl group, tolyl group, xylyl group, mesitylene group, chlorophenyl group, ethylphenyl group, methoxyphenyl group, naphthyl group, etc.) or -OR, group (I12 is represented by R+) ), -OH group, -5
H group, -NH-R3 group (R is a hydrogen atom or a carbon number such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.)
4)] and /mouth\ /S\ -CL-CH, -CII2 C1l, -NCO, -N
When containing at least one combination of functional groups each selected from the group with C3, or -CONIICI+2
111. (R is a hydrogen atom, a methyl group, an ethyl group,
Examples include cases containing an alkyl group having 1 to 6 carbon atoms such as a butyl group, a butyl group, a hexyl group, etc.) or a polymerizable double bond.

Specific examples of the polymerizable double bond group include those mentioned above as specific examples of the polymerizable functional group.

Furthermore, for example, Tsuyoshi Endo [Refinement of thermosetting polymers (C
, M, C■, 1986), Yuji Harasaki, "Latest Binder Technology Handbook" Chapter n- (Sogo Technological Center, 1985)
(published in 1985), accompanied by Otsu, "Synthesis, design and development of new uses for acrylic resins" (Chubu Business Development Center Publishing Department, published in 1985), Eizo Omori "Functional acrylic resins" (Technosystem, published in 1985), Hideo Inui, Nagamatsu Gentabe "Photosensitive Polymers" (Kodansha, 1977), Kaku 10 Takahiro "New Photosensitive Resins" (Printing Society Publishing Department, 1981), G.
,E.

Green and Ro, P, 5Lar R, J
, Macro, Sci Revs 1acro.

Chem,, C21 (2>, 187-273 (1
981-82), C.G., Roffey,
I"Photopolymerization of S
surface coatingsJ (A, Wiley
Interscienca Pub.

(1982), etc., can be used.

These crosslinkable functional groups may be contained in one copolymer component, or may be contained in separate copolymer components to carry out the crosslinking reaction.

Specific examples of the monomer corresponding to the copolymer component containing these crosslinkable functional groups include, for example, general formula CI
Examples include vinyl compounds containing the functional group that can be copolymerized with the monomer.

For example, see the Polymer Data Handbook by the Society of Polymer Science m.
Basic Edition] Baifukan (published in 1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2-dimethyl) form, α-chloro form, α-bromo form, α -fluoro form, α-tributylsilyl form, α-
Cyano form, β-chloro form, β-bromo form, α-chloro-
β-methoxy form, α, β-dichloro form, 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-octene etc.>, maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenylboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, vinyl group or allyl group of dicarboxylic acids Examples include half ester derivatives of , ester derivatives of these carboxylic acids or sulfonic acids, and compounds having the crosslinkable functional group in a substituent of an amide derivative.

The proportion of the above-mentioned "copolymer component containing a crosslinkable functional group" in the resin [B) of the present invention is preferably 1 to 80% by weight/h1% in the resin [B]. More preferably 5 to 50
Weight%.

When producing such a resin [BE, a reaction accelerator may be added, if necessary, in order to promote the crosslinking reaction. For example, acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), peroxides,
Examples include azobis compounds, crosslinking agents, sensitizers, photopolymerizable monomers, and the like.

Specifically, as the crosslinking agent, it is possible to use the same crosslinking agent as that used in the production of the network hydrophilic resin particles having the above-mentioned high-order network structure.

When containing a photocrosslinking-reactive functional group, the compounds cited in the above-mentioned review of photosensitive resins can be used.

In addition, the resin CB] includes a monomer corresponding to the repeating unit represented by the general formula CI) and the polyfunctional monomer described above, as well as other monomers other than these (for example, the resin (A
, ) may be contained as a copolymerization component.

As described above, the resin [B] of the present invention is characterized by having a crosslinked structure in at least a part of the polymer, and further includes a photoconductive layer forming periphery containing at least an inorganic photoconductor and the binder resin. It is necessary for the material to be soluble in the organic solvent during preparation. Specifically, for example, toluene solvent 10
Any solvent that can dissolve at least 5 parts by weight of the resin (BE) at a temperature of 25°C with respect to 0 parts by weight may be used.Solvents for these coatings include halogens such as dichloromethane, dichloroethane, chloroform, methylchloroform, and trichlene. Hydrocarbons, alcohols such as methanol, ethanol, propatool, butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethers such as tetrahydrofuran and cytoxane,
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate,
These include esters such as methyl propionate, glycol ethers such as ethylene glycol monomethyl ether and 2-methoxyethyl acetate, and aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, which may be used alone or in combination. can be used.

In the present invention, in addition to resin (A] and resin CB] (including resin CB')), other resins can also be used in combination. Examples of such resins include Arnot resin, polybutyral resin, polyolefins, ethylene divinyl acetate copolymer,
Examples include styrene resin, styrene-butadiene resin, acrylate butadiene resin, vinyl alkanoate resin, and the like.

If the other resins mentioned above exceed 30% (weight ratio) of the total binder resin amount using resins [A] and [B] of the present invention, the effects of the present invention (especially improvement of electrostatic properties) will be lost. .

The ratio of resin (A) and resin [B] used in the present invention varies depending on the particle size and surface condition of the photoconductive zinc oxide used, but in general, the ratio of resin [A] and resin [B] used is The ratio is 5 to 80 to 95 to 20 (weight ratio), preferably 15 to 60 to 85 to 40 (weight ratio).

