JPH05210266A - Orignal plate for planographic printing - Google Patents

Abstract

PURPOSE:To improve electrostatic characteristics, to reproduce the copied image faithful to an original picture and to prevent surface staining as an offset original plate by providing a specific photoconductive layer on a conductive base and further providing a specific surface layer on the uppermost layer thereof. CONSTITUTION:This original plate contains specific nonaqueous dispersion resin particles in the surface layer and contains a specific resin A as a binder resin in the photoconductive layer. The nonaqueous dispersion resin particles are obtd. by bringing a monofunctional monomer C which contains the specific functional groups soluble in a nonaqueous solvent and insolubilized in this nonaqueous solvent when polymerized and a monofunctional monomer D which contains a substituent contg. a silicon atom and a fluorine atom and is copolymerizable with this monofunctional monomer C into a dispersion polymn. reaction in the presence of a resin for stabilizing dispersion soluble in the nonaqueous solvent. The specific functional groups form a thiol group, etc., by decomposition. The resin A has is a resin of a low mol.wt. formed by bonding a polymer component of the repeating unit expressed by formula and a polar group at the one terminal of the polymer main chain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic lithographic printing plate precursor prepared by electrophotography, and more particularly to an improvement of a photoconductive layer and a surface layer having specific properties on the photoconductive layer. The present invention relates to a lithographic printing plate precursor.

[0002]

2. Description of the Related Art At present, various types of offset original plates for direct plate making have been proposed and put into practical use. Among them, photoconductive particles such as zinc oxide and a binder resin are main components on a conductive support. The photoconductor provided with the photoconductive layer was subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface was treated with a desensitizing solution called an etchant. A technique for obtaining an offset original plate by selectively hydrophilizing a non-image portion is widely used.

In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoconductor is easily compatible with the desensitizing solution, and the non-image area is sufficiently hydrophilized. It has water resistance, and in printing, the photoconductive layer with the image does not come off, it is well compatible with fountain solution, and it is sufficiently non-image area so that stains do not occur even when the number of printed sheets increases. It is necessary to have such properties as maintaining the hydrophilicity of.

In recent years, a method of preparing a printing plate of a hydrophilic treatment type on the surface of a non-image area which is easy to make by providing a specific resin layer on an ordinary electrophotographic photosensitive member is disclosed in JP-B-45-560.
No. 6 publication. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether, a maleic anhydride copolymer, and a hydrophobic resin compatible with the vinyl ether is provided on the electrophotographic photosensitive layer. This layer is a layer that can be made hydrophilic by hydrolyzing the acid anhydride ring portion by treating the non-image portion with an alkali after forming a toner image (hydrophilizable layer).

The vinyl ether-maleic anhydride copolymer used therein becomes water-soluble in the state of being ring-opened and hydrophilized, so that even if it is miscible with other hydrophobic resin, the layer is formed. The water resistance is extremely poor, and the printing durability is 500 at most.
The limit was ~ 600 sheets.

Further, Japanese Patent Laid-Open Nos. 60-90343 and 60-
159756, 61-217292, etc.,
A method of providing a surface layer (hydrophilizable layer) containing a silylated polyvinyl alcohol as a main component and a crosslinking agent together is disclosed. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. Further, in order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual image hydroxyl groups are crosslinked with a crosslinking agent. And, it is described that, by these, the background stain property of the printed matter is improved and the number of printed sheets is improved.

However, when actually evaluated, it is still unsatisfactory, especially in the background stain. Also,
Silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol with a silylating agent to a desired ratio, but it is difficult to produce it stably because it is a polymer reaction. Furthermore, since the chemical structure of the hydrophilic polymer is limited, 1) chargeability and 2) quality of copied image (halftone dot reproducibility / resolution of image area, Fog in the image area, etc.), 3)
There is a problem that it is difficult to prevent the surface layer from affecting the exposure sensitivity and the like.

In order to improve the problems of the above electrophotographic lithographic printing plate precursor, the present inventors have
An electrophotographic lithographic printing plate precursor using a resin containing a functional group capable of generating a carboxyl group as a main component of the surface layer by decomposition has been proposed (JP-A-62-28345).

Further, as the surface layer resin, a combination of a resin containing a functional group capable of generating a hydrophilic group by decomposition and a compound capable of crosslinking the resin in the photosensitive layer is examined. Those containing a functional group to be generated (JP-A-1-245970, JP-A-1-262556), those containing a functional group to generate a carboxyl group by decomposition (JP-A-1-283527, 1-28).
4860 each), those containing a functional group which produces a thiol group, an amino group, a phosphono group, a sulfo group and the like by decomposition (JP-A-1-304465 and 1-306855).
Each publication) etc.

Further, it has been investigated to use a small amount of fine particles having a functional group capable of generating a hydrophilic group by decomposition in the surface layer and forming a higher order network structure. For example, those containing a functional group capable of generating a carboxyl group by decomposition (JP-A-2-13965), those containing a functional group capable of generating a hydroxyl group by decomposition (JP-A-2-13966), and sulfo by decomposition. A group containing a functional group that generates a group, a phosphono group, etc. (JP-A-2-13967) is disclosed.

These binder resins or resin particles form a hydrophilic group by being hydrolyzed, hydrolyzed or photolyzed by a desensitizing solution or immersion water used for printing. When these are used as the surface layer resin of the lithographic printing plate precursor, in any case, deterioration of electrophotographic properties (dark charge retention amount and photosensitivity) caused when the hydrophilic group itself is contained from the beginning can be avoided. The hydrophilicity of the non-image area which is hydrophilized by the desensitizing liquid is more expressed by the hydrophilic group produced by decomposition in the binder resin or resin particles in the surface layer, thereby improving the hydrophilicity of the image area. The oiliness and hydrophilicity of the non-image area become clear, the printing ink is prevented from adhering to the non-image area at the time of printing, and the surface layer has a crosslinked structure, so that the resin hydrophilized Further, it becomes water-insoluble, and due to the cross-linking effect, the hydrophilic cross-linking resin contains water and swells, water retention is created, and the hydrophilicity of the surface layer is sufficiently maintained. As a result, it becomes possible to print a large number of printed matter with clear image quality without scumming.

[0012]

The resin of the type which produces a hydrophilic group by the above decomposition reaction is decomposed by a treatment liquid to decompose a carboxyl group or a hydroxyl group masked with a protecting group in advance, thereby leaving the protecting group. It is what makes them. Therefore, this type of resin is stable and does not hydrolyze under the influence of atmospheric humidity (moisture) during storage, and the deprotection group reaction proceeds rapidly during the hydrophilization process to make it hydrophilic. It is required as an important property that a group is generated and the hydrophilicity of the non-image area can be improved.

However, if a hydrophilic group-forming functional group (protecting group) that stably exists without being decomposed even under severe conditions such as storage in a hot and humid environment for a long period of time is used, a rapid decomposition by the treatment liquid and a hydrophilic group It has been found that difficulties arise in rapid onset. In view of such a situation, the present invention is more effective due to the hydrophilicity of the non-image area, more stable even when stored under extremely severe conditions, and easily hydrophilic in a short time during the hydrophilic treatment. The object of the present invention is to provide a lithographic printing plate precursor that can exhibit the above.

That is, the object of the present invention is to have excellent electrostatic characteristics (especially dark charge retention and photosensitivity), to reproduce a copy image faithful to the original image, and of course, to obtain a uniform stain as an offset original plate. Another object of the present invention is to provide a lithographic printing plate precursor that is excellent in desensitization and does not generate dot-like background stains.
Another object of the present invention is to provide a lithographic printing plate precursor having high printing durability, in which the hydrophilicity of the non-image area is sufficiently maintained and scumming does not occur even when the number of printed sheets is increased in printing. .

Another object of the present invention is to provide a lithographic printing plate precursor having a clear and high-quality image even when the environment at the time of forming a copy image changes such as low temperature / low humidity or high temperature / high humidity. is there. Another object of the present invention is to provide a lithographic printing plate precursor that is not easily affected by the types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even in a scanning exposure system using a semiconductor laser beam.

[0016]

SUMMARY OF THE INVENTION The present invention is directed to the above object of utilizing an electrophotographic photosensitive member comprising a conductive support, at least one photoconductive layer provided thereon, and a surface layer provided on the uppermost layer thereof. In the lithographic printing plate precursor, at least one of the following non-aqueous solvent-based dispersed resin particles [L] is contained in the surface layer, and the following resin [A] is used as the binder resin of the photoconductive layer. This is achieved by a lithographic printing plate precursor containing at least one kind.

The non-aqueous dispersion resin particles [L] are soluble in the non-aqueous solvent but insoluble in the non-aqueous solvent by polymerization, and are insoluble in the non-aqueous solvent by decomposition, thiol group, sulfo group, amino group and -P. _{(= Z 0) (- Z} 0 -H) R '1
The group [Z ₀ represents an oxygen atom or a sulfur atom. R _'1 is -Z ₀ -H, a hydrocarbon or -Z ₀ -R' functional for generating at least one group (hydrophilic group) of ₂ (R _'2 represents a hydrocarbon group) represent a] A monofunctional monomer (C) containing at least one group and a monofunctional monomer containing a substituent containing a silicon atom and / or a fluorine atom and copolymerizable with the monofunctional monomer (C) A copolymer resin particle obtained by subjecting a monomer (D) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, wherein the resin [A] is 1 × 10 ³ It has a weight average molecular weight of 2 to 10 ⁴ and contains 30 wt% or more of the repeating unit represented by the following general formula (I) as a polymer component, and at one end of the polymer main chain, -PO ₃ H _2, -SO ₃ H, -C
OOH, -P (= O) (OH) R ₀₁ [R ₀₁ represents a hydrocarbon group or -OR ₀₂ (R ₀₂ represents a hydrocarbon group)] [-P (= O) (OH) R ₀₁ above] Is

[0018]

[Chemical 4]

Is shown. ] And at least one polar group selected from cyclic acid anhydride-containing groups.

[0020]

[Chemical 5]

[However, in the above formula (I), a ₁ , a
Each ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. Furthermore, it is preferable that the non-aqueous solvent-based dispersed resin particles form a crosslinked structure. Furthermore, it is preferable that the dispersion stabilizing resin contains at least one polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain.

[0022]

[Chemical 6]

[In the general formula (II), V ₀ is -O
-, - COO -, - OCO -, - (CH 2) p OCO
_{-, - (CH 2) p} COO -, - SO 2 -, - CONR
_{1 -, - SO 2 NR 1} -, - C 6 H 5 -, - CONHC
Represents OO- or -CONHCONH- (provided that p is
Represents an integer of 1 to 4, and R ₁ is a hydrogen atom or has 1 carbon atom.
Represent to 18 hydrocarbon group), b _1, b ₂ is through one another may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₂ or a hydrocarbon group -COO-R ₂ (R ₂ represents a hydrogen atom or a hydrocarbon group which may be substituted)] Furthermore, the above resin [A] is the following as a copolymer component represented by the general formula (I): It is preferable to contain at least one of the aryl group-containing methacrylate components represented by the general formula (Ia) and the following general formula (Ib) (resin [A ′]).

[0024]

[Chemical 7]

[In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR ₀₄ or-
COOR ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ are each -COO-
Represents a single bond or a connecting group having 1 to 4 connecting atoms for connecting the benzene ring. The present invention utilizes an electrophotographic photoreceptor including a photoconductive layer containing a resin [A] as a binder resin and further provided with an uppermost layer (surface layer) containing non-aqueous dispersion resin particles [L]. A lithographic printing plate precursor for an electrophotographic plate making system.

That is, after forming a toner image according to a usual electrophotographic process (plate making), the non-image portion is contained in the uppermost layer of non-aqueous dispersion resin particles [L] (hereinafter abbreviated as resin particles [L]). In some cases), the lipophilic surface is modified to a hydrophilic surface by a desensitizing treatment to obtain a printing original plate.

Usually, in the electrophotographic photoreceptor, if one more layer (surface layer) is provided on the photoconductive layer for the purpose of improving the quality of the printed matter, the electrostatic properties (particularly the photosensitivity, residual potential, etc.) will decrease. Since the faithful image reproducibility is deteriorated, various improvements are attempted, and the influence is great.

As a result of various studies by the present inventors on this problem, the use of the resin [A] makes it possible to improve the electrostatic characteristics of the photoconductive layer, and when the image is actually taken, the copy image is reproduced. Faithful reproducibility is not impaired, and further, the resin particles [L] of the present invention are produced in the presence of a dispersion stabilizing resin containing silicon atoms / fluorine atoms to produce the uppermost layer. By containing the specific resin particles [L] in the surface layer, the necessary amount that can be efficiently used for water retention can be suppressed to a smaller amount as compared with the conventional resin or resin particles that cause hydrophilicity. Thus, the conventional drawbacks were overcome, and water retention and printing durability were improved without adversely affecting the photoconductive layer.

The resin particles [L] in the surface layer used in the present invention have an average particle diameter of 1 μm or less and a narrow distribution of particle diameters, and as the resin particles [L], It has at least two important properties. One of them is the above-mentioned hydrophilic group [monofunctional monomer (C, which is protected by a chemical reaction such as hydrolysis, nucleophilic substitution reaction, redox reaction or photolysis reaction during desensitization. )] Is a thiol group, a sulfo group, an amino group, -P (=
Z ₀ ) (-Z ₀ -H) R ' ₁ groups are generated and converted from hydrophobic to hydrophilic nature.

The resin particles [L] can exhibit hydrophilicity and, at the same time, when the resin particles [L] have a crosslinked structure, at this time, the resin particles [L] have hydrophilicity and are insoluble or hardly soluble in water. It also has water swelling properties.

As another one, a substituent having strong lipophilicity,
That is, by combining with a polymer component [monofunctional monomer (D)] containing at least a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom, the fluorine atom and / or Or, due to the large lipophilicity of the silicon atom-containing substituent, it migrates to the surface portion of the photoconductive layer.
This shows that a concentration phenomenon occurs.

Further, a dispersion stabilizing resin for stabilizing dispersion of the non-aqueous dispersion resin particles is adsorbed on the insolubilized copolymer portion in the reaction process of polymerization granulation and / or represented by the above formula (II). In the case of the dispersion-stabilizing resin containing a polymerizable double bond group portion, both polymer components are chemically bonded.

Due to both the effects of concentrating the resin particles [L] on the surface portion and making the resin particles [L] hydrophilic by the desensitizing treatment as described above, the water retentivity of the non-image area of the surface layer is improved. It is fully achieved.

In the present invention, the binder resin for the photoconductive layer contains a specific polymer component represented by the formula (I) and has the specific polar group bonded to at least the side chain of the polymer. It is to contain a low molecular weight polymer resin [A].

As a result, the electrostatic properties are improved, and the photoconductive layer further contains photoconductive zinc oxide particles, a spectral sensitizing dye,
And a low molecular weight resin [A] having a specific polar group bonded to one end of the main chain of the polymer when the resin [A] is dispersed.
Compensates for trapping of photoconductive zinc oxide by adsorbing on stoichiometric defects of photoconductive zinc oxide and appropriately covering and adsorbing the interaction state of zinc oxide and dye. At the same time, it is considered that while the humidity characteristics are dramatically improved, the photoconductive zinc oxide is sufficiently dispersed and the aggregation is controlled.

Particularly, in the case of the conventional binder resin, when the kind of the spectral sensitizing dye is changed, the interaction such as adsorption is hindered and satisfactory electrophotographic characteristics cannot be obtained. However, when the resin [A] of the present invention is used, remarkably excellent performance can be satisfied even with a dye used for spectral sensitization for semiconductor laser light. Further, when the resin [A '] is used, the electrophotographic characteristics (particularly V) are further improved as compared with the case of the resin [A].
₁₀ , D.I. R. R. , E _1/10 ) can be improved.

The reason for this is unknown, but one reason is that the planar curing of the benzene ring or naphthalene ring, which is the ester component of the methacrylate, causes the alignment of these polymer molecular chains at the zinc oxide interface in the film. Probably due to being done properly.

The non-aqueous solvent-based dispersed resin particles contained in the surface layer in the present invention will be described in detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization.

The non-aqueous solvent-based dispersed resin particles (hereinafter sometimes referred to as resin particles [L]) contained in the surface layer in the present invention will be described in detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. The non-aqueous solvent-based dispersed resin particles of the present invention are decomposed to give a thiol group, a sulfo group, an amino group and -P (= Z ₀ ).
(-Z ₀ -H) R _'1 group [Z ₀ represents an oxygen atom or a sulfur atom. R _'1 is -Z ₀ -H, a hydrocarbon or -Z ₀
-R ' ₂ (R' ₂ represents a hydrocarbon group)] containing at least one functional group forming at least one group, and a monofunctional compound which is insoluble in the non-aqueous solvent after polymerization. Copolymerization with a polymer component consisting of a monomer (C) [abbreviated as polymer component (C)] and the monofunctional monomer (C) containing at least a fluorine atom and / or a silicon atom as a substituent. It is obtained by polymerizing a possible monofunctional monomer (D) in the presence of a dispersion stabilizing resin which is soluble in the non-aqueous solvent.

The molecular weight of the dispersed resin particles is 10 ⁴ to 10 ⁶ ,
It is preferably 10 ^{4 to} 5 × 10 ⁵ . The proportion of the monomer (C) as a polymerization component in the resin particles is 30% by weight or more, preferably 50% by weight or more, and the monomer (D) is used.
Is 0.5 to 30% by weight, preferably 1
% By weight to 20% by weight. When containing other copolymerizable monomers, the content is at most 30% by weight or less.

The solubility of the dispersion-stabilizing resin of the present invention in the non-aqueous solvent may be at least 5% by weight in 100 parts by weight of the solvent at a temperature of 25 ° C.

The weight average molecular weight of the dispersion stabilizing resin is 1 × 10 ³ to 1 × 10 ⁵ , preferably 2 × 10 ^3.
To 5 × 10 ⁴ , particularly preferably 3 × 10 ³ to 2 × 10 ^4.
Is.

The weight average molecular weight of the dispersion stabilizing resin is 1 × 1.
When it is less than 0 ³ , the generated dispersed resin particles agglomerate, and fine particles having a uniform average particle diameter cannot be obtained. On the other hand, when it exceeds 1 × 10 ⁵ , the effect of the present invention that the water retention is improved while satisfying the electrophotographic characteristics when added to the surface layer is diminished.

In the total sum of the repeating units of the monomer (D) of the present invention, the repeating unit having a substituent containing a fluorine atom and / or a silicon atom is preferably contained in an amount of 40% by weight or more based on the whole. , And more preferably 60
~ 100 wt% or more.

When the amount of the above components of the present invention is less than 40% by weight based on the total weight, the effect of concentrating on the surface portion when the resin particles are dispersed in the surface layer decreases, and as a result, the effect of improving water retention as a printing original plate. Will fade.

For the monomer (C) and the monomer (D) which are insolubilized as described above, preferably one dispersion stabilizing resin is used.
.About.50% by weight, more preferably 2 to 30% by weight.

Next, the resin particles [L] of the present invention will be described in detail. As used in the present invention, at least one thiol group, sulfo group, amino group, -P (=
The functional group which forms at least one hydrophilic group of the Z ₀ ) (-Z ₀ -H) R ' ₁ group (hereinafter sometimes simply referred to as a hydrophilic group-forming functional group) will be described in detail.

The hydrophilic group-forming functional group of the present invention decomposes to form at least one hydrophilic group, and the number of hydrophilic groups formed from one functional group may be one or two or more.
Hereinafter, the functional group that generates at least one thiol group by decomposition (thiol group-forming functional group) will be described in detail.

According to one preferred embodiment of the present invention, the thiol group-forming functional group-containing resin has, for example, the following general formula (C
-I) - at least a functional group represented by [S-L ^A]
It is a resin containing seeds.

The general formula (C-I): - in [S-L ^A] expression, L ^{A _{is, -Si (R A 1) (}} R A 2)
_{^{(R A 3), - CO}} -R A 4, -CO-R A 5, -CO
_{^{-O-R A 6, -CS-}} O-R A 7, -S-R A 8, -
CS-N ( ^RA ₉ ) ( ^RA ₁₀ ) or

[0051]

[Chemical 8]

Represents However, R ^A ₁ , R ^A ₂ and R ^A
₃ may be the same or different, each represents a hydrocarbon group or ^{-O-R A '(R A} ' represents a hydrocarbon _{^{group), R A 4, R A}} 5, R A 6, R A 7 , R ^A ₈ ,
R ^A ₉ , R ^A ₁₀ , R ^A ₁₁ , R ^A ₁₂ and R ^A ₁₃ each independently represent a hydrocarbon group, and Y ₁ represents an oxygen atom or a sulfur atom.

[0053] functional group of the general formula [-S-L ^A] is degraded by, is intended to generate a thiol group, is described below in more detail. L ^A is -Si (R ^A ₁ ) (R ^A ₂ )
In the case of representing ( ^RA ₃ ), R ^A ₁ , R ^A ₂ and R ^A ₃ may be the same or different from each other, preferably a hydrogen atom or an optionally substituted straight chain having 1 to 18 carbon atoms. Or a branched alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), substituted Alicyclic group (eg cyclopentyl group, cyclohexyl group etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group etc.) or substituted Aromatic groups such as phenyl, naphthyl, chlorophenyl, tolyl, methoxyphenyl, methoxycarbonylphenyl, diphenyl Rorofeniru group) or -O-
R ^A ′ ( ^RA ′ represents a hydrocarbon group, and specifically, the substituents of the hydrocarbon group of R ^A ₁ , R ^A ₂ and R ^A ₃ can be mentioned as an example).

L ^A is --CO-- ^RA ₄ , --CO-- ^RA ₅ ,
_{^{-CO-O-R A 6,}} -CS-O-R A 7, or -S-
In the case of representing R ^A ₈ , R ^A ₄ , R ^A ₅ ,
R ^A ₆ , R ^A ₇ , and R ^A ₈ are each preferably a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, trichloromethyl group, trifluoromethyl group, methoxy). Methyl group, ethyl group, propyl group, n-butyl group, hexyl group, 3-chloropropyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexylfluoro-i-propyl group Group, octyl group, decyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group, etc.) An optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphene) Group, represents methoxyphenyl group, butoxyphenyl group, chlorophenyl group, dichlorophenyl group, a trifluoromethylphenyl group).

[0055] In the case where L ^A represents a _{^{-CS-N (R A 9)}} (R A 10), R A 9 and R ^A ₁₀ may be the same or different from each other, the preferred examples R ^A ₄ ~
It represents a preferred substituent for R ^A ₈ .

L ^A is

[0057]

[Chemical 9]

In the case of representing, Y ₁ represents an oxygen atom or a sulfur atom. R ^A ₁₁ , R ^A ₁₂ and R ^A ₁₃ may be the same or different from each other, preferably a hydrogen atom,
It represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted.

As a preferred example, the same contents as R ^A _{4 to} R ^A ₈ are represented. p represents an integer of 5 or 6. Another preferable thiol group-forming functional group-containing resin of the present invention is a resin containing at least one thiirane ring represented by the general formula (C-II) or the general formula (C-III).

[0060]

[Chemical 10]

In the formula (C-II), R ^A ₁₄ and R ^A
₁₅ may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above R
^The preferred substituents for ^A _{4 to} R ^A ₈ are shown.

In the formula (C-III), X ^A represents a hydrogen atom or an aliphatic group. Preferably as an aliphatic group,
It represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.).

Still another preferred thiol group-forming functional group-containing resin of the present invention is a resin containing at least one sulfur atom-containing heterocyclic group represented by the general formula (C-IV).

[0064]

[Chemical 11]

[0065] formula (C-IV), Y ^A represents an oxygen atom or -NH- group. R ^A ₁₆ , R ^A ₁₇ , and R ^A ₁₈
May be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, a hydrogen atom or the above R ^A ₄
Represent preferred and the substituents to R ^A _8.

R ^A ₁₉ and R ^A ₂₀ may be the same or different and each represents a hydrogen atom, a hydrocarbon group or —O—R ^A ″.
( ^RA "represents a hydrocarbon group), preferably the substituents mentioned above as preferred in ^RA _{1 to} ^RA ₃ .

According to yet another preferred embodiment of the present invention, the thiol group-forming functional group-containing resin has a form in which at least two thiol groups sterically close to each other are simultaneously protected by one protecting group. It is a resin containing at least one functional group.

Examples of the functional group having at least two thiol groups sterically close to each other simultaneously protected by one protecting group include, for example, the following general formula (CV),
The thing represented by (C-VI) and (C-VII) can be mentioned.

[0069]

[Chemical 12]

In formulas (C-V) and (C-VI), Z ^A represents a carbon-carbon bond which may have a heteroatom or a C-S bond which directly connects the two bonds (provided that sulfur is present). The number of atoms between the atoms is 4 or less). Further, one of the-(Z ^A ... C) -bonds represents only a bond, and may be, for example, as shown below.

[0071]

[Chemical 13]

In the formula (C-VI), R ^A ₂₁ , R ^A ₂₂
May be the same or different and each represents a hydrogen atom, a hydrocarbon group or -O- ^RA "( ^RA " represents a hydrocarbon group). In formula (C-VI), R ^A ₂₁ and R ^A ₂₂ may preferably be the same or different from each other, and a hydrogen atom,
Alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, octyl group, etc.), carbon number 7
To 9 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group, chlorobenzyl group, etc.), alicyclic groups having 5 to 7 carbon atoms (eg, cyclopentyl group, cyclohexyl group) Or an optionally substituted aryl group (eg, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group,
A cyanophenyl group) or -O- ^RA "( ^RA " is ^RA
_{21 has} the same meaning as the hydrocarbon group for R ^A ₂₂ ).

In the formula (C-VII), R ^A ₂₃ , R ^A
₂₄ , R ^A ₂₅ and R ^A ₂₆ may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Preferably, it has the same meaning as the hydrogen atom or the hydrocarbon group described above as preferred in R ^A ₂₁ and R ^A ₂₂ .

General formula (C-I) used in the present invention:
Examples of the monomer (C) containing at least one functional group represented by (C-VII) include those described in Yoshio Iwakura and Keisuke Kurita, “Reactive Polymer”, pages 230 to 237 (Kodansha: 1977), Japan. Chemistry Society, "New Experimental Chemistry Course Vol. 14, Synthesis and Reactions of Organic Compounds [III]", Chapter 8, pp. 1700-
1713 (Maruzen Co., Ltd., 1978), J. F.
W. McOmie "Protective Group
s in Organic Chemistry "No. 7
Chapter (Plenum Press. 1973), S.
Patai "The Chemistry of the
e thiol group Part 2 "Chapter 12,
Chapter 14 (John Wiley & Sons, 19
1974) and the like can be applied.

More specifically, general formulas (C-I) to (C
Examples of the monomer containing the functional group of -VII) include the following compounds.

[0076]

[Chemical 14]

[0077]

[Chemical 15]

[0078]

[Chemical 16]

[0079]

[Chemical 17]

[0080]

[Chemical 18]

[0081]

[Chemical 19]

[0082]

[Chemical 20]

Next, at least one -P is decomposed.
_{(= Z 0) (- Z} 0 -H) R '1 groups are, for example will be described in detail a functional group generating a group of the following general formula (C-VIII) or (C-IX).

[0084]

[Chemical 21]

In the formula (C-VIII), R ^B is a hydrocarbon group or —Z ^B ₂ —R ^B ′ (where R ^B ′ represents a hydrocarbon and Z ^B ₂ represents an oxygen atom or a sulfur atom). Represents.

Q ^B ₁ represents an oxygen atom or a sulfur atom. Z ^B ₁ represents an oxygen atom or a sulfur atom. Formula (I
In X), Q ^B ₂ , Z ^B ₃ and Z ^B ₄ each independently represent an oxygen atom or a sulfur atom.

Preferably, R ^B is an optionally substituted alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group) or —Z ^B ₂ —R ^B ′ (where Z is Z).
^B ₂ represents an oxygen atom or a sulfur atom.

R ^B 'represents the same contents as R ^B. Q
^B ₁ , Q ^B ₂ , Z ^B ₁ , Z ^B ₃ , and Z ^B ₄ each independently represent an oxygen atom or a sulfur atom.

By the above decomposition, the formula (C-VIII) is obtained.
Alternatively, the functional group which forms a phospho group represented by (C-IX) includes a functional group represented by the general formula (X) and / or (XI).

[0090]

[Chemical formula 22]

In formulas (C-X) and (C-XI),
Represents a ^{_{Q B 1, Q B 2,}} Z B 1, Z B 3, Z B 4 and R ^B are each formula (C-VIII) and content as defined in (C-IX).

L ^B ₁ , L ^B ₂ and L ^B ₃ are each independently-[C (R ^B ₁ ) (R ^B ₂ )] _n -X ^B ₁ ,

[0093]

[Chemical formula 23]

-Si (R ^B ₃ ) (R ^B ₄ ) (R ^B ₅ ),
_{^{-CO-R B 6, -CS-}} R B 7, -CO-O-
R ^B ₈ , -CS-O-R ^B ₉ , -S-R ^B ₁₀ ,

[0095]

[Chemical formula 24]

Represents L ^B _{1 to} L ^B ₃ are-[C (R ^B
₁₎ (R ^B _{2)] n} -X ^B ₁ or

[0097]

[Chemical 25]

In the case of representing, R ^B ₁ and R ^B ₂ may be the same as or different from each other and represent a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom, fluorine atom, etc.) or a methyl group. X ^B ₁ and X ^B ₂ are electron withdrawing groups (here, the electron withdrawing group is a substituent having a positive Hammett substituent constant, for example, a halogen atom or —COO).
-, - CO -, - SO 2 -, - CN -, - NO 2 , etc. represent like is) is preferably a halogen atom (e.g. a chlorine atom, a bromine atom, a fluorine atom, etc.), - CN -, - CO
NH _2, -NO ₂ or _{^{-SO 2 R B "(R B}} " is such as methyl group, ethyl group, propyl group, butyl group, hexyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group Represents a hydrocarbon group). n is 1 or 2
Represents. Further, when X ^B ₁ is a methyl group, R ^B ₁
And R ^B ₂ is a methyl group and n = 1.

L ^B _{1 to} L ^B ₃ are —Si (R ^B ₃ ) (R ^B
₄ ) (R ^B ₅ ), R ^B ₃ , R ^B ₄
And R ^B ₅ may be the same or different from each other, preferably a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group). Group, hexyl group, octyl group,
Decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (eg cyclopentyl group, cyclohexyl group, etc.), optionally substituted carbon number 7 to 12 aralkyl groups (eg, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, etc.) and optionally substituted aromatic groups (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonyl group) Phenyl group, dichlorophenyl group, etc.) or −
O—R ^B ″ ″ (R ^B ″ ″ represents a hydrocarbon group, and specifically, the substituents of R ^B ₃ , R ^B ₄ , and R ^B ₅ can be mentioned as an example). Represent.

L ^B _{1 to} L ^B ₃ are -CO-R ^B ₆ , -CS.
_{^{-R B 7, -CO-O-}} R B 8, -CS-O-R B 9,
Or in the case of representing the _{^{-S-R B 10, R B}} 6, R B
₇ , R ^B ₈ , R ^B ₉ and R ^B ₁₀ each independently represent a hydrocarbon group. Preferably, it has 1 to 1 carbon atoms which may be substituted.
6 linear or branched alkyl groups (for example, methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group, phenoxymethyl group, 2,2,2-trifluoroethyl group, ethyl group, propyl group, hexyl group) Group, t-
Butyl group, hexafluoro-i-propyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group, methoxybenzyl group) Etc.), an optionally substituted aryl group having 6 to 12 carbon atoms (eg, phenyl group, tolyl group, xylyl group, nitrophenyl group, cyanophenyl group, methanesulfonylphenyl group, methoxyphenyl group, butoxyphenyl group, chlorophenyl group). , Dichlorophenyl group, trifluoromethylphenyl group, etc.).

Further, L ^B _{1 to} L ^B ₃ are

[0102]

[Chemical formula 26]

In the case of representing Y ^B ₁ and Y ^B ₂
Represents an oxygen atom or a sulfur atom. The monomer (C) containing at least one functional group used in the present invention can be synthesized by introducing a protecting group according to a conventionally known method. As a method for introducing a protecting group, the same synthetic reaction can be used. Specifically, J.
F. W. McOmie "Protective gro
ups in Organic Chemistry "
Method described in Chapter 6 (Plenum Press, published in 1973), or "Chemical Experimental Society of Japan, Volume 14, New Synthetic Chemistry, Vol. 14, Synthesis and Reaction of Organic Compounds [V]", page 2497, published by Maruzen Co., Ltd., 1978. ) And the like, a synthetic reaction similar to the method of introducing a protective group into a hydroxyl group, or S.I. Patai "The Chemistry of
the Triol Group Part 2 "13th
Chapter, Chapter 14 (Wiley-Interscience
1974), T.S. W. Greene "Protec
TIVE GROUPS ORGANIC SYN
thesis ”Chapter 6 (Wiley-Intersci
ence 1981) and other methods for introducing a protective group into a thiol group.

The following examples are given as specific examples of the compound which can be a repeating unit of the polymerization component containing the functional group of the general formula (C-X) and / or (C-XI) used for the protecting group. You can

[0105]

[Chemical 27]

[0106]

[Chemical 28]

[0107]

[Chemical 29]

Then, by decomposition, an amino group such as --NH
Examples of the functional group that forms ₂ groups and / or —NHR ^c group include the following general formulas (C-XII) to (C-XIV).
The group represented by can be mentioned.

[0109]

[Chemical 30]

Formula (C-XII) and formula (C-XIV)
In the formula, R ^c ₀ is a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2 -Chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 2-cyanoethyl group, 2
-Methoxyethyl group, 2-ethoxyethyl group, 2-methoxycarbonylethyl group, 3-methoxypropyl group, 6
-Chlorohexyl group, etc.), an alicyclic group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), and an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, 3- Phenylpropyl group, 1-
Phenylpropyl group, chlorobenzyl group, methoxybenzyl group, bromobenzyl group, methylbenzyl group, etc.), aryl group having 6 to 12 carbon atoms which may be substituted (eg phenyl group, chlorophenyl group, dichlorophenyl group, tolyl group, xylyl Group, mesityl group, chloromethyl group, chlorophenyl group, methoxyphenyl group, ethoxyphenyl group, chloromethoxyphenyl group, etc.) and the like.

When R ^c ₀ preferably represents the hydrocarbon group, hydrocarbon groups having 1 to 8 carbon atoms can be mentioned. In the functional group represented by the formula (C-XII), R ^c ₁ represents an optionally substituted aliphatic group having 2 to 12 carbon atoms,
More specifically, R ^c ₁ represents a group represented by the following formula (C-XV).

[0112]

[Chemical 31]

In formula (C-XV), A ₁ and A ₂ are each a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, etc.) or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted (eg, methyl group). Group, ethyl group, propyl group, butyl group, hexyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-chloroethyl group, 3-bromopropyl group, cyclohexyl group, benzyl group, chlorobenzyl group, methoxy Benzyl group, methylbenzyl group, phenethyl group, 3-phenylpropyl group, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, methoxyphenyl group, dichlorophenyl group, chloromethylphenyl group, naphthyl group, etc., Y ^c is a hydrogen atom,
Halogen atom (eg, fluorine atom, chlorine atom, etc.), cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), aromatic group which may have a substituent (For example, phenyl group, tolyl group, cyanophenyl group, 2,6-dimethylphenyl group, 2,4,6-
Trimethylphenyl group, heptamethylphenyl group, 2,
6-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2-propylphenyl group, 2-butylphenyl group, 2-chloro-6-methylphenyl group, furanyl group) or -SO ₂ -R ^c ₆ (R ^c ₆ has the same ^{meaning as} the hydrocarbon group of Y ^c ) and the like. n represents 1 or 2.

More preferably, when Y ^c is a hydrogen atom or an alkyl group, a ₁ and a ₂ on the carbon adjacent to the oxygen atom of the urethane bond represent a substituent other than a hydrogen atom. When Y ^c is not a hydrogen atom or an alkyl group, A
₁ and A ₂ may be any of the groups described above.

That is,-[C (A ₁ ) (A ₂ )] _n -Y ^c
In the above, it is shown that the case where a group containing at least one or more electron-withdrawing groups is formed or the case where the carbon adjacent to the oxygen atom of the urethane bond forms a sterically bulky group is a preferable example. is there.

R ^c ₁ is an alicyclic group (eg, a monocyclic hydrocarbon group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methyl-cyclohexyl group, 1-methylcyclobutyl group, etc.) Or a bridged cyclic hydrocarbon group (bicyclooctane group, bicyclooctene group,
Bicyclononane group, tricycloheptane group and the like).

In the general formula (C-XIII), R ^c ₂
And R ^c _{3, which} may be the same or different, each represents a hydrocarbon group having 1 to 12 carbon atoms, and specifically, is represented by the formula (C-
It has the same meaning as the aliphatic group or aromatic group in Y ^c of XII).

In formula (C-XIV), X ^c ₁ and X ^c ₂ may be the same or different and each represents an oxygen atom or a sulfur atom. R ^c ₄ and R ^c ₅ may be the same or different and each represents a hydrocarbon group having 1 to 8 carbon atoms, specifically, an aliphatic group or an aromatic group for Y ^c of formula (C-XII). Represents.

Specific examples of the functional groups of the formulas (C-XII) to (C-XIV) are shown below.

[0120]

[Chemical 32]

[0121]

[Chemical 33]

[0122]

[Chemical 34]

[0123]

[Chemical 35]

Functional groups used in the present invention which generate an amino group (for example, --NH ₂ group and / or --NHR group) by decomposition, such as the above general formulas (C-XII) to (C-XI).
The monomer (C) containing at least one functional group selected from the group V) is, for example, “New Experimental Chemistry Lecture Vol. 14, Organic Compound Synthesis and Reaction [V]” No. 2555, edited by Nippon Kagaku.
Page (published by Maruzen Co., Ltd.), J. F. W. McOmie P
protective groups in Organ
ic Chemistry "Chapter 2 (Plenum P
(Res. 1973), "Protective
groups in Organic Sinthes
is ”Chapter 7 (John Wiley & Sons, 1
981) and the like.

Further, as the functional group capable of generating at least one sulfo group by decomposition, for example, a general formula (C-X
VI) or a functional group represented by (C-XVII).

[0126] Formula _{(C-XVI) -SO 2 -O} -R D 1 formula _{(C-XVII) -SO 2 -S} -R D 2 formula (C-XVI) Medium R ^D ₁ is - [C ( R ^D ₃ )
(R ^D _{4)] n} -Y ^D,

[0127]

[Chemical 36]

[0128] or represents a -NHCOR ^D _7. Formula (C-
In XVII), R ^D ₂ represents an aliphatic group having 1 to 18 carbon atoms which may be substituted, or an aryl group having 6 to 22 carbon atoms which may have a substituent.

The above general formulas (C-XVI) and (C-XVI)
The functional group of I) produces a sulfo group by decomposition, and will be described in more detail below. R ^D ₁ is-[C
In the case of representing ( ^RD ₃ ) ( ^RD ₄ ) -Y ^D , R
^D ₃ and R ^D ₄ may be the same or different and each is a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.).
Alternatively, it represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group). Y ^D is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, trifluoromethyl group, methanesulfonylmethyl group, cyanomethyl group,
2-methoxyethyl group, ethoxymethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, 2-methoxycarbonylethyl group, 2-propoxycarbonylethyl group, methylthiomethyl group, ethylthiomethyl group, etc.), carbon number 2 To 18 optionally substituted alkenyl groups (eg vinyl group, allyl group, etc.), aryl groups having 6 to 12 carbon atoms and optionally substituted groups (eg phenyl group,
Naphthyl group, nitrophenyl group, dinitrophenyl group,
Cyanophenyl group, trifluoromethylphenyl group, methoxycarbonylphenyl group, butoxycarbonylphenyl group, methanesulfonylphenyl group, benzenesulfonylphenyl group, tolyl group, xylyl group, acetoxyphenyl group, nitronaphthyl group, etc.) or -CO-R ^D ₈ (R
^D ₈ represents an aliphatic group or an aromatic group, and specifically represents the same as the content of the substituent of Y ^D ).
n represents 0, 1 or 2. More preferably, the substituents:
- In _{^{[C (R D 3) (R}} D 4) ] _n -Y ^D, include functional group containing at least one electron withdrawing group. Specifically, when n is 0 and Y ^D is a hydrocarbon group containing no electron-withdrawing group as a substituent,-[C
_{^{(R D 3) (R D}} 4) ] _n - in, it contains at least 1 pc or more halogen atoms. N is 0, 1 or 2
And Y ^D contains at least one electron withdrawing group. Furthermore, in n = 1 or 2, or -CO-R ^D ₈ - [C (R ^D
₃ ) (R ^D ₄ )]-CO-R ^D _{8 and the} like.

Another preferred substituent is --SO.
_{In 2-} O- ^RD , the carbon atom adjacent to the oxygen atom is substituted with at least two hydrocarbon groups, or n =
The case where it is 0 or 1 and Y ^D is an aryl group having a substituent at the 2-position and the 6-position of the aryl group can be mentioned.

R ^D ₁ is

[0132]

[Chemical 37]

In the case of representing, Z ^D represents an organic residue forming a cyclic imide group. Preferably, it represents an organic residue represented by the general formula (C-XVIII) or (C-XIX).

[0134]

[Chemical 38]

In the formula (C-XVIII), R ^D ₉ , R ^D ₁₀
May be the same or different, and each is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), and a carbon number of 1 to 1.
8 optionally substituted alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group) Base,
2-cyanoethyl group, 3-chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.), and aralkyl group having 7 to 12 carbon atoms which may be substituted (eg, benzyl group, phenethyl group). Group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), an alkenyl group having 3 to 18 carbon atoms which may be substituted (eg, allyl group, 3- Methyl-2-propenyl group, etc.), and R ^D ₁ represents —N═C (R ^D ₅ ) (R ^D ₆ ), R ^D ₅ and R ^D ₆ are each a hydrogen atom or an aliphatic group (specifically, Represents the same contents as those of R ^D ₃ , R ^D ₄ ) or an aryl group (specifically R ^D ₃ , R ^D ₄
Represents the same content as that of). However, R ^D ₅
Neither R ^D ₆ represents a hydrogen atom.

When R ^D ₁ represents —NHCOR ^D ₇ , R ^D ₇ represents an aliphatic group or an aryl group, and specifically has the same contents as those of R ^D ₃ and R ^D ₄ . In formula (C-XVII), R ^D ₂ represents an optionally substituted aliphatic group having 1 to 18 carbon atoms or an aryl group having 6 to 22 carbon atoms which may have a substituent.

More specifically, the above-mentioned formula (C-XVI)
The same content as the aliphatic group or aryl group in Y ^D represented by The general formula used in the present invention [-SO
₂ -O-R ^D ₁₎ or (-SO ₂ -O-R ^D _2] monomer containing at least one functional group selected from the group (C) is based on the knowledge of the conventionally known organic reactions Can be synthesized.

For example, J. F. W. McOmie, "P
rotary group Organi
c Chemistry "; Prenum Press
(Published in 1973), T.W. W. Greene, "Prot
active groups Organic S
"Thensis" John Wiley & So
It can be synthesized in the same manner as the carboxyl group protection reaction such as ns (published in 1980).

More specifically, the general formula (C-XVI) -SO
_2- O-R ^D ₁ or general formula (C-XVII) -SO _2-
Examples of the functional group of O—R ^D ₂ include the following, but the scope of the present invention is not limited to these.

[0140]

[Chemical Formula 39]

[0141]

[Chemical 40]

[0142]

[Chemical 41]

[0143]

[Chemical 42]

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

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

The amount of these other monomers is 60 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total insoluble polymer component. If the amount of the other monomer exceeds 60 parts by weight, the effect of improving the water retention property as the original plate for offset printing decreases.

It contains a substituent containing at least two fluorine atoms and / or silicon atoms, which is copolymerizable with the functional group-containing monomer (C) which decomposes to form a hydrophilic group. Explaining the monofunctional monomer (D), the monofunctional monomer (D) of the present invention may be any compound as long as it satisfies the above requirements. The specific contents of the substituents will be described below, but the present invention is not limited to these chemical structures.

Examples of the fluorine atom-containing substituent include -C _h F _{2h + 1} (h represents an integer of 1 to 12),-(CF
₂ ) _j CF ₂ H (j represents an integer of 1 to 11), -C ₆
H _l F _{l ′} [(l and l ′ are each an integer of 1 to 5, where l + l ′ =
5) or (l = 5-l ', l'is an integer of 1 to 5)] and the like.

Examples of the substituent containing a silicon atom include:
−Si (R₃) (R_Four) (R_Five), − Si (R ₆) (R₇) O_k-R₈
(K represents an integer of 1 to 20), polysiloxane structure
Etc.

However, R ₃ , R ₄ and R ₅ may be the same or different and may be an optionally substituted hydrocarbon group or —OR.
_{Represents 9} groups (R ₉ represents the same content as the hydrocarbon group of R ₃ ).

R ₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2 -Chloroethyl group, 2-
Bromoethyl group, 2,2,2-trifluoroethyl group, 2
-Cyanoethyl group, 3,3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2
-Methoxycarbonylethyl group, 2,2,2,2 ',
2 ′, 2′-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg,
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4
-Methyl-2-hexenyl group, etc.), an aralkyl group having 7 to 12 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro) Benzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.) and an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, a cyclohexyl group, 2- A cyclohexyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg,
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propylamidophenyl group, dodecyloylamidophenyl group, etc.).

In the —OR ₉ group, R ₉ has the same meaning as the hydrocarbon group for R ₃ above.

R ₆ , R ₇ and R ₈ may be the same or different and represent the same symbols as R ₃ , R ₄ and R ₅ .

Next, specific examples of the repeating unit having a substituent containing a fluorine atom and / or a silicon atom as described above are shown below. Here, b represents H or CH ₃ , and Rf is
_{-CH 2 C h C 2h + 1} - (CH 2) 2 - (CF 2) shows a _{j CF 2 H, R 1 '} , R 2', R 3 ' represents an alkyl group having 1 to 12 carbon atoms, R ″ represents —Si (CH ₃ ) ₃ and h is 1 to 1.
2 is an integer, j is an integer of 1 to 11, and i is 1 to
3 is an integer, 1 is an integer of 1 to 5, and q is 1 to 2.
Represents an integer of 0, r represents 0 or an integer of 1 to 20, and t represents an integer of 2 to 12. However, the scope of the present invention is not limited to these.

[0155]

[Chemical 43]

[0156]

[Chemical 44]

[0157]

[Chemical 45]

[0158]

[Chemical 46]

[0159]

[Chemical 47]

In addition to the polar group-containing monomer (C) and the fluorine atom and / or silicon atom-containing monomer (D) as described above, other copolymerizable monomers other than these are added. You may contain as a united component.

The other monomer may be a compound represented by the general formula (X) described below.
And a monomer corresponding to the monomer represented by the formula (X).

What is important as the polymerization component which is insoluble in the non-aqueous solution is that it can satisfy the hydrophilicity represented by the contact angle to distilled water of 50 degrees or less.

The dispersion stabilizing resin of the present invention is used in the non-aqueous solvent.
Any soluble polymer may be used, but specifically
K. B. J. Barrett "Dispersio
n Polymerization in Organ
ic Media "John Wiley and So
ns (1975), R.N. Dowpenco, D.M.
P. Hart, Ind. Eng. Chem. Prod.
Res. Development.12, (No. 1), 14
(1973), Tokichi Tange, Journal of Japan Adhesion Society23
(1), 26 (1987), D.I. J. Walbridge
e, NATO. Adv. Study Inst. Se
r. E. No. 67, 40 (1983), Y. Sasa
ki and M.K. Yabuta, Proc, 10t
h, Int. Conf. Org. Coat. Sci. T
echnol,10, 263 (1984) etc.
Each example polymer may be mentioned.

For example, olefin polymer, modified olefin polymer, styrene-olefin copolymer, aliphatic carboxylic acid vinyl ester copolymer, modified maleic anhydride copolymer, polyester polymer, polyether polymer, methacrylate homopolymer. Examples thereof include polymer, acrylate homopolymer, methacrylate copolymer, acrylate copolymer, and alkyd resin.

More specifically, the polymer component used as the repeating unit of the dispersion stabilizing resin of the present invention includes a component represented by the following general formula (X).

[0166]

[Chemical 48]

[0167] formula (X), X ₂ represents the same content as V ₀ which Formula (II), details are given in the description of V ₀ which formula (II).

R ₂₁ is an optionally substituted alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, dosaconyl group, 2- (N, N-dimethylamino) ethyl group, 2
-(N-morpholino) ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2- (α-thienyl) ethyl group, 2-carboxyethyl group, 2-methoxycarbonylethyl group,
2,3-epoxypropyl group, 2,3-diacetoxypropyl group, 3-chloropropyl group, 4-ethoxycarbonylbutyl group, etc., and an alkenyl group having 3 to 22 carbon atoms which may be substituted (eg, allyl group, Hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group,
Octadecenyl group, oleyl group