JPH0213965A - Electrophotographic planographic plate - Google Patents

Abstract

PURPOSE:To obtain a planographic plate not causing background stains and having high printing resistance by incorporating resin particles having functional groups producing carboxylic groups upon decomposition in a surface layer. CONSTITUTION:The surface layer contains the particles of the resin having at least one kind of the functional group producing at least one carboxylic group upon decomposition or having at least one part of the resin molecule cross-linked with the other molecule, and these resin particles are dispersed into the surface layer and other than the binder resin of the matrix of said layer, thus permitting a copied image faithful to an original image to be reproduced, background stains not to occur because the hydrophilicness of the nonimage area is rich, electrostatic characteristics of a photoconductive layer lying under the surface layer to be kept good, and printing resistance to be enhanced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an electrophotographic printing original plate made by an electrophotographic method, and in particular, a surface layer having specific properties on a photoconductive layer. This invention relates to a lithographic printing original plate which is provided with a lithographic printing plate.

(Prior art and its problems) Currently, various types of offset blanks and plates for die-cut plate making have been proposed and put into practical use.
A photoreceptor having a photoconductive layer mainly composed of photoconductive particles such as zinc oxide and a binder resin on a T-type support is subjected to a normal electrophotographic process, and a highly lipophilic toner is applied to the surface of the photoreceptor. A widely used technique is to form an image, then treat the surface with a desensitizing liquid called an etchant, and selectively convert non-image areas into aqueous, thereby obtaining an offset master plate.

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, the photoconductive layer with the image does not separate during printing, has good compatibility with dampening water, and maintains sufficient hydrophilicity in the non-image area to prevent staining even if a large number of sheets are printed. It is necessary to have performance such as being able to be used.

In particular, as an offset master plate, background smearing due to insufficient desensitization is a major problem, and in order to improve this problem, the development of a zinc oxide binding resin that improves desensitization has been extensively studied. For example, Tokuko Sho 50-3101
No. 1, Japanese Patent Application Publication No. 5S-S4oz7F, 54-20755
No. 57-202544, No. 58-68046, etc. However, even if these resins are said to be effective in improving desensitization properties, when actually evaluated, they are still unsatisfactory in terms of scumming and printing durability.

On the other hand, using organic photoconductive compounds as photoconductive particles,
It is also possible to use an electrophotographic body in which a photoconductive layer is provided together with a binder resin on a grained aluminum substrate.

To make this type of original plate, as described above, after forming a toner image on the photosensitive layer by the usual electrophotographic method,
Dissolve and remove the non-image area with a processing solution. As a result, the non-image portion becomes an aluminum substrate and becomes hydrophilic. For example, Special Publication No. 37-17162, No. 46-59
No. 405, JP-A No. 52-2437, JP-A No. 56-1072
Oxadiazole compound b shown in No. 46 etc. is used when using a photosensitive layer in which an oxazole compound is bonded with an alkali-soluble resin such as styrene-maleic anhydride copolymer, or JP-A-55-105254, 55-1
No. 6125, No. 5B-150953, No. 58-162
It is known that a photolayer comprising a phthalocyanine pigment or an azo dye and an alkali-soluble phenol resin as shown in the specification of No. 961 is used.

However, in this plate-making process, the photosensitive layer in the non-image area must be dissolved and removed, which requires a large-scale apparatus and is time-consuming, which increases the plate-making speed. Furthermore, since ethylene glycol, glycerin, methanol, ethanol, etc. are used as the processing liquid (the above-mentioned organic solvent), problems remain with this plate-making method in terms of cost, safety, pollution, labor hygiene, etc.

Furthermore, Japanese Patent Publication No. 5606/1989 discloses a method of creating a printing plate with hydrophilic treatment on the surface of the non-image area, which is easy to make by providing a specific resin on an ordinary electrophotographic photoreceptor. There is. That is, vinyl ether is applied on the electrophotographic photosensitive layer.
- A printing plate is disclosed which is provided with a surface layer consisting of an anhydrous MAV acid copolymer and a hydrophobic resin compatible therewith. After the toner image is formed, this material can be made hydrophilic by treating the non-image area with an alkali to open the sialic acid anhydride ring portion with water. V (hydrophilicizable layer).

The vinyl ether-maleic anhydride compound used therein is ring-opened and becomes hydrophilic, and becomes water-soluble in the disc, so even if it is compatible with other hydrophilic resins, the layer will not form. Even if it had been formed, its water resistance was extremely poor, and its printing life was limited to 500 to 600 sheets at most.

Furthermore, % Kai No. 60-90345, No. 6Q-15975
No. 6, No. 61-217292, etc., disclose a method of providing a surface XJ (hydrophilicizable, v) using silylated polyvinyl alcohol as a main component and also using a crosslinking agent.

That is, in this layer, after the toner image is formed, the silylated polyvinyl alcohol/L/ is hydrolyzed in the non-image area to form a liquid. In addition, in order to maintain the tensile strength after hydrolysis, the degree of silicification of the polyvinyl alcohol is adjusted, and the remaining hydroxyl groups are crosslinked using a crosslinking agent.

However, although it is stated that these methods improve the scumming resistance of printed matter and increase the number of printed sheets, actual evaluation shows that they are still unsatisfactory, especially in terms of scumming. Furthermore, silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol in a desired proportion with a silylating agent, but since it is a polymer reaction, it is difficult to produce it stably. Furthermore, since the chemical structure of the hydrolyzed polymer is limited, in order not to jeopardize its function as an electrophotographic photoreceptor, it is important to (resolution, blurring of non-image areas, etc.), 3) u+! There was a condyle, etc., where it was difficult to ensure that the surface had no effect on light sensitivity.

In order to improve the problems of electrophotographic lithographic printing original plates as described above, the present inventors first developed a functional method in which a force~boxy/l/group is generated by decomposition as the main component of the surface layer. proposed an original plate for electrophotographic planographic printing using a resin containing (Tokuhon Sho 62-28345).

The present invention uses the same resin as in this earlier application, but does not use the resin as the main component of the surface layer (i.e., matrix) as in the earlier application, but disperses it as particles in the matrix, thereby solving the above problems. This solves the problem.

That is, an object of the present invention is to provide an insensitizing material that reproduces a copy image that is faithful to the original image, and that does not cause not only full-surface smudges but also spot-like smudges as an offset original or plate. The purpose is to provide an excellent lithographic printing system 5th edition.

Another object of the present invention is to maintain sufficient hydrophilicity in non-image areas and prevent background smudges even when the number of printed sheets increases.
The present invention provides a lithographic printing plate having high printing durability.

(Means and effects for solving the problems) The present invention achieves the above objects: (1) Provide at least one photoconductive layer on a conductive support, and further coat a surface layer on the uppermost layer lΔ. The electrophotographic lithographic printing original plate provided above is characterized in that the surface layer contains at least one type of resin particle containing at least one type of functional group that generates a carboxyl group upon decomposition. or (2) the above-mentioned resin particles are resin particles containing at least one kind of functional group that generates a decomposable μ-boxy μ group and at least partially cross-linked. This is achieved by an electrophotographic lithographic printing original plate having the following properties.

In the present invention, at least one force due to decomposition! Contains at least one functional group that produces levoxy tvg,
Furthermore, it is important that the resin particles, at least a portion of which are cross-linked, are dispersed as particles within the surface 1Δ, separately from the binder resin that is the matrix of the surface layer.

As a result, the lithographic printing substrate according to the present invention reproduces a copy image that is faithful to the original image, has good hydrophilicity in the non-image area, and does not cause background smudge, and furthermore, the light beneath the surface layer can be easily reproduced. It has the advantage of maintaining good electrostatic properties of the conductive layer and also has excellent printing durability.

Furthermore, the lithographic printing original plate of the present invention is not affected by the environment during plate-making processing and has excellent storage stability before processing.

Below, the functional group used in the present invention that decomposes to produce at least one carboxyl group (hereinafter sometimes simply referred to as a carboxyl group-producing functional group) will be explained in detail.

The carboxyl group-forming functional group of the present invention can be decomposed to produce a force p.
Although a boxy/l/ group is generated, the number of carboxyl groups generated from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, carboquine A
/ group-forming functional group-containing resin is -clothing cost (1) (-COO-
It is a resin containing at least one functional group 'y5 represented by LI].

In general formula (1) (-coo-L,], -N"C
H-Qt, -C-(h, -NH-OH.

I. O However, R1* R1 may be the same or different from each other,
It represents a hydrogen atom or an aliphatic group, X represents an aromatic group, and Z represents a hydrogen atom or a halogen atom.

)') Hao) ChiN group, AlVkiiV group, -CN,
-Noh-SO,R, (however, Rr represents a hydrocarbon group), -cooR; (however, R represents a hydrocarbon group) or -〇-R; (however, R3' represents a hydrocarbon group) ), and n and m represent 0, 1 or 2.

83m''4 #R11 may be the same or different and represent a hydrocarbon group or -〇-R4' (however, ``horse'' represents a hydrocarbon group), and M represents Si, Sn or T1.

Ql and Ql each represent a hydrocarbon group.

Yl represents an oxygen atom or a sulfur atom, R6, R7,
Rs may be the same or different and each represents a hydrogen atom or an aliphatic group, and p represents an integer of 5 or 6.

Y represents an organic residue forming a cyclic imide group.

The functional group of the general formula (-Coo-L, ) generates a force μ phoxyl group upon decomposition, and will be explained in more detail below.

R1# "l may be the same or different, preferably a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethiA
/ group, propyvMm chloromethyμ group, dichloromethyA
/ group, trichloromethy/l/ group.

trifluoromethyl group, buty μ group, hexy)v −, t
g *Octyl group, deci~ group, hydroxyethyl μ group.

3-chloropropyμ group, etc.), and X is preferably an optionally substituted phenyl group or a naphthiμN group (e.g., phenyl group, methylphenyl group).

chloropheni/L/xe (dimethylphenyl group, chloromethylphenyl group, naphthiμ group, etc.), and Z preferably represents a hydrogen atom, a halogen atom (e.g., chlorine atom, fluorine atom, etc.), a trihalomethiμ group (e.g., trichloromethyμ
groups, trifluoromethyl groups, etc.), optionally substituted linear or branched alkyl/L/ groups having 1 to 12 carbon atoms (e.g., methyl groups, chloromethyl groups, dichloromethy groups, ethyl groups, propyl groups) .Buty μ group, Pekin μ group.

Tetofufu~Oroethyl group, Octiμ group, Nanoethyl A/
group, chloroethyl group, etc.), -CN, -No! .

-8o! R1'(R1' is an aliphatic group (for example, 1 carbon number
~12 optionally substituted alkyl groups: specifically methyl group, ethyl group, propyl group, buty/I/ group.

Chloroethyl group, bench μ group, octyl group, etc., carbon number 7
-12 optionally substituted affu-μ groups: specifically benzyl group, phenethi-μ group, chlorobenzyl group, methoxybenzi-μ group, chloropheneti-fi7 group, methylphenethyl group, etc.) or aromatic groups (e.g., substituted A phenyl group that may contain a V group or a naphthyl group: specifically, a phenyl group.

chlorophenyl yv group e dichloropheni y group, methi μ phenylene group, metquinpheni/L/ISG# acetyphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group], -COOR1'
(R,' has the same meaning as R1' above) or -0-R,' (R/ has the same meaning as R1' above). n and m represent 0, 1 or 2.

To explain the signature more specifically, the following examples of substituents can be given.

For example, β, β, β-trichloroethyl/L/N.

β, β, β-trifluoroethyl/L/group, hexafluoro-1-propyA/group, -〇H! -(-CF鵞CFI-H group (indicating n'ld1 to 5), 2-cyanoethyl group.

2-2) RoxflVQ, 2-methanesulfonyN-
IVN, 2-ethanesulfonylethyl/'112-butanesulfonylethyl A/x*benzenesulfony~ethyl A/[
,,4-Nitrobenzene~honiμtech/L'm#4-
Cyanobenzenesulfonylethyl group, 4-methylbenzenesulfonylethyl group, benzyl group which may contain a substituent (e.g. benzyl group, methoxybenzi/L/ group, trinothylpendi~ group, pentamethylbenzi/L'&, nitrobenzyl/L/group, etc.), phenacyl group which may contain a substituent (e.g. il' phenacyl group, glomofenacyl group,
l/Tl, etc.), Phenyl/I/ which may contain a substituent
For example, N11 is a feniμ group, a nitrophenyl group, or a cyanopheniμ group. Methane ~ honi p phenylene ~ group.

(trifluoromethylphenyl group, dinitrophenyl group, etc.).

In addition, when Ll represents -M -R4, Rs
.

R.

R4e "l may be the same or different, preferably an optionally substituted aliphatic group having 1 to 18 carbon atoms [
The aliphatic group represents an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group, and examples of substituents include a halogen atom, -CN group, -〇HTb-〇-Q'(Q' is an alkyl μ
C6-C18 optionally substituted aromatic groups (e.g., t-haphenyl group, tri/I/X, chlorophenylene group), etc. ) or -〇-R4'(R4'
is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted aykenyl group having 2 to 12 carbon atoms, an optionally substituted araμ group having 7 to 12 carbon atoms, a carbon number 5~1
8, an optionally substituted alicyclic group, and an optionally substituted ary/L/ group having 6 to 18 carbon atoms.

M represents each atom of Si, Ti, or Sn, and more preferably represents an S1 atom.

L again! When represents -N-CH- or -C-Q2, Ql and Qz preferably each have 1 to 1 carbon atoms.
18 optionally substituted aliphatic groups (as aliphatic groups,
Indicates Aμ/L/ group, alkenyl group, aralkylv group, alicyclic group, and examples of substituents include halogen atom, CN
) or an optionally substituted aryl group having 6 to 18 carbon atoms (e.g. phenyl lv group, methoxy phenyl/L/ group, tolyl group, chlorophenyl group, naphthyl group, etc.) represent.

h@Yl represents an oxygen atom or a sulfur atom. "4, R7
, R1 may be the same or different, preferably a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, Hexyμ group, octyμ group, decyl group, dodecyl group.

Octadecyl group. Chloroethyl/I/ group, methoxyethyl/
(L/group, methoxypropyl group, etc.), optionally substituted alicyclic groups (e.g., cyclobenti group, cyclohexyl group, etc.), optionally substituted alkyl groups having 7 to 12 carbon atoms/%
/ group (e.g. benzyl group).

Phenethyl group, chlorobendi μ group, methoxybendi A/
group), an optionally substituted aromatic group (e.g., ethyl group, naphthyl group, chlorophenyl group, triμ group, methoxyphenyl group, methoxycarponyphenyl group, dichlorophenyl group e), or -〇-R, (h' represents a hydrocarbon group, specifically the same substituents as the above-mentioned hydrocarbon groups of R6, Ra, and Horse).

p represents an integer of 5 or 6.

Yl represents a specific residue forming a cyclic imide group.

Preferably, all organic residues represented by (II) or (III) are represented.

In formula (n), R1 and R1° may be the same or different, and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or a substituted atom having 1 to 18 carbon atoms. L/group [e.g. methyl group.

Ethyl group, propy/L/ group, buty~ group, hexyl group.

Octyl group, deV/V group, dodecy~ group, hexadecyl μ group, octadecyl group, 2-chloroethyl group.

2-MeFxyethyl group, 2-cyanoethyl group.

3-chloropropyl group, 2-(methanesulfonyIV)-flV group, 2-(ethoxyoxy)ethyl group, etc.),
An optionally substituted aphkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group).

5-phenylpropyμ group, methyμbendi7+4. .

Dimethy benzyl group, methoxybendi/L/weir, chlorobendi N group, bromobendi μ group Kl), carbon number 6~
1.
group, 3-methy1v-2-propenyl group, 2-hexenyl group, 4-propy/L/-2-benteny/"l; e12
-octadecenyl group, etc.), -8-Rn'(Rs' is mJg R*, SL is RIO (7) 7 tV Ki IV
Base.

(represents the same content as aralkylv group, alkeni/l/ group), optionally substituted aryl group (e.g. pheny/l/
'M%)! J group, chlorophenyl group, promophenyl group
JL methoxyphenyl group, ethoxypheny/I/ group, ethoxycarbonylphenyl group, etc.), or -NI(R7'
(R, 'represents the same content as '' above). 3'J S may also be represented by R9 and RIG forming a ring [for example, a 5- to 6-membered monocyclic ring (e.g., cyclopentyl ring, cyclohexyl ring), or a 5- to 6-membered bicyclo ring (e.g., ebabicyclo). (hebutane ring, bicycloheptine ring, bicyclooctane ring, bicyclooctene ring, etc.); furthermore, these rings may not be substituted, and the substituents include the same as those described above for R9 and RIG]
.

q represents an integer of 2 or 3.

In formula (1[1), R11 and Rtz may be the same or different, and represent the same content as R9 and R1°. Furthermore, R11 and RtZ may represent an organic residue that consecutively forms an aromatic ring (for example, a benzene ring, naphthalene ring, etc.).

Another preferred embodiment of the present invention is: - Clothes cost (f)
(-Co-R2: At least one functional group represented by l
It is a resin containing seeds.

In general formula (h) (-Co-L!), R2 is R14:Rti
Represents R11R1.

However, Rtx # R14 # R11e RIM e
R17 each represents a hydrogen atom or an aliphatic group.

The aliphatic group preferably represents the same content as -5R7 and horse above. Also, R14 and RIM and R1- and R
17 represents an organic residue which may be linked to form a condensed ring. Preferably a 5- to 6-membered single 11 Lttf cyclopentyl ring, cyclohexyl ring, etc.), a 5- to 12-membered aromatic ring (for example, a benzene ring, a naphthalene ring, a thiophene ring, a pillow μ ring, a biran ring, a 9-quinoline ring, etc.) etc.

Furthermore, as another preferred embodiment of the present invention, the following-
It is a resin containing at least one type of oxacylone ring represented by Fukuyo (V).

-Fukudai (V) In the general formula (V), R11s Rts may be the same or different, and each represents a hydrogen atom or a hydrocarbon group, or R1 and R19 together form 1. Good too.

Preferably, RIIs R11 may be the same or different and each represents a hydrogen atom, an optionally substituted C1-C12 alkyl A/group (e.g. methyl/L' group, ethyl group, propyμ group, butyvxehexy~ group, 2-chloroethyμ group, 2-methoxyethyl group,
2-methoxy group, 3-hydroxy V propyN group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, 4-chlorobenzi group, 4-acetamidobenzyl group), group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2
-12 alkenyl groups (e.g. ethylene group, ali A/ group, isoprobeni group, butene diμ group, hexeni fv group, etc.)
, optionally substituted 5- to 7-membered alicyclic group (e.g., cyclobenzi μ group, cyclohexyl group, chlorocyclohexy μ group, etc.), optionally substituted aromatic Ml'lLt haphenyl group, chloropheni tvxe Methoxypheny group, acetamidopheny/L/ie methyNpheny/I/ group. Dichlorophenyl group, nitrophenyl group, naphthi/L
/ group, butylphenyl A/group e dimethymu phenyl A/ group, etc.)
or R18 and 9 together form a ring (for example, a tetwomethyV group).

pentamethylene group, hexamethylene group, etc.) may also be formed.

The resin containing at least one functional group selected from the group of functional groups represented by the general formulas (1) to (V) used in the present invention can be prepared by reacting the carboxyl group contained in the polymer with the general formula ( -Coo-LI] or (-Co-I
4) A method using a so-called polymer reaction to convert into a functional group, or - formula (-Coo-Ll:] or C-C
by the polymerization reaction of one or more monomers containing one or more functional groups, or of this monomer and other monomers copolymerizable therewith. ) can be obtained by a method of making a polymer.

These methods are described, for example, in Nippon Kagaku Kinpaku [New Experimental Chemistry Course Vol. 14, Synthesis and Reactions of Organic Compounds [■]” No. 2535.
(published by Maruzen Co., Ltd.), Yoshiyu Iwakura and Keisuke Kurita, "Reactive Polymers", page 170 (published by Kodansha), etc.

General formula (-Coo-I43 or (-Co
-L, ) can be arbitrarily adjusted or contains no impurities.
A method of manufacturing by polymerization reaction from monomers containing one or more functional groups of (o-Ll) or (-Co-L) is preferred.Specifically, carboxylic acids containing polymerizable double bonds are preferred. Alternatively, the carboxyl group of the acid hafide can be converted to the general formula (-Coo-L, ) or (:
-〇〇-L, ) can be converted into a functional group and then subjected to a polymerization reaction to produce it.

In addition, the resin containing the oxacylone ring represented by the formula (V) is made of one or more monomers containing the oxacylone ring, or the monomer and other monomers copolymerizable therewith. It can be obtained by a method in which the polymers are synthesized into a single unit by a polymerization reaction.

The monomer containing this oxacylone ring can be produced by a dehydration ring closure reaction of an N-acyloyl-α-amino acid term containing a polymerizable unsaturated bond. Specifically, it can be produced by the method described in ``Reactive Polymers'' by Yoshio Iwa and Keisuke Kurita, Chapter 3 (published by Kodansha).

Examples of other monomers that can be copolymerized with these monomers include vinyl acetate A/, vinyl propionate, vinyl propionate, and vinyl butyrate μ.
, allyl acetate, propio/allyl acid, etc.
Vinyl or allyl esters/1/, acrylic acid, methacrylic acid.

Esters or amides of unsaturated acidic acids such as crotonic acid, itaconic acid, maleic acid, fumer/I/acids, etc.
Styrene, vinyl μtoene, styrene derivatives such as α-methylstyrene, α-OVfins, acrylonitrile, methano, lylonitrile. Examples thereof include vinyl/L/group-substituted heterocyclic compounds such as N-vinylpyrrolidone.

As mentioned above, to describe more specifically the copolymer components containing the functional groups of general formulas (1) to (V) used in the method of producing a desired resin by polymerization reaction, for example, the following - Examples include components as shown in formula (Vl). However, it is not limited to these copolymer components.

General formula (■) x’　−y’　−w In formula (Vl), X' is -o-, -co-, -coo-.

b goose Indicates an aromatic group or a heterocyclic group [however, dl.

'l # dsa d4 are each hydrogen! Kyoko, a hydrocarbon group, or +Y'-WIl in formula (Vl), t)I
I bt may be the same or different, and a hydrogen atom,
represents a hydrocarbon group or +Y'-W) in formula (Yl),
t represents an integer from 0 to 18].

Y' represents a carbon-carbon bond which may be via a hetero atom connecting the bonding group X' and the bonding group [W]; the hetero atom is an oxygen atom, a sulfur atom, or a nitrogen atom -
), for example bS ■ -O-, -8-, -N-, -COO-, -CONH-,
-so! −.

-8O! It is composed of bonding units such as NH-, NHCOO-, -NHCONH-, etc., singly or in combination (
However, bS m b4 # bm are respectively 011 bl
e bt).

W represents a functional group represented by formulas (1) to (V).

al e 'l may be the same or different, and may include a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an ano group, a hydrocarbon group (e.g., a mena group, an ethylvm#prohiI
v group, butyl group, methoxycarbonyl group, ethoxycarbonylv group, propoquinecaponiμ group, butoxycaIL
/yg nyl group, hexyμoxycarbonyl group, methoxycarbonymethyN group, ethoxycarbonyμmethyl group. an optionally substituted alkyl group having 1 to 12 carbon atoms such as a butoxycarbonyl μmethium group; an aralkyl group such as a benzyl group and a phenethyl μ group; and a phenyl group. tolyl group, silyl group, ary μ group such as chlorophenyl group) or - in formula (vI)
Aki μ group having 1 to 18 carbon atoms which may be substituted with a substituent including a W group.

It represents an alkenyl lv group, an arapkiμ group, an alicyclic group, and an aromatic group.

Further, the (-X'-Y'-1 bonding residue in formula (Vl) may directly connect the al+C+ moiety and -W.

The word W represents the symbol content expressed by general formulas (1) to (V).

Specific examples of the functional groups represented by general formulas ([) to (V) [W group in formula (Vl)] of the present invention will be described below.

However, the scope of the present invention is not limited to these.

CHs H3 CH, C, Hs CH.

舊 18)　　　　　-〇〇〇-81-Ca■ Hs C,H.

Strive +9+ -Coo-8i -C,H.

03H.

C, H islands d-Coo-3i-C horse C,H.

C)1. C,)(.

(Ill -Coo-8i-CH.

0HxCaHi fig -COOCRlCF.

C.F.

/ +131 -COOCR \ CF3 N CH, CI (3 CaH* CH.

d H3CH3 CH.

C! H Osamu CAH book number CH, C’, H explosion U 8) -C○OCH, OCH.

OCH.

@-cooc(c@Hs)s tsD　　　　　-COOCH(C,H,).

The polymer component containing a carboxyl group-forming functional group in the resin of the present invention should be 10 to 95% by weight, particularly 20 to 90% by weight, of the total copolymer when the resin is a copolymer. is preferred.

The resin of the present invention is further characterized in that at least a portion thereof is crosslinked.

A resin in which at least a portion of the polymer is crosslinked in advance (a resin having a crosslinked structure in the polymer) is used when the carboxyl group-forming functional group contained in the resin generates a μ boxyl group that is not susceptible to decomposition. In particular, resins that are sparingly soluble or insoluble in acidic and alkaline aqueous solutions are preferred.

Specifically, the solubility in distilled water is preferably 90% by weight or less, more preferably 70% by weight or less at a temperature of 20 to 25°C.

As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used.

That is, a method in which a functional group that undergoes a crosslinking reaction is contained in a polymer containing a functional group that generates a carboxyl group upon decomposition, and a polymer containing both of these functional groups is crosslinked using various crosslinking agents or curing agents. Alternatively, a method of subjecting these polymers to a polymerization reaction (a method of crosslinking by polymer reaction, or a method containing at least a monomer corresponding to a polymer component containing a functional group that produces a sulfuric acid to boxylv group upon decomposition) It can be synthesized by a method of crosslinking between molecules by coexisting a polyfunctional monomer or polyfunctional oligomer containing two or more polymerizable functional groups during a polymerization reaction. .

In the present invention, the functional group that progresses the crosslinking reaction may be any conventional polymerizable double bond group or a reactive group that can be bonded through a chemical reaction.

Specifically, as the polymerizable double bond group, CH, -CH-
CH, -1CH, -CH-C-0-1CH, -CH-1
CH3 Glance CH! -CH-C0NH-, CH2-C-C0N)(-
, CH-CH-CONH-, CH, -CT(-0-C-
, CH TS, -C-0-C-1CH! -low C) (-CH
,-0-C-1CH! -CH-NHCO-, CH,, -
CH-C'H, NHCO-, CH---CH-8O,-
, CH, -CH-C0-, CH -CH-0-1CH!
-CH-8-, etc. can be formed: In addition, when a chemical bond is formed by a reaction between reactive groups and a bridge is formed between polymers, a reaction of ordinary organic low-molecular compounds can be used. If you do the same thing, you will get a toe. Specifically, Yoshiyu Iwakura and Keisuke Kurita, “Reactive Polymers,” Kodansha (1977), Ryohei Oda, “Polymer Fine Chemicals,” Kodansha (1977),
(published in 1976), etc., are detailed in the bottom book.

For example, in Table 1, chemical bonding by combining a group A functional group and a group B functional group is listed as a commonly known method.

Table 1 In addition, -CONHCH snow 0R (R represents a hydrogen atom or an alkyl group such as a methyμ group, an ethyl/' group, a propyl group, or a butyl group) is also mentioned as a reactive group, and this reactive group It is known as a group that bonds in a condensation type reaction, and this can also be used.

As the crosslinking agent in the present invention, compounds commonly used as crosslinking agents can be used. Specifically, Shinzo Yamashita and Tosuke Kaneko ed. “Crosslinking Agent Handbook” published by Taiseisha (
Compounds described in "Polymer Data Handbook, Basic Edition" edited by the Polymer Science Society of Japan (1981), Baifukan (1986), etc. can be used.

For example, organic silane compounds (e.g., vinyltributoxysilane, vinyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyμtriethoxysilane, γ-aminopropyptriethoxysilane, etc.) y coupling agent, etc.), polyisoanate-based compounds (e.g. toluylene diisocyanate,
0-μ ylene diisonanate, diphenylene μmethane diisocyanate F1 triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.) , polyol compounds (e.g. 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol,
1,1.1-)limethylolbroban, etc.), polyamine compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine, hexamethylenediamine, N-aminoethylpivefudine, modified aliphatic polyamines, etc.), Epoxy group-containing compounds and epoxy resins (for example, compounds described in Hiroaki Kakiuchi's "New Epoxy Resin" Shokodo (published in 1985), Kuniyuki Hashimoto (ed.) "Epoxy Resin" Nikkan Kogyo Shimbunsha (published in f969), etc.), Melamine resin (for example, "Uria Melamine Resin" edited by Kazuhiro Miwa and Hideo Matsunaga, Nikkan Kogyo Shimbunsha (1969)
Poly(meth)acrylate compounds (e.g. Shin Okawara, Takeo Saegusa, Toshinobu Tsukamura "Oligomer" Kodansha (1976), Eizo Omori "
Compounds described in ``Functional Acrylic Yarn Resin'' Technosystem (published in 1985), etc.), specifically polyethyl glycol diacrylate, neobentyl glycol diacrylate, t6-hexanesiol diacrylate , trimethylolbroban triacrylate, pentaerythritol polyacrylate, bispheno-μ-human-diglycidi-ether diacrylate, oligoester μ-acrylate: These methacrylates include.

In addition, examples of polyfunctional monomers or oligomers having two or more polymerizable functional groups used in the above combination reaction include monomers having the same polymerizable functional groups such as divinylbenzene and trivinylbenzene. Styrene derivatives such as:
Polyvalent - rw Co/I/ (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol - μ÷200, ÷400, ÷600.1.
3-butylene glyco-μ, neobentyl glycol, dipropylene glyco-μ, polypropylene glycol, trimethylo-μ propane, trimethylo-ethane, pentaerythritol, etc.) or polyhydroxyphenol-/I/
(e.g. evahydroquinone, resorcin, catechol μ and their derivatives), methacrylic acid, acrylic acid/L/1 or crotonic acid, vinyl ethers or allyl ethers; dibasic acids (e.g. malonic acid, succinic acid) , guri μ acid, adipic acid, pimelic acid, maleic acid,
Lid/L/ (4, itaconic acid, etc.) vinyl esters, allyl esters/I/neck, vinylamides or allylamides: polyamines (e.g. ethylenediamine, 1.3
- propylene diamine, t4-butylene diamine, etc.) and vinyl group-containing acids (e.g. methacrylic acid,
acrylate, crotonic acid, allyl acetic acid, etc.).

Further, examples of polyfunctional monomers or oligomers having different polymerizable functional groups include vinylyvlJ.

Hydroponic acid [e.g. methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconylyl acetic acid, itaconylloylpropionic acid, hydrocarbon acid anhydride and alcohol or amine] Reactants (e.g. allyloxycarboxypropionic acid, allyloxycarboxylic acid)
vinyl acetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) or amide derivatives containing vinyl groups (e.g. vinyl methacrylate, acrylic acid, vinyl itaconate, vinyl itaconate, methacrylic acid, etc.). acid allyl, acrylic/'f'l antyl
1 Alli N itaconate, Hinyl methacryloyl acetate, Vinyl methacryloylpropionate, Allyl methacryloylpropionate, Methacrylate/l/+Vinyl oxidation carbonyl methyl ester, Vinyl oxycarbon acrylate methyl methacrylate to oxycarbon ethylene ester IV , N-allylacrylamide, N-aryl methacrylamide, N
52- is aminoaconate tvJ
(e.g. aminoethanol, 1-aminopropano-μ,
1-aminobutano-μ, 1-aminohexanol, 2-
aminobutanol, etc.)! :, a condensate of acid-bonic acid containing Hini/L/ groups, and the like.

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is 10% or less of the total monomers,
Preferably, the amount of 5-1% or less is used for polymerization to form a resin.

As described above, the resin particles of the present invention contain a polymer component containing a functional group that can be decomposed to produce a μpoquinyl group, and have a crosslinked groove structure inside the particles.

It is preferable that the resin particles of the present invention have an average particle size of 0.05 to 1.0 μm. If the weight is larger than 1.0 weight m, the smoothness of the surface layer will decrease, resulting in a decrease in the strength of the toner!
This causes the strength of the causal image to decrease. On the other hand, α05μm
If it is too small, there will be no significant difference from the case of molecular dispersion.

The resin particles of the present invention having such a small particle size can be made to have a desired particle size by being dispersed in the coexistence of the resin powder as is when preparing the composition for forming the surface 1. Alternatively, conventionally known dry and wet microparticulation methods or methods for forming polymer gel latex may also be used.

That is, a method of directly pulverizing the resin powder with a conventionally known pulverizer/disperser to form fine particles (e.g., Boμ Mill, Paint Shaker, Sound Mill, Hammer Mill, Jet Mill, Kedemi, etc.); Latex particles from conventionally known paints or liquid developers for electrostatic photography! ! A method of building can be used. The latter method of producing polymer latex is a method in which the resin powder is dispersed in combination with a dispersion polymer, and the resin powder and the dispersion-assisting polymer are kneaded in advance to form a kneaded product, which is then pulverized. There is a mechanical method such as a method of dispersing in the coexistence of a dispersion polymer.

Specifically, Kenji Ueki supervised translation of "Paint Flow and Pigment Dispersion" Kyoritsu Shuppan (1971), "Solomon, Chemistry of Paint", [
Pa1nt and 5 surface coating
Theory and Practice J, Yuji Harasaki, “Coating Engineering,” Chokoku Shoten (1971), Yuji Harasaki, “Basic Science of Coatings,” Maki Shoten (1977)
, JP-A-62-96954, JP-A-62-115171, JP-A-62-75651, etc.

Further, latex particles of the resin of the present invention can be easily obtained by conventionally known polymerization reactions such as suspension polymerization and dispersion polymerization.

Specifically, So Muroi - "Chemistry of Polymer Latex" Kobunshi Publishing (1970), Taira Okuda, Hiroshi Inagaki "Synthetic Resin Emulsion" Kobunshi Publishing (1978), So Muroi - "
"Introduction to Polymer Latex" Kobunsha (1983), etc.

In the present invention, the method of producing polymer latex particles is preferred, and resin particles having an average particle diameter of 1.0 μm or less can be easily produced by the method.

When the latex particles of the present invention are non-aqueous latex, the non-aqueous solvent used in the non-aqueous latex may be any organic solvent with a boiling point of 200°C or less, and these may be used alone or in combination of two or more. You may also use it.

Specific examples of organic solvents include methanol, ethanol, propatool, alcohols such as butano-μ, fluorinated alcohol, and benzyl alcohol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diethyl ketone, and diethyl ether Ethers such as hydrofufuran and dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyacetate, and methyl propionate, and carbon atoms of 6 and more such as hexane, octane, decane, dodecane, tridecane, cyclohexane, and cyclooctane. 14 aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, methylene chloride,
dichloroethane, tetrachloroethane, chloroform,
Examples include halogenated hydrocarbons such as methylchloroform, dichloropropane, and trichloroethane.

The method of synthesizing polymer latex using dispersion polymerization in these non-aqueous solvent systems allows the average particle size of latex particles to be easily reduced to 1 μm or less, and furthermore, the particle size distribution is extremely narrow, and monodisperse particles are produced. It can be done. Specifically, L
E., J. Barr-ett, [Dispers.
ion Polymerization inOrga
nic Media J John WLley (
1975), Koichi Murata, Polymer Processing, 2S,
20 (1974), Tsunetaka Matsue, Toyokichi Tange, Japan Adhesive Association Law 9, 185 (1973), Toyokichi Tange, Japan Adhesive Association Law 23°26 (1987), D, J, Walbridge.
, NATOAdv, 5tudy, Iust, Ser.
, E. m 67, 40 (1983), B.
P, No. 895429, B, P, 9!14 0
No. 38, USP 1 f 22397, USP 39
The method is disclosed in US Pat.

If the amount of the resin particles of the present invention is too small, the effect will be lost, and if the amount is too large, the hydrophilicity of the non-image area will improve, but the etching rate will decrease, so The amount is 20 to 200 weight percent, preferably 80 to 150 weight percent.

As described above, the resin particles of the present invention have the following properties:
By making the group a protected functional group (i.e., a functional group that generates υ carboxyl group by decomposition), strong interaction with each component in the photoconductive layer is suppressed, while desensitization treatment By generating a hydrophilic group VIL/group, it has the effect of improving the hydrophilicity of the non-image area.

Furthermore, since the resin particles of the present invention have a cross-w structure in at least a part of the polymer in the original, the force generated by the desensitization treatment ~ phoxyl group-containing resin while retaining hydrophilicity. becomes water-soluble and has the effect of preventing it from being eluted from the non-image area.

Therefore, the hydrophilicity of the non-image area is further enhanced by the carboxyl groups generated in the resin, and the durability is improved.

Furthermore, the resin containing a functional group that generates carboxyl groups upon decomposition is used as the main component (matrix) of the surface layer.
In the first patent application (Japanese Patent Application No. 62-2B545), the resin is molecularly dispersed, but in contrast, in the present invention, the resin is dispersed in particles with a fine particle size, and is desensitized. The ease of generating μ-phoxyl groups due to the force, and the degree of hydrophilization due to the generated force ~ poxy A/weir, are more than −1
be enhanced. This is presumed to be due to the fact that the specific surface area of particles dispersed in the form of small particles is significantly greater than that dispersed in the form of molecules.

As the matrix resin provided for the surface layer of the present invention, all conventionally known binder resins can be used. Typical examples include vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl butyral, alkyto resin, These include silicone resin, epogyne resin, epoxy ester resin, polyester resin, etc.

Specifically, Ryuji Kurita, Tsugube Ishiwatari, and polymers.

Volume 17, page 278 (1968), Harumi Miyagi, Hidehiko Takei, Imaging, 1973 (Encyclopedia 8), page 9, Takashi Nakatoshi-ed. "Practical technology of binders for trimming materials" Chapter 10, C
, H, C Publishing (published in 1985), D, D, Tatt,
S., C. Heldecker, Tappi.

49 (Collection 10), 439 (1966), E, S.

Baltazzi, R.G., Blanclott.
e etal, Photo.

SCi, F, ng, 16(In2), 354 (1972
), Genin Chan Ke, Isamu Shimizu, Hide Inoue, Niko Photographic Society Journal 18 (Ugly 2), 28 (1980), Tokuko Sho 50
-31011, JP-A No. 53-54027, JP-A No. 54-
No. 20735, No. 57-202544, No. 58-68
Materials disclosed in No. 016 and the like may be mentioned.

It may also contain a copolymer component containing a functional group that generates a pupillary group upon decomposition. Specifically, as mentioned above, as a copolymer containing a functional group that generates a carboxy μ group upon decomposition, Japanese Patent Application No. 62-28345 and No. 62-62-
No. 226694, etc., as a copolymer containing a functional group that generates hydroxyl v tv yield upon decomposition.
-106417, No. 62-151507, etc., as a copolymer containing functional groups that produce amino groups, thiol stripes, sulfo groups, phosphor stripes, etc. upon decomposition.
No. 3-42455, No. 62-270308, No. 65-
A monomer corresponding to the functional group-containing copolymer component described in No. 42454 or the like may be contained in the binding resin.

(Specifically, 30% of the total amount of the copolymer is used as a copolymer component, with the monomer shown in the following - Clothes cost (■))
A (meth)acrylic copolymer containing above, or -
An example is a single association of monomers indicated by Fukudai (■).

- Clothes cost (■) CH = C 'COO-R' In the general formula (■),
4 alkyl group or -CHIC0OR# group (R1 is an optionally substituted alkyl group having 1 to 6 carbon atoms) VM (e.g. methyl group, ethyl group, propyl group, butyl group, hebutymu group, hexy ~ group, (2-methoxyethyl group, 2.-chloroethyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyA/ group, phenethyl group, 3-)dinylpropyl group, 2-phenylpropyl group.

chlorobenzyl group, bromobenzyl group, methoxybenzyl group, methylbenzyl group, etc.) or an optionally substituted aryl group having 6 to 12 carbon atoms (e.g., phenyl group, tri-N group, xylyl group, chlorophenylene/L/ms dichlorophenyl group, methoxyphenyl tvme bromophenyl μ group, naphthi 1VTs, etc.).

R' is optionally substituted alkyl having 1 to 18 carbon atoms/l
/ group (e.g. methyl group, ethyl group, propyl group, butyf
V group, pentyl group, hexyiv-M, octyl group,
deci/L/% dodecyl group, tridecyl group, tetotudecy/l/group, 2-methoxyethyl group, 2-ethoxyethyl/L/group, etc.), optionally substituted γ having 2 to 18 carbon atoms
μkenyl group (e.g. vinyl group, A!J yvM, isoprobeni) V group, butenyl 1%7 group, hexenyl group! V group, heptenyl group, octenyl μX, etc.), an optionally substituted arafurekyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, methoxybenzi/L'!, methoxybenzi N group, methylbenzi Iv group, etc.), An optionally substituted cycloalkyl group having 5 to 8 carbon atoms (e.g., cyclobenti/l/group, cyclohexyne Ivu% cyclohebuty/I/ group, etc.),
Aryl group (e.g. phenyl group, triμ group, xyN group,
(mesityl group, naphthyl group, methoxyethyl group, ethoxyphenyl group, chlorophenyl group, dichlorophenyl group, etc.).

- Examples of other monomers to be copolymerized with the monomer represented by the formula (■) include vinyl acetate, propionic vinyl,
, aliphatic acid such as acetate, allyl propionate, or allyl acetate 1
vRA% Unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, zuma-μ acid, etc., or esters/L/s or amides of these unsaturated μ-acids, styrene, vinyltoluene, α-methyl Ionanutylene derivatives of styrene, α-olefins, acrylonitrile,
Examples include vinyl group-substituted heterocyclic compounds such as megclonitri 17% N-vinylpyrrolidone.

The molecular value of the matrix resin provided for the surface layer of the present invention is preferably 103 to 10, more preferably 5X10.
The glass transition point of this resin is preferably -10°C to 120°C, preferably 0°C.
~85°C.

The above-mentioned resin particles dispersed in the surface layer of the present invention are resins that are hydrolyzed or hydrolyzed by a desensitizing liquid and a dampening solution used during printing to produce carboxyne A/groups.

Therefore, in a wood lithographic printing original plate containing the resin particles on the surface 1, the non-image area is made hydrophilic by the force or phoxyl group generated in the resin, and is clearly distinguished from the lipophilicity of the image area, and printing Sometimes, printing ink stops adhering to non-image areas.

In addition, in order to improve the strength of the surface layer itself, its adhesion with the electrophotographic photosensitive layer, or its photographic properties, resins other than the resin particles of the present invention and the matrix resin described above may be added, plasticizers, etc. may be added.

Furthermore, the surface of the surface layer may be mechanically matted for the purpose of improving development characteristics during toner development, adhesion of toner particles, water retention after hydrophilic treatment, etc.
A matting agent may be contained in the layer. As matting agents, fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina, gray, etc.
Polymethyl methacrylate, Boristine, Phenol
Examples include polymer particles such as IV resin.

What is important when forming the surface layer is that the non-image area becomes sufficiently hydrophilic after the desensitization treatment, as described above.

That is, this hydrophilicity can be confirmed, for example, by measuring the contact angle with respect to water. Before the desensitization process, the contact angle of the surface of 1 with water is about 60 to 120', but after the desensitization process, it is 20
'It degrades to below levels and becomes highly perishable in water. For this reason, the printing plate has an image area consisting of lipophilic toner and a highly hydrophilic non-IIS! This means that a quadrant i is formed on its surface. Therefore, the surface layer after desensitization treatment may have a contact angle with water of 20 degrees or less.

The present invention is particularly superior in that its hydrophilicity is even better than conventional ones.

For the photoconductive layer used in the present invention, any photoconductive substance can be used, regardless of whether it is an inorganic photoconductive compound or an organic photoconductive compound.

Examples of inorganic photoconductive substances include zinc oxide, titanium oxide, zinc sulfide, selenium, selenium alloys, cadmium sulfide, cadmium selenide, and silicon, which together with binder resins have photoconductive and intelligent properties. Alternatively, υ alone may be used to form a photoconductive layer by vapor deposition, sputtering, or the like. Organic light guide 1! Examples of polymeric substances include the following (1) to (5).
) can be mentioned.

(1) Polyvinylcarbazole and its derivatives described in Japanese Patent Publication No. 34-10966, (2) Japanese Patent Publication No. 45-18674 and Japanese Patent Publication No. 45-19192
Polyvinylpyrene, polyvinylanthracene, poly-2-viny/I/-4-(4'-:/methyμ aminopheniw)-5-phenyl-oxazole, poly-3-vinyl-N-nitylcarpazo μ described in the publication No. etc. vinyl lv
& coalescence, (3) Polymers such as polyacenaphthynones, polyindenes, copolymers of acenaphthylene and styrene, etc., described in Japanese Patent Publication No. 19193/1983.

(4) Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbachy-formaldehyde resin described in Japanese Patent Publication No. 56-13940, etc.; (5) JP-A-56-90833;
Various triphenylmethane polymers described in Japanese Patent No. 56-161550, and low molecular weight ones include, for example, the following (6) to α-high polymers.

+6) TriacyN derivatives described in USF No. 3112197, etc., oxadiazo-N derivatives described in USP No. 3189447, etc., (8) imidazo-N derivatives described in Japanese Patent Publication No. 57-16096, etc. , +9) USP No. 3615402, USP No. 382098
No. 9, Specification No. 5542544, Japanese Patent Publication No. 45-555
No. 51-10983, JP-A-51-93224, JP-A No. 55-17105, JP-A No. 56-4148, JP-A No. 5
No. 5-108667, No. 55-156953, No. 56
Polyaryl-)v alkane derivatives described in JP-A-56656, etc., HUSP No. 3180729, HUSP 4278746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105557, JP-A-55-51086 , 56-800! M No. 56-88141, No. 57-
No. 45545, No. 54-112637, No. 55-74
Birazoline derivatives and pyrazolone derivatives described in Publication No. 546, etc., αI) USF No. 5615404, Mei.
No. 1-10105, JP-A-54-83435, JP-A No. 54
-110836, No. 54-119925, Special Publication No. 4
Phenyl diamine derivatives described in No. 6-3712, No. 47-28536, etc., +12 USP No. 3567450, Japanese Patent Publication No. 49-3
No. 5702, West German Patent (DAS) No. 1110518, USP No. 5180705, same! No. 5240597,
No. 3658520, No. 4252103, No. 4175
No. 961, Specification No. 4012376, JP-A-55-1
No. 44250, No. 56-119132, Special Publication No. 1977-
Arylamine derivatives described in JP-A-56-22457, etc., (13USF 5
Amino-substituted μco/derivatives described in No. 526501, a4) Described in USF No. 5542546' JA MB, etc. (7) N.

N-bicalpadi/I/derivatives, αS Oxazole derivatives described in USP 3257203, etc., 0e Stiri μ antofcene derivatives described in JP-A-56-46254, etc., α1 JP-A-54-110857, etc. Fluorenone derivatives described in U8USP No. 3717462, JP-A-54-54
No. 9145 (corresponds to USP 41 s oq a)
, JP 55-52063-1 JP 55-52064, JP 55-46760, JP 55-85495,
Vidrazone derivatives disclosed in Japanese Patent No. 57-t1350, Japanese Patent No. 57-148749, etc. Two or more of these photoconductive substances can be used in combination depending on the case.

Among these photoconductive materials, Bo! Triarylamines such as J-N-vinylcabazoletri-p-tolylamine and triphenylamine; 4. Polyaryl-methanes such as 4'-bis(diethylamine)-2,2'-dimethyltriphenylmethane; and 3 -(4-
dimethy~aminopheny)v)-1,5-dipheny)v-
Unsaturated heterocycle-containing compounds represented by pizzoline derivatives such as 2-pizzoline and the like are preferably used.

As the binder that can be combined, all conventionally used binders can be used. Typical examples are vinyl chloride μ-vinyl acetate copolymer, styrene-butacyene ffi metal, nutylene-butyl methacrylate copolymer, polymethacrylate, polyacrylic l/-), polyvinyl acetate, polyvinyl butyral, Alkyto resin, silicone resin, :r-
These include polyester resin, epoxyester/I/vIi resin, and polyester resin. It is also possible to combine an aqueous acrylic emulsion and an acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see
Research-Disclosure
Electrophotographic Elements, Materials and Methods, Vol. 109, pp. 61-67.

Generally, the base of binders present in the photoconductive compositions of the present invention can vary. Typically useful amounts of binder are:
For the amount of photoconductive material and binder mixture, approximately 10
It is within the range of 90% by weight.

Furthermore, conventionally known compounds can be added as spectral enhancers. Examples include xanthine dyes, triphenylmethane dyes, azine dyes, phthalocyanine dyes (metal-containing), and polymethine dyes.
8), 2, “Recording material and photosensitive resin JC, J, You
ng, R.

C, A Review 15.469 (1954) Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers, r6s-c (2),
97 (1980) Yuji Harasaki et al., Industrial Chemistry Magazine, 66.78 and Tadaaki Ichitani,
Journal of the Photographic Society of Japan, 35.20B (1972), Re5earch, Disclosure, 19 B
2, 216, 117-118, general technical data collection, "Recent Development and Practical Application of Photoconductive Materials and Photoreceptors," Nihon Kagaku Information ■Publishing 1st Edition (1986), etc., include known materials.

The photoconductor may be formed from one layer, or may be formed from two or more layers.

In the case of a multilayer structure, for example, the charge generating layer 1 is composed of the vapor-deposited photoconductor or an organic layer such as a phthalonanine pigment or an azo material, and a binder resin added as necessary, and the charge generating layer 1 is composed of the above-mentioned polymer compound or low-molecular compound. One possible example is a so-called resin-separated type photoconductor in which a charge-transporting layer consisting of a molecular compound and a binding resin is laminated.

The photoconductor 11 used in the present invention can be provided on a commonly used and known support. - In general, the support for the electrophotographic photosensitive layer is preferably electrically conductive, and the electrically conductive support is the same as conventional ones, such as metal, paper, plastic sheet, etc., impregnated with a low-resistance substance. those coated with at least 1N3 or more for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and further preventing curling;
A water-resistant adhesive layer is provided on the surface of the support, a pre-coat layer of at least 1.1 or more is provided as necessary on the surface layer of the support, a plastic substrate on which A/, etc. is vapor-deposited. You can use paper laminated.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakaki, Electrophotography 14, (-1), pp. 2-11 (1
975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers”, Kobunshi Publishing (1975), M, F.

Hoover%J, Macromol, Sci, Che
m, A-4(6), pp. 1327-1417 (197
0) etc. can be used.

The coating thickness of the photoconductive composition on a suitable support can vary widely. Normally, about 10 to 300μffl (
However, it can be applied within the range (before drying). The preferred range of coating thickness before drying is within the range of about 50-150 pm. However, useful results can be obtained even outside this range. The dry thickness of this coating may be in the range of about 1 to 50 pm.

The thickness of the surface layer of the present invention is 10 pm or less, and is preferably 1 to 5 .mu.m especially for the Carlson process.

If it is thicker than 5 μm, disadvantages may occur such as a decrease in the sensitivity of the planographic printing original plate as an electrophotographic circle+g light body and an increase in residual potential.

In order to make the lithographic printing original plate of the present invention at the edge of fire, - numerically,
First, a photoconductor 1 is formed on a conductive support according to a conventional method. Next, on this layer, the above-mentioned resin particles, matrix resin, and optionally the above-mentioned additives are dissolved or dissolved in the above-mentioned organic solvent (volatile hydrocarbon solvent) with a boiling point of 200°C or less. It can be manufactured by dispersing it, coating it, and drying it.

A toner image is formed on the original plate obtained as described above in accordance with a conventional electrophotographic method.

A printing plate can be obtained by treating this with a desensitizing treatment liquid (for example, an acidic or alkaline aqueous solution or an aqueous solution containing a reducing agent) to make the non-image area hydrophilic.

In addition to the above-mentioned normal electrophotographic method, methods for forming toner images include (a) electrostatic latent image formed on another electrophotographic photoreceptor and developing it. (b) A method of applying an electric signal to a multi-needle electrode to form an electrostatic latent image according to the electric signal and developing it to obtain a toner image; (c) A method of obtaining a toner image by applying an electric signal to a multi-needle electrode; (c) a method of obtaining a toner image by developing the image. -30320
No. 48-5063, JP-A No. 51-341, etc., an electrostatic latent image is formed on a screen-shaped Nariko photoreceptor having a large number of fine openings, and this electrostatic layer (image There is a method of modulating the ion flow of the corona to form an electrostatic latent image υ by performing corona charging treatment through the medium. A lithographic printing original plate can be used.

As described above, according to the present invention, any conventionally known electrophotographic + g-photo material can be used as a high-quality lithographic printing original plate. The surface layer in the present invention is a skin pattern that exhibits both high hydrophilicity and water resistance after hydrophilic treatment, and also has extremely good adhesion to the substrate and toner image. The generation of stains is extremely suppressed and: it has high printing durability.

Furthermore, since the printing plate of the present invention can maintain almost the original sensitivity of the electrophotographic photosensitive layer, a printing plate material with significantly higher sensitivity than conventional printing material plates for electrophotographic engraving can be obtained. In addition, conventionally, one 11 must have the properties of photoconductivity and hydrophilicity,
Previously, only limited materials such as zinc oxide could be used, but since the printing original plate of the present invention has separate functions into a photoconductive layer and a hydrophilic layer, the range of choices for the photoconductive layer is expanded, and therefore, for example, If you select a material that is highly sensitive to long wavelength light,
Writing can now be performed using a He-Ne laser or a semiconductor laser, which was previously impossible.

In addition, in the printing original plate of the present invention, the non-image area can be made hydrophilic by simply immersing it in a hydrophilic treatment solution for a few seconds, so it is small and
Plate making becomes possible with a simple device.

(Example) Production example 1 of resin particles Dodecyl methacrylate) 95F, acrylic/I/acid 5F and toluene 200? The mixed solution was heated to 70°C with stirring under a nitrogen stream.

To this was added 2,2'-azobis(isobutyronitrile) (abbreviated as B, N) 1.5 F, and the mixture was reacted for 8 hours. Glycidyl methacrylate 12 is added to this reaction mixture solution.
f, t-butylhydroquinone 1? and N,N-dimethyldodecylamine 0.82 was added, and the temperature was 100°C.
The reaction was carried out for 5 hours (dispersion resin (1)).

Next, the above-mentioned dispersion resin (1) a Ot (as solid content), the following simple modification (M-1) 35F, methyl methacrylate) 15? , diethylene glycol dimethacrylate 1
．． A mixed solution of 250 t of Of and n-hebutane was heated to 60° C. with stirring under a nitrogen stream. 2.21-
Azobia, (isovaleronitrile) (abbreviation 1.V,
N, )α3f was added and reacted for 6 hours.

Twenty minutes after the addition of the initiators (V,N), the homogeneous solution became cloudy and the reaction temperature rose to 90''C.

After cooling, a white dispersion was obtained by passing it through a 200 mesh nylon cloth. The average particle size of the latex was 125 μm.

(Monomer M-1) CH3 Production Examples 2 to 11 of Resin Particles In Production Example 1 of Resin Particles, the following production examples were followed except that monomer M-1 was replaced with the following monomer Resin particles were produced in the same manner as in Example 1.

Table-2 Production example 12 of resin particles Ethylene glyco-IV 31.5 f% Anhydrous lid/I/
Acid 51.8? , methacrylate/L/acid &02, trichlorethylene 10f, p-)/Rae/Shonphon fi 0.71 was added, and the mixture was reacted for 6 hours. The reaction temperature is 107”
C, and the temperature was raised to 150°C in 6 hours (the water by-produced by the reaction is De an -ST+ a
A dispersion resin (removed by rk method) was obtained.

This dispersion resin 1134 (as solid content), the following monomer (M-12) 30? , 1,6-hexanedio-cyacrylade [L03f and ethyl acetate/I/150f mixed solution was heated to 60°C under a nitrogen stream. To this, 1.
V, N, and 0.05F were added and reacted for 4 hours to obtain a white dispersion.

After cooling, the average particle size of the resulting dispersion, which was passed through a 200 mesh nylon cloth, was 115 μm.

(Monomer M-12) C'H1 CH! ■C Production example of resin particles 13 Dispersed resin ■7.5? , 40% of the following monomer M-13
t1 styrene/10t1 diviny benzene 1.01F
A solution containing 500% of n-octane was heated to 50''C under a nitrogen stream.To this, 1n-butyllithium α
5f (as solid content) was added and reacted for 6 hours. The average particle size of the obtained white dispersion was Q, 17 μm.

Production Example 14 of Monomer M-13 Hs Resin Particles A solution containing 20f of monomer M-1, α5 of diethylene glyco-μ dimethacrylate, and 1002 of tetrahydrofuran was heated to 75°C under a nitrogen stream. . To this, 1. B, N, and cL2t were added and reacted for 6 hours.

After cooling, the mixture was reprecipitated in Methanol A1500, and the white material was removed and dried. The yield was 16 tons.

Example 1 4,4′-bis(diethylamino′)-2,2′-dimethyμtripheniμmethane 5 as an organic photoconductive substance
t1 bispheno-1vA polycarbonate) (C) Manufactured by E Company, trade name Lexan 121) 5 f.

Spectral sensitizing dye (A) 40 Misaki with the following structural formula, anilide compound (B) Q, 2f with the following structural formula as a chemical sensitizer, methylene chlorphyte 30- and ethylene chloride 30-
- was dissolved in a mixture with - to form a photosensitive liquid.

(Spectral sensitizing dye (A)) (Anilide compound (B)) This photosensitive solution was applied to a conductive transparent support (100 pm polyethylene terephthalate V-) using a wire round rond.
A vapor-deposited film of indium oxide is provided on the support. An organic thin film having a +g optical layer of approximately 4 μm was obtained by coating on a surface (surface resistance: 10 3 Ω).

On the surface of the electrophotographic + g light body obtained here, 5% of Copolymer P-1 (Binding Tree @) of Mizohiro, shown below, and 5% of the particles of Production Example 1 of Resin Particles ( A mixture containing α5 wt.

The j&optical material was immersed in an aqueous solution containing oxalic acid [137 l/ml] for 2 minutes at room temperature to desensitize it.

Copolymer P-1 A 2 μt droplet of distilled water was placed on the copolymer P-1, and the contact angle with the water formed was measured with a goniometer and was found to be 15° or less. The contact angle before the anti-fat treatment was 88°, clearly indicating that the surface layer of the photosensitive material was very well rendered hydrophilic.

The original plate obtained in this way was processed using a fully automatic plate making machine ELP404V (Fuji Photo Film ■) using a negatively charged liquid developer.
(manufactured by Sakurai Seisakusho, Ltd.) to form a toner image, which was desensitized under the same conditions as above, and used as an offset master to print on high-quality paper using an offset printing machine (manufactured by Sakurai Seisakusho@, model 52).

The number of prints that could be printed without causing problems with background stains in the non-image area and image quality in the image area was 10,000.

Example 2 Bisazo @ material 5 of the following structural formula? , tetofhydrofuran 9
A mixture of 30 t of a 5% by weight tetofhydrofuran solution of 5f and polyvinyl μ Butyral LV resin (Denka Kagaku Kogyo 4R: Denka Butyral ÷ 4000-1) was thoroughly ground in a ball mill, and then this mixture was taken out and stirred. Below, 520f of tetrahydrofuran was added. This dispersion was applied onto the conductive transparent support used in Example 1 using a wire round rod to form a charge-generating IJ with a diameter of about α7 μm.

(Bisazonodidae) Next, hydrazone compound 20 of the fjg formula below? , polycarbonate resin (manufactured by E Company, trade name: Lexan 121)
) A mixed solution of zor and tetrahydrofuran 160f was applied onto the charge generation layer using a wire round rod to form a charge transport layer of about 18 μm, thereby obtaining an electrophotographic photoreceptor having a photosensitive layer consisting of 2 layers. Ta.

(Hydrazone Compound) Next, a 5% toxin solution of the hexamethylene diisocyanate-containing copolymer used in Example 1 was applied onto the photosensitive layer using a doctor blade, and the temperature was 100°C. So 2
After drying for hours, a surface layer of about 2 μm was formed.

The photosensitive material prepared in this way was charged to -6 KV with a vapor analyzer (manufactured by Kawaguchi Electric, 5P-428), and the initial potential (Vo) and dark charge retention rate (D, R, R,) were determined.
and the light attenuation exposure amount (El/1°) were measured, each V
o=-560V, D,R,R,=83% and El
/1011.3 (1ux-sec).

Furthermore, as in Example 1, this was performed using fully automatic plate making mELP4.
When the plate was made using ELF-T)+- at 04V, the density of the obtained offset printing master plate was 1.
The image quality was clear when it was 0 or more. Furthermore, the printed matter after being etched and printed with a printing machine, on the other hand, is
There was no capri in the non-image area, and the image was clear.

The above electrostatic property evaluation items were measured as follows.

In a dark room at a temperature of 20°C and 165% RH, each photosensitive material was subjected to corona discharge at 16 KV for 20 seconds using a vapor analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Denki ■), and then left for 10 seconds. , the surface potential V at this time
IO was measured.

Then, the potential V after being left undisturbed for 60 seconds in a dark room
70 was measured, and the potential retention after dark decaying for 60 seconds, that is, the dark decay retention rate (D, R, R, (%)) was expressed as (Vyo
/Vto)xloo (%).

After the surface of the photoconductive layer was charged to -400 V by corona discharge, the surface of the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux until the surface potential (Vl.) attenuated to 1/10. Find the time and from this, the exposure ft Et /10 (
/L/tux・sec).

Example 3 [Benzyl methacrylate V-)/ethyl methacrylate/acrylic acid (!19/60/1 weight ratio)] copolymer (weight average molecular weight 3aOOOO) 45F, zinc oxide 200f, 0
-Zubengai ivα03t1 tetrabromophenol blue 1021. Phthalic anhydride (Llof and toluene 30
A photosensitive layer-forming product was prepared by dispersing the mixture of No. 02 for 2 hours in a POLMI μ, and this was applied to conductive-treated paper with a wire spar so that the dry adhesion amount was 25 f/m'', and the mixture was heated at 100°. It was dried at C for 30 seconds.

5% by weight of copolymer P-2 having the following structure was placed on the photoreceptor.
, Applying a toluene solution containing 5% by weight (solid content) of the particles of Resin Particle Production Example 2 and 4% by weight of hexamethylene diisocyanate IIL with a doctor blade,
Dry and heat for 1.5 hours at a temperature of 100°C to approximately 2μm.
A surface layer was formed.

[Weight ratio]

The electrostatic properties of the lithographic printing original plates prepared in this manner were measured using a paper analyzer under the same conditions as in Example 2. =-530V%D.

R,R,=83% and E,A(,9,6(1ux-s
ec ] De Atsu Kuji, fully automatic plate making machine ELP-404V
When the same operation as in Example 2 was carried out, the density of the obtained offset printing master plate was 1.0 or more, and the image quality was satisfactory. Furthermore, when etching was performed and printed using a printing press, the printed matter after cane printing had no fog in the non-image area and the image was clear.

Examples 4 to 11 In Example 2, operations were performed in the same manner as in Example 2, except that particles shown in Table 3 below were used instead of the resin particles of the present invention (particles of Resin Particle Production Example 1). Each electrophotographic light-sensitive material was produced in this manner.

Table 3 When this plate was made using a fully automatic plate making machine ELF404V in the same manner as in Example 2, the density of the obtained offset printing master and star plate was 1.0 or more and the image quality was clear. Furthermore, when the image was etched and printed using a printing press, the printed matter after printing 10,000 sheets had no fog in the non-image area and had a clear image quality.

Further, this photosensitive material was left for two weeks under conditions of (45 DEG C., 175%'RR), and then treated in exactly the same manner as above, but there was no change at all compared to before aging.

Example 12 The surface of the photoreceptor obtained in Example 3 (5 weights of the particles of Production Example 13 of the resin particles of the present invention, 5X (as Ig weight), 6 weights of copolymer P-3 having the following structure) % and toluene diisocyanate and 0.6% by weight of toluene diisocyanate was applied with a doctor blade and dried at 110 °C for 1.5 hours to form a surface layer of approximately 2 μm.

Copolymer P-3 This was plate-made using the same apparatus as in Example 1, then etched and printed using a printing press. The offset printing master tab V-) obtained after plate making had a yield of 1.0 or more and a clear image quality. Moreover, the image quality of the printed matter after printing 10,000 copies was that of a clear image with no blurring.

Example 13 The powder of Production Example 14 of resin particles was mixed with 102 and the following prepared compound i.
A mixture of 6f of K-combined P-4 and 64t of μ-works/
Dispersion was carried out in a ball mill for 24 hours.

Copolymer P-4 A toluene mixture containing 6% of this dispersion (based on solids) and 1v15% of the market weight of ethylene glyco-μ diglycidyl ether was obtained using a doctor blade as in Example 3; 1 at 110°C after 30 minutes at 80°C.
．． After drying for 5 hours, a surface of about 2 μm was completely formed.

When this was plate-made using the same apparatus as in Example 3, the density of the obtained offset printing master plate was 1.0 or more, and the image quality was fair. Further, when etching was performed and printed on a printing press, the printed matter after printing 10,000 sheets had clear image quality with no fogging.

Furthermore, this l.5 light material oblique ft (45°C175%RH)
After being left for 2, d, and 1 hour under the conditions described above, the same treatment as above was performed, but there was no change at all compared to before the passage of time.

(Effects of the Invention) From the above, the original plate for electrophotographic lithographic printing having the hydrophilizable 1 containing the resin particles of the present invention on the surface 1 has high hydrophilicity and water resistance after hydrophilic treatment. Since the film is compatible with the above, and also has extremely good adhesion to the substrate and toner image, the resulting lithographic printing original plate has excellent quality in terms of both scumming and printing durability.

Claims (2)

[Claims] (1) In an electrophotographic lithographic printing original plate comprising at least one photoconductive layer on a conductive support and a surface layer on the top layer, carboxyl groups are formed in the surface layer by decomposition. An original plate for electrophotographic lithographic printing, characterized in that it contains at least one kind of resin particle containing at least one kind of functional group that generates. (2) In an electrophotographic lithographic printing original plate comprising at least one photoconductive layer on a conductive support and a surface layer on the uppermost layer, carboxyl groups are formed in the surface layer by decomposition. An original plate for electrophotographic lithographic printing, characterized in that it contains at least one type of resin particle which contains at least one type of functional group that produces , and which is at least partially crosslinked.