Furthermore, when the aforementioned resin [A] is a resin containing a copolymer component (i) corresponding to one repeating unit represented by the above formula (III or formula (III)), the presence of the copolymer component The proportion is 30% by weight or more, preferably 50 to 97% by weight, and the above-mentioned polar group-containing copolymer component (i
In the case of the resin containing i), the proportion of the copolymer component (11) is 0.5 to 20% by weight, preferably 1 to 10% by weight.

In formula [III, preferred X and X are hydrogen, chlorine, and bromine atoms, respectively, and preferred hydrocarbon groups include alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (e.g. evahensyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group,
dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, etc.), aryl group (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group) groups, etc.), and -c
oy, and -COOY2 (preferred Yl and Y2 include those described above as preferred hydrocarbon groups). However, x
Both l and x2 do not represent hydrogen atoms.

In formula [■], Il is a direct bond or -←C112→n (n represents an integer of 1 to 3), -C1l-C1l*C0, which connects -CD rho and a benzene ring.
-1 gate CH2O7 (m represents an integer of l or 2),
Represents a linking group having 1 to 4 linking atoms such as -C11, CH, 0-, etc.

Stomach in formula [III) represents the same content as L.

Specific examples of the repeating unit (i) represented by formula [1) or [III] used in the present invention are listed below. However, the scope of the present invention is not limited thereto.

C11゜ i-3) i-4) CH.

” i-6) i-7) ! i-H) i-14) i-15) i-16) [:l+.

CII 2 C, It S C1[.

i-10) C11゜ i-11) C.I. C11゜ C.I.

amount CH3 C11゜ i-19) CH.

120) CH.

1 L υr CH3 113 C11゜ C11゜ C1(.

C11゜ l ! C11゜ C1+3 126) C11゜ heat r i-23> L i-27) C11゜ ■ I i-24) CH3 i-28) C) 1° =29) C11゜ C11゜ C11゜ -fcL-C→ Otori C11゜ , -(-C1,-[:→ ! i-35) CH.

i-36) C11゜ amount -f CH.

C→ ShiUUL: t13 ShiI r 1r i -37) C11゜Also, the resin "A" is [repeating unit containing a polar group (ii
) J, preferred acidic groups are -P03H2 group, i
-3H) CH3 i~39) C11゜i~40) CH.

ShiUULII3 It is a containing group.

-P-OH group, R is a hydrocarbon group or OR'OR
'(R' represents a hydrocarbon group), and R and R' are preferably aliphatic groups having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, Decyl group, dodecyl group, octadecyl group, 2-
Chloroethyl group, 2-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 a substituted aryl group (e.g. phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophyll group, fluorophenyl group, bromophenyl group, chloro-
methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, fluorophenyl group, butoxyphenyl group, etc.).

In addition, 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 acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic dicarboxylic acid anhydrides include succinic acid anhydride ring ζ glutaconic acid anhydride ring, maleic acid anhydride ring, cyclobencune-1,2-dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride ring Examples include acid anhydride, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-bicyclo[2,2゜2]octanedicarboxylic anhydride, and these rings contain, for example, a chlorine atom, A halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group, etc. may be substituted.

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

The copolymerization component corresponding to the "repeating unit containing a polar group (ii)" of the present invention is, for example, the formula [■] or the formula (II [
) may be any vinyl compound containing the polar group that can be copolymerized with the methicrylate monomer corresponding to the repeating unit represented by M edition] Baifukan (1986), etc.

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α
-(2-amino)methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β- Methoxy form, α.

β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amide neck, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, -octenoic acid, 4
-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid Examples include half-ester derivatives of vinyl or allyl groups of acids and dicarboxylic acids, and compounds containing the acidic group in the substituent of these carboxylic or sulfonic acid ester derivatives and amide derivatives.

The "polar group-containing repeating unit (ii)" will be exemplified.

1i-1) -fc11. -C→ C00lI BL: 11° CL( below, same) ii-2) C113 →C) I-CH-+ 0OII if-3) ii-4) b.

-(-C112-C→ Iwao COD (Cll 2) ,,C00IIo:2~11
An integer of

-f CH2-C→ 0OII(CH2)I, COO11 0: Integer from 2 to 11 C00(CH2)20CO(C112) ,,CDDH
b2=H, CH, , -CH, C00CI1. (below,
Same) n = integer from 1 to 3 COD (Cll, ), SO, l+ n = integer from 2 to 4 C00 (Cll2) 20COCH-C11-COOHC
H.

SO3 has CIl ) fcH2-cH→- C112COD It amount C0NII (CI+2) 2Sn, integer R from 112 to IO m: integer R from 2 to IO: C, ~6 alkyl group, benzyl group, phenyl group, and furthermore, resin [B] As a preferred embodiment, the general formula [■]
A polymer containing at least one type of repeating unit represented by, which is partially crosslinked, and which has -PO,H, group, -3O,H group, - at one end of at least one main chain.
COOH group, -old 1 group, -3l+ group, -P-OH group OR
'(R' indicates a hydrocarbon group, more specifically indicates the same as R above), a cyclic acid anhydride-containing group (specifically, as described in component (ii) of resin [A] (b+, b2 may be the same or different and represent a hydrogen atom or a hydrocarbon group), and preferably have a weight average molecular weight of 5 x 104 or more. Polymers (hereinafter referred to as resins [B']) having a weight average molecular weight of 8 x 104 to 6 x 10 s can be mentioned.

The glass transition point of the resin [B'] is preferably 0°C to 120°C.
℃ range, more preferably 10℃ to 95℃. b,
Specific examples of and b2 include hydrogen atoms as well as carbon atoms with 1 to 1 carbon atoms.
10 optionally substituted aliphatic groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-cyanoethyl group, 2-chloroethyl group, 2-ethoxycarbonylethyl group, benzyl group, phenethyl group) basis,
chlorobenzyl group, etc.), optionally substituted aryl groups (eg, phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, cyanophenyl group, etc.).

Further, preferable terminal polar groups are -1'0dlz group, -C
00H group, -80,11 group, -Go, -811 group, -P
-011 group, OR' -CONI+2 group and -5O2Ni12 group.

The specific polar group bonded to only one end of the polymer main chain has a chemical structure in which it is bonded directly to one end of the polymer main chain or via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, diagonal atoms, nitrogen atoms, and silicon atoms).
, z, which is composed of any combination of atomic groups of heteroatom-heteroatom bonds. For example, fC-)-[R11,R,2 is hydrogen pressure R, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g. methyl group, ethyl group, Propyl group, etc.)
, fC) I=CI+, I3 11R13 R11 -N11COO-1-Nl-1[:0NH-1-3i-
In Niko, Ls is a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, phenyl group, tolyl group, etc.) or -〇R,4(R,, is R1
(represents the same content as the hydrocarbon group in 1)], etc.

The resin CB of the present invention, which has a specific polar group bonded only to at least one end of the polymer main chain, can be obtained by reacting various reagents to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or the above-mentioned ionic polymerization method. It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a legal or radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss, RlP, 0ui
rk, Bncycl.

Polym, Sci, Bng, 7; 551 (
19, 87), Yoshiki Nakajo, Yuya Yamashita "Dye and Medicine",
30.232 (1985), Akira Ueda and Susumu Nagai, "Science and Industry" 60.57 (1986), and other reviews and documents cited therein.

Specifically, the polymer of the resin [B'] used in the present invention includes monotooth bodies corresponding to the repeating units represented by the general formula [■], and polyfunctional monomers for forming the above-mentioned crosslinked structure. A polymerization initiator (for example, an azobis compound,
peroxide, etc.), or polymerization using a polymerization initiator containing the polar group without using the above chain transfer agent, or a method in which the chain transfer agent and the polymerization initiator contain the polar group. A method using a compound containing a group, and furthermore, in the above three methods, a compound containing an amino group, a halogen atom, an epoxy group, an acid halide group, etc. is used as a substituent of the chain transfer agent or polymerization initiator. After the polymerization reaction, the polar group can be produced by further reacting with these functional groups in a polymer reaction to introduce the polar group. Examples of the chain transfer agent used include mercapto compounds containing the polar group or a substituent derived from the polar group (e.g., thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid,
-Mercaptopropionic acid, 3-mercaptoacetic acid, N-
(2-mercaptopropionyl)glycine, 2-mercaptonicotine'f/I, 3-CN (2-mercaptoethyl)carbamoyl]propionic acid, 3-CN-(
2-Mercaptoethyl)aminocopropionic acid, N-(
3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1°2-propanediol, 1-mercapto-2-propane tool, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or iodized alkyl compounds containing the above polar groups or substituents (e.g., iodoacetic acid, (iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 1 to 10 parts by weight.

In the present invention, various dyes can be used in combination as spectral sensitizers, if necessary. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (No. 8) p. 12, C.
, J. Young et al.: RCA Revie 15
, 469 (1954), Wataru Kiyota: Telecommunications Journal J63-C (No.

2) 97 (1980), Yuji Harasaki et al., Industrial Chemistry Journal 66, 78, and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 35.208 (1972), etc., carbonium dyes, diphenylmethane dyes, and triphenyl Methane pigments, xanthine pigments, phthalein pigments,
Polymethine colors 1 (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like can be mentioned.

More specifically, examples using mainly carbonium dyes, triphenylmethane dyes, bovine santhene dyes, and phthalein dyes include Japanese Patent Publication Nos. 51-452, 50-90334, and 50-50. -114227, same 5
No. 3-39130, No. 53-82353, U.S. Pat. No. 3,052,540, U.S. Pat.
-16456 etc. are mentioned.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as rhodacyanine dyes include F, M
, Hammer, rThe Cyanine Dy
es andRelated Compounds J
It is possible to use the pigments described in et al., and more specifically,
U.S. Patent No. 30473H4, U.S. Patent No. 3110591,
Same No. 3121008, Same No. 3125447, Same No. 3
No. 128179, No. 3132942, No. 3622
317, British Patent No. 1226892, British Patent No. 1309
No. 274, No. 1405898, Special Publication No. 1978-781
Examples include dyes described in No. 4, No. 55-18892, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
No. 47-44180, Japanese Patent Publication No. 51-41061, Japanese Patent Publication No. 49-5034, Japanese Patent Publication No. 49-45122, Japanese Patent Publication No. 57-46245, Japanese Patent Publication No. 56-35141, Japanese Patent Publication No. 57-
No. 157254, No. 61-26044, No. 61-27
551, U.S. Patent No. 361954, U.S. Patent No. 41759
No. 56, r Re5earch 1 closure
J 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 aforementioned Imaging 1973 (No.
8) Electron-accepting compounds (e.g. halogens, benzoquinone, cranyl, acid anhydrides, organic carboxylic acids, etc.) cited on page 12, Hiroshi Komon et al., "Recent development and practical application of photoconductive materials and photoreceptors" Chapters 4 to 6 2 Japanese Science Information - Publishing Department (1
986), the cited polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, etc.

The amount of these various additives added is not particularly limited, but usually o, ooot to 100 parts by weight of photoconductive zinc oxide.
~2.0 parts by weight.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

Further, when a photoconductive layer is used as a charge generation layer in a laminated structure consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.
01-1μ, particularly 0.05-0.5μ is suitable.

In some cases, an insulating layer is added mainly for the purpose of protecting the photoreceptor, improving its durability, dark decay characteristics, etc.

At this time, the insulating layer is set to be relatively thin, and when the photoreceptor is used for a specific electrophotographic process, the insulating layer provided is set to be relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70μ, in particular 1
It is set to 0 to 50μ.

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

Typical resins used to form the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl oxide copolymer resin, Thermoplastic resins and curable resins such as polyacrylic resins, polyolefin resins, urethane resins, polyester resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photoconductive layer is preferably electrically conductive, and the electrically conductive support can be made by impregnating a low-resistance substance with a base material such as metal, paper, or plastic sheet, just as conventionally. Those that have been subjected to conductive treatment such as coating, those that have been coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photoconductive layer is provided) and further preventing curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. Supports with a water-resistant adhesive layer on the surface, at least one pre-coat layer if necessary, and paper laminated with a conductive plastic base coated with AI or the like can be used. .

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (No. 1), No. 2-11
Page (1975), Hiroyuki Moriga, "Introductory Chemistry of Special Papers", Kobunshi Publishing Association (1975), M, F, Ho.

var, J, lJacromol, Sci, Chem
, A-4(6), pages 1327-1417 (1970), etc. are used.

Known methods can be applied to produce a lithographic printing plate using the electrophotographic lithographic printing original plate of the present invention described above. That is,
It is charged substantially uniformly in the dark and forms an electrostatic latent image upon imagewise exposure. The exposure method is semiconductor laser, tl
Examples include scanning exposure using an e-N e laser, reflection image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, etc. as a light source, and contact exposure using a transparent positive film.

Next, the electrostatic latent image is developed with toner. As the developing method, various conventionally known methods such as cascade development, magnetic brush development, powder cloud development, and liquid development can be used.

Among these, liquid development is capable of forming fine images and is suitable for producing printing plates.

The formed toner image can be fixed by a known fixing method, such as heat fixing, pressure fixing, solvent fixing, or the like.

The printing plate having the toner image formed in this manner is then subjected to a hydrophilic treatment for non-image areas by a conventional method. A so-called desensitizing treatment liquid is usually used for the hydrophilic treatment.

Conventionally, this type of desensitizing treatment liquid includes ferrocyanate, cyanide compound-containing treatment liquid containing ferricyanate as the main component, cyanide-free treatment containing ammine cobalt complex, phytic acid and its derivatives, and guanidine derivative as main component. Treatment liquids containing inorganic or organic acids as main components that form chelates with zinc ions, and treatment liquids containing water-soluble polymers are known.

For example, as a cyanide-containing treatment liquid,
No. 9045, No. 46-39403, JP-A-52-76
No. 101, No. 57-107889, No. 54-1172
Examples include those described in No. 01.

As a treatment liquid containing a phytic acid compound, JP-A-53-
No. 83H07, No. 53-83H05, No. 53-102
Examples include those described in No. 102, No. 53-109701, No. 127003, No. 54-2803, No. 54-44901, and the like.

As a treatment liquid containing a metal complex compound such as a cobalt complex, JP-A-53-10. '1301, 53-14010
No. 3, No. 54-18304, Special Publication No. 43-28404
Examples include those listed in the No.

As a treatment liquid containing an inorganic or organic acid, Japanese Patent Publication No. 39-13
No. 702, No. 40-10308, No. 43-28408
No. 40-26124, JP-A-51-118501
Examples include those listed in the No.

As a treatment liquid containing a guanidine compound, JP-A-58-1
Examples include those described in No. 11695 and the like.

As a treatment liquid containing a water-soluble polymer, JP-A-52-1
No. 26302, No. 52-134501, No. 53-49
No. 506, No. 53-59502, No. 53-10430
No. 2, Japanese Patent Publication No. 3H-9665, No. 39-22263, No. 40-763, No. 40-2202, Japanese Unexamined Patent Publication No. 49/1973
-36402 etc. are mentioned.

In any of the desensitizing solutions mentioned above, zinc oxide in the surface layer, which is the photoconductive layer, is ionized to become zinc ions, and these ions are chelated with the chelate-forming compound in the desensitizing solution. It is believed that a reaction occurs to form a zinc chelate, which is deposited in the surface layer and becomes hydrophilic.

Therefore, the printing original plate of the present invention becomes a printable printing plate by performing desensitization treatment using a desensitization treatment liquid.

(Example) Production Example 1 of Resin Particles A mixed solution of 95 g of dodecyl methacrylate, 5 g of acrylic acid, and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. This is followed by 2,2-azobis(isobutyronitrile) (abbreviations A, I, B).

1.5 g of N, ) was added and reacted for 8 hours. To this reaction mixture solution, 12 g of glycidyl methacrylate, 1 g of t-butylhydroquinone, and 0.8 g of N,N-dimethyldodecylamine were added, and the mixture was reacted at 100° C. for 15 hours (dispersed resin α).

Next, 7.5 g of the above dispersion resin α (as solid content), 2
A mixed solution of 50 g of -hydroxyethyl methacrylate and 200 g of n-hebutane was heated to 65° C. with stirring under a nitrogen stream. To this, 0.7 g of 2.2-azobis(isovaleronitrile) (abbreviation A, 1.V, N,)
was added and reacted for 6 hours.

20 minutes after addition of initiator (^, 1. V, N, ) -
The solution began to become cloudy and the reaction temperature rose to 90°C. After cooling, it was passed through a 200 mesh nylon cloth to obtain a white dispersion. The latex had an average particle diameter of 0.19 μm.

Production example 2 of resin particles 2-phosphonoethyl methacrylate 50g 1 dispersion resin α
A mixed solution of 8 g (as solid content), 150 g of ethyl acetate, and 150 g of n-hexane was heated to 55° C. with stirring under a nitrogen stream. A.I.

0.5 g of V and N were added and reacted for 4 hours to obtain a white dispersion. After cooling, pass it through a 200 mesh nylon cloth.
The resulting dispersion was a latex with an average particle size of 0.45 μm.

Production Example 3 of Resin Particles The reaction was carried out in the same manner as Production Example 1, except that a mixed solution of 50 g of N-vinylpyrrolidone, 1 Og of dispersed resin (as solid content), and 200 g of toluene was used, and the average particle size was 0.30.
A white latex of μm was obtained.

Production example 4 of resin particles: 31.5 g of ethylene glycol, 51.8 g of phthalic anhydride
g, methacrylic acid 6.0g, )lichloroethylene 10g
, p-) A mixture of 20.7 g of luenesulfone was heated and reacted for 6 hours. The reaction temperature was set to start at 107°C and rise to 150°C in 6 hours (water by-produced by the reaction was removed by the Dean-3 tark method).

Next, 6 g of methacrylic acid, 76 g of chloroform, 11.6 g of ethanol, and the dispersion resin β obtained in the above reaction were added.
5.8 g (as solid content) of the mixed solution was refluxed under a nitrogen stream. To this, A, 1. 0.8 g of B and N were added and reacted for 3 hours to obtain a white dispersion. Average particle size 0
．． It was 40 μm latex.

Production example of resin particles 5 N,N-dimethylciminoethyl methacrylate 50g1
A mixed solution of 15 g of poly(dodecyl methacrylate) and 300 g of toluene was prepared, and the following operations were conducted in the same manner as in Production Example 1 to obtain a white dispersion with an average particle size of 0.28 μm.

Production Example 6 of Resin Particles 10 g of (2-hydroxyethyl acrylate/methyl methacrylate) copolymer (weight composition ratio l/1) powder, (
A mixture of 2 g of dodecyl methacrylate/acrylic acid) copolymer (weight composition ratio 9515) and 100 g of toluene was processed in a ball mill for 48 hours to obtain a dispersion. The latex had an average particle diameter of 0.3 Hμm.

Production example 7 of resin particles 10 g of (vinyl alcohol/methacrylic acid) copolymer (weight composition ratio 7/3), (decyl methacrylate/N, N
-dimethyl acrylate) copolymer (weight ratio 95
15) A mixture of 1.8 g and 100 g of toluene was processed in a ball mill for 56 hours to obtain a dispersion. Average particle size 0.
It was 32 μm latex.

Resin particle production example 8 Resin particle production example 1 is exactly the same as resin particle production example 1 except that 1 g of ethylene glycol dimethacrylate is added to the dispersed resin α in addition to 2-hydroxyethyl methacrylate and n-hebutane. The following operations were performed to obtain latex particles having an average particle diameter of 0.25 μm.

Production example 9 of resin particles Production example of resin particles except that in production example 2 of resin particles, 1.2 g of divinylbenzene was added to the dispersion resin α in addition to 2-phosphonoethyl methacrylate, ethyl acetate, and n-hexane. The same operation as in 1 was performed to obtain latex particles with an average particle diameter of 0.40 μm.

Production Example 10 of Resin Particles In Production Example 3 of Resin Particles, the procedure is exactly the same as Production Example 3 of Resin Particles, except that 1.5 g of ethylene glycol dimethacrylate lamp is added to the dispersed resin α in addition to N-vinylpyrrolidone and toluene. The following operations were performed to obtain latex particles having the same average particle diameter as in Production Example 3 of Resin Particles.

Production Example 11 of Resin Particles Production of resin particles in Production Example 4 of Resin Particles except that 0.05 g of 1,6-hexanethiol diacrylate (1,6-hexanethiol diacrylate) was added to lt&resin β in addition to methacrylic acid, chloroform, and ethanol. The same operation as in Example 4 was performed to obtain latex particles with an average particle size of 0.45 μm.

Production Example 12 of Resin Particles In Production Example 5 of Resin Particles, the same operation as in Production Example 5 of Resin Particles was performed except that 0.8 g of triethylene glycol dimethacrylate was added, and the average particle diameter was 0.4.
Latex particles of 3 μm were obtained.

Production example 13 of resin particles 50 g of the following monomer (a), 30 g of methyl methacrylate)
A mixed solution of 17 g of 2-hydroxyethyl methacrylate, 3 g of allyl methacrylate, and 300 g of tetrahydrofuran was heated to 80° C. under a nitrogen stream. ^、l、
After adding 1.5 g of B and N and reacting for 6 hours, n-
It was reprecipitated in hexane and the solid was filtered. After drying, 84 g of powder was obtained.

H3 c+12=c A mixture of 20 g of tolyl was subjected to homopolymerization at 100° C. for 7 hours. The obtained reaction product was reprecipitated in methanol, and the solid matter was filtered. After drying, 4.1 g of powder was obtained.

The resin (hydrogel) obtained in this production example has the following structure.

Production Example 14 of Resin Particles A mixture of 50 g of (2-hydroxypropyl methacrylate/ethyl methacrylate) copolymer (weight composition ratio 7/3) and 200 g of methyl cellosolve was heated to 40° C. and dissolved. 1.6-Hexamethylenecyisocyaner) 1
．． 0 g was added and stirred for 4 hours. After the mixture was cooled, it was reprecipitated with water, and the solid matter was filtered.

After drying, 35 g of powder was obtained.

Production example 15 of resin particles 2-methyl-2-year-old xacillin 5 g, 1,4-tetramethylene-2,2'-bisoxazoline 1, og,
0.1 g of methyl triflate and acetonylate (Ct12
) * BeN-C112CH2-) Production Example 16 of Resin Particles A mixed solution of 50 g of 2-methanesulfonyl ethyl methacrylate, 0.8 g of dil:'nylsuccinic acid, and 200 g of dimethylformamide was heated to 70°C under a nitrogen stream. ,
1. 1.5 g of B and N were added and reacted for 8 hours. The obtained reaction product was reprecipitated in hexane, and the solid matter was filtered. After drying, a powder of 3Hg was obtained.

Synthesis Example 1 of Resin [B]: Resin [B)-1 100 g of methyl methacrylate, ethylene glycol dimethacrylate 1. After heating a mixed solution of Og and 200 g of toluene to a temperature of 75° C. under a nitrogen stream, azobisisobutyronitrile 1. Og was added and reacted for 10 hours. The weight average molecular weight of the obtained copolymer [B)-1 was 4.2 x 1
It was 0'.

Synthesis example 2 of resin [B]: Resin [:B] -2-functional methyl methacrylate 99 g 1 divinylbenzene Ig,) toluene 1
A mixed solution of 50 g and 50 g of methanol was heated under a nitrogen stream for 7 days.
After heating to a temperature of 0°C, 4.4'-azobis(4-
1.5 g of cyanopentanoic acid) was added and reacted for 8 hours.

The Fk so of the obtained copolymer was 1.2 x 10'.

Synthesis Examples 3 to 6 of Resin [B]: Resin [B]-3 to 6 In Synthesis Example 2 of the above resin [B], polymerization initiator: 4.4'
The resin [
B]-3 to 6 were each produced. ~ of each resin is 1.0X1
It was 03-3X103.

Synthesis example 7 of resin [B]: Resin [1(]-]7n-propyl methacrylate 9!Ig thioglycolic acid 1.0 g
, divinylbenzene 2.0 g FjL and toluene 2
00g of mixed solution was heated to 80°C while stirring under nitrogen flow.
It was heated to 2.2'-azobis(cyclohexane-1)
-carbonitrile) (abbreviated as ACIIN) was added and reacted for 4 hours.1. Further A, C3lI, N.

0.4g of was added for 2 hours, then A, l:, It,
0.2 g of N was added and reacted for 2 hours.

The spacing of the obtained polymer was 1.2 X l 11'.

Synthesis examples 8 to 17 of resin [B]: Resin [131-8 to 17
Each copolymer was produced using each compound in Table 2 instead of the methacrylate and divinylbenzene (monomer for bridge 14) used in Synthesis Example 7 of Resin [B].

The positive of the obtained polymer is 1. OXl 05~3XlO
'Met.

Example 1 and Comparative Examples A-B 2.6-cyclophenyl methacrylate 85 g, 6-
After heating a mixed solution of 10 g of hydroxyhexamethylene methacrylate, 5 g of acrylic acid, and 200 g of toluene to a temperature of 90°C under a nitrogen stream, 6 g of 2,2'-azobis(isobutyronitrile) was added, and 8 Allowed time to react.

The obtained resin (A-1) had a ≦7,800.

A mixture of resin (A-11 methylene cyanine dye [: 1.02 g of Al, 0.02 g of phthalic anhydride, and 300 g of toluene) was dispersed in a ball mill for 2 hours to prepare a photosensitive layer-forming product, which was subjected to conductive treatment. By applying it to paper with a wire bar so that the dry adhesion amount is 20 g/m', drying it at 110°C for 1 minute, and then leaving it in the dark for 24 hours at 20°C and 65% RH. An electrophotographic light-sensitive material was produced.

(Cyanine dye [A]) 1 The solid content of the above copolymer [A-1] is 66 g),
The resin produced in Synthesis Example 2 of Resin [B] (Bl-2 was
g (as solid content), 20 g (as solid content) of the particles of Resin Particle Production Example 1O, 200 g of zinc oxide, Hepta Comparative Example A represented by the following structural formula, and the particles of Resin Particle Production Example 1 in Example 1. An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except for the following.

Comparative Example B In Example 1, copolymer [A]-1 and copolymer (B
)-1, copolymer (R-1) 40 with the following structure
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that G was used.

Copolymer [R-1] CH.

Table 3 Mw: 34,000 The film properties (surface smoothness), electrostatic properties, imaging performance, and environmental conditions of these photosensitive materials were examined at 30° C. and 80% RH. Furthermore, the desensitization property of photoconductivity (expressed as the contact angle with water of the photoconductive layer after desensitization treatment) when these photosensitive materials are used as original plates for TOFSEC masters.
and printability (scumming, printing durability, etc.) were investigated.

The above results are summarized in Table 3.

The implementation aspects of the evaluation items shown in Table 3 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was tested for its smoothness (
sec/cc) was measured.

Note 2) Mechanical strength of photoconductive layer: The surface of the obtained photosensitive material was repeatedly tested 1000 times with emery paper (#1000) with a load of 50 g/cl using Hayton-14 type surface test material (Shinsha Kagaku ■rm>). Abrasion and abrasion powder were removed, and the residual film rate (%) was determined from the weight loss of the photosensitive layer, which was taken as mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 65% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper cynalyzer (Paper Analyzer-3P-428 model manufactured by Kawaguchi Electric). The surface potential immediately after heating is VG, and the surface potential after being left for 10 seconds is V. was measured. Then 9 in the dark
The potential after standing still for 0 seconds is V. 0 and dark decay for 90 seconds, that is, the dark decay retention rate [0
,R,R(%)](L../V,.)X100(%)
I asked for it. In addition, the surface of the photoconductive layer is heated to 40° by corona discharge.
After charging to 0V, the surface of the photoconductive layer was heated with a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 830 r++
n) Irradiate with light, calculate the time until the surface potential (V,.) attenuates to 1710, and calculate the exposure amount B, 7. . (e
rg/cm”).

The environmental conditions at the time of measurement were 20℃, 65% old 1 (I) and 30
℃.

It was carried out at 80% RH (II).

Note 4) Imaging properties: After leaving each photosensitive material for one day and night under the following environmental conditions, each photosensitive material was charged at -6 kV, and a 2.8 mW gallium-aluminum-arsenide semiconductor laser (oscillation wavelength: 830 nm) was used as a light source. ) on the surface of the photosensitive material, 64
After exposure under an irradiation dose of erg/cm' at a pitch of 25 μm and a skiing speed of 300 m/sec, ELF-T (Fuji Photo Film) was used as a liquid developer.
! 31! The copied image (fogging, image quality) obtained by developing and fixing using 1) was visually evaluated. The environmental conditions during imaging were 20°C 65% (1) and 30°C 80%.
Performed on RH(II).

Note 5) Contact angle with water: Each photosensitive material was passed once through an etching processor using a solution prepared by diluting the desensitizing liquid BLP-8 (Fuji Photo Film side) to twice the volume with water. After the surface of the conductive layer is desensitized, a drop of 2 μl of distilled water is placed on it, and the contact angle with the water formed is measured using a goniometer.

Note 6) Durable printing After making the plate in the same way as the imaging performance in Note 4 above,
) was desensitized under the same conditions as the offset printing machine (Oliver 5 manufactured by Sakurai Manufacturing Co., Ltd.) and used as an offset master.
2 type) and using high-quality paper as the printing paper, it indicates the number of sheets that can be printed without causing background stains in the non-image areas of the printed matter or problems with the image quality of the image areas (the higher the number of sheets printed, the better the printing durability. ).

As shown in Table 3, in the photosensitive material of the present invention, the strength and electrostatic properties of the smooth film of the photoconductive layer were good, and the actual copied images were clear with no ground blur. This means that the photoconductor and resin particles and the binder resin are sufficiently adsorbed, and
This is presumed to be due to the fact that the surface of the photoconductive zinc oxide particles is coated. For the same reason, even when used as an offset master original, the desensitizing treatment with the desensitizing treatment liquid progresses sufficiently, and the contact angle with water in the non-image area is as small as 10 degrees or less, making it sufficiently hydrophilic. It can be seen that Even after 10,000 sheets were actually printed, no background stains were observed when observing the printed matter.

Comparative Example A, in which only the resin particles of the present invention were removed, had extremely good electrostatic properties, but when printed using it as an offset master master plate, the image quality of the printed matter deteriorated after 5000 sheets.

Comparative Example B was glued for 90 seconds and +1. R was significantly reduced, and B17. . has also grown larger. The actual copy images were also not very satisfactory.

Furthermore, in Comparative Example C, in which the weight average molecular weight was increased using a copolymer exhibiting the chemical structure of the resin of Comparative Example B, the electrostatic properties were significantly deteriorated. It is presumed that as the molecular weight of the binder resin increases, adsorption to the photoconductive zinc oxide particles and aggregation between the particles are caused, resulting in an adverse effect.

As a result of the above, an electrophotographic photoreceptor satisfying electrostatic properties and printability can be obtained only in the case of the present invention.

Examples 2 to 13 In Example 1, copolymers shown in Table 4 were produced in the same manner as in the synthesis example of resin [A-1].

The weight average molecular weight of each of the obtained resins [8-2 to 22] was 7.000 to 8.000.

Table 4 In Example 1, instead of the particles of Resin (A-1), Resin [B]-2, and Resin Particle Production Example 1, the resin (A16g, resin (B'134g, and resin particles) shown in Table 5 was used. 18g
Each photoreceptor was manufactured in the same manner as in Example 1, except that (each as solid content) was used, and each characteristic was measured in the same manner as in Example 1.

The surface smoothness of the photoconductive layer of each photoreceptor is 80 (sec).
/cc) or more, it was smooth. Moreover, the film strength was 85% or more, indicating sufficient strength. Table 6 shows the results of electrostatic properties under environmental conditions (30° C., 80% RH).

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).
Even under severe conditions (%RH), it provided clear images with no occurrence of ground blur or fine line skipping.

Further, when printing was performed as an offset master in the same manner as in Example 1, more than 10,000 prints with clear images and no background smudges were printed on each photosensitive material.

Example 14 8 g of the following resin [A-131, resin [B]-9332
g, 20 g (solid content) of the particles of Resin Particle Production Example 2, 200 g of zinc oxide, 0.02 g of cyanine dye [, B) having the following structure, and 0.20 g of phthalic anhydride.
Mix 300 g of toluene and 300 g of
Spread out time.

This was applied to electrically conductive treated paper using a wire bar so that the dry adhesion amount was 22 g/m', and heated at 100° C. for 30 seconds. Next, an electrophotographic light-sensitive material was prepared by leaving it for 24 hours at 20° C. and 65% RH.

Resin [Δ-133 Cyanine Dye [B] Each characteristic was measured in the same manner as in Example 1. However, a gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) was used as the light source.

Smoothness of photoconductive layer: 102 (cc/5ec)
Strength of photoconductive layer = 94% Electrostatic resistance V. (V) D, R, R
B./.

(%) (erg/cm”) I (20℃, 65% old 1) -5408332■
(30℃, 80%RH) -5008036 photo
Image properties: (20°C, 65% R11) and (30°C.

80% old 1) Good under all conditions A copy image was obtained.

Printing durability: Good printed images were obtained up to 1000 sheets.

As described above, the photosensitive material of the present invention was able to exhibit excellent electrophotographic characteristics and high printing durability.

Example I5 The following resin (A-1(i) was 7F?%il! fat [B]
-16 to 33g1 resin particle I! Jli granulation example 5) Granulation 5
18g (as solid molecule IL), oxidized 1111 fl
211 [) g'+0.50 Rose Bengal
g, Detlab ■1 Muphenol Blue 11.25
g % uranine to 0. A mixture of 13.18 g of phthalic anhydride and 240 g of toluene was dispersed in a ball mill. This was coated on electrically conductive treated paper with a wire bar so that the dry smoke weight was 211 g/m', and heated for 30 seconds using a wire bar. Then, 2 (lt=, ri
596121 (24 hours) to produce an electrophotographic light-sensitive material.

Resin [△-1[i] Fi・l li,! 1ll11 Each of the photosensitive feeds of the present invention has: 1) electrical conductivity, electrical conductivity of 11v;
Retention rate and photosensitivity are 1.1! In addition, even under harsh conditions of high temperature and high humidity (30°C, 80% l?H), the reproduced images of the actual t, f, jilii are clear and free from soil blurring.
The statue is 111.

Furthermore, when this was printed using Offset Master 11: (plate), clear prints with rt were obtained even on 1001111 sheets.

However, for photosensitive material plate making, all self-axial plate making is required.
04V (7i Photo Film L, manufactured by Qη) II”, L
I) -1' was used as a toner to form -C,) S- images.

(Effects of the Invention) As described above, according to the present invention, it is possible to provide a lithographic printing machine that exhibits extremely poor printing characteristics. .

The present invention also provides hydrophilic iJI If? fJ J'
is the non-image part.

Maintain optimal desensitization. Furthermore, when this resin particle is partially crosslinked, it can be used in the above-mentioned dampening solution.

It will not dissolve into the water. Therefore, the printing durability of lithographic printing using the original plate of the present invention is significantly improved, and the original plate of the present invention can be repeatedly used as a lithographic printing original plate in good condition. .

Claims (5)

[Claims] (1) In an electrophotographic lithographic printing original plate comprising a photoconductive layer containing at least one photoconductive zinc oxide layer and a binder resin on a conductive support, the photoconductive layer contains the photoconductive layer. Contains hydrophilic resin particles having an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is at least one of the following resins [A] and the following resins [B] A lithographic printing original plate comprising at least one of the following. Resin [A]: has a weight average molecular weight of 10^3 to 2 x 10^4, and -PO_3H_2 group, -SO_3H group, -COOH group,
-OH group, -SH group▲There are mathematical formulas, chemical formulas, tables, etc.▼Resin containing 0.5 to 20% by weight of a copolymer component containing at least one type of polar group [B]: 5 A resin having a weight average molecular weight of ×10^4 or more, containing at least a repeating unit represented by the following general formula [I] as a polymer component, and having a crosslinked structure. General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, T is -COO-, OCO-, CH_2CO-,
-CH_2COO-, -O- or -SO_2-. V represents a hydrocarbon group having 1 to 22 carbon atoms. a_1 and a_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano atom, or a carbon number of 1 to 8.
represents a hydrocarbon group, -COO-Z or -COO-Z via a hydrocarbon group having 1 to 8 carbon atoms (Z represents a hydrocarbon group having 1 to 18 carbon atoms). ] (2) The lithographic printing original plate according to claim (1), wherein the resin [A] contains the following repeating units (i) and (ii) as copolymer components. (i): 30% by weight or more of one repeating unit represented by formula [II] or formula [III] Formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X_1 and
_2 each represents a hydrocarbon group having 1 to 10 carbon atoms. However, both X_1 and X_2 do not represent hydrogen atoms. W_1 and W_2 each represent a direct bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring. ] (ii): -PO_3H_3 group, -SO_3H group, -COOH group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R is 1 to 1 carbon number
0 hydrocarbon group or -OR'(R' represents a hydrocarbon group having 1 to 10 carbon atoms). ], 0.5 to 15% by weight of at least one repeating unit among polar groups such as -SH group and phenolic -OH group, and cyclic acid anhydride-containing group (3) Resin [B] is further added to -PO_3H_2, -3O_3H, -C only at one end of at least one polymer main chain.
OOH, -OH, -SH, ▲Mathematical formulas, chemical formulas, tables, etc.▼(R'' represents hydrocarbon) Cyclic acid anhydride, -CH
At least one polarity selected from O, -CONH_2, -SO_2, NH_2 and ▲Mathematical formula, chemical formula, table, etc.▼ (b_1 and b_2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group) The lithographic printing original plate according to claims (1) to (2), which is a resin [B'] formed by bonding groups. (4) The resin [B] is a resin that does not contain, as a polymer component, a repeating unit containing a polar group or a cyclic acid anhydride-containing group represented by the resin [A]. Original plate for lithographic printing. (5) The lithographic printing original plate according to any one of claims (1) to (4), wherein the hydrophilic resin particles form a high-order network structure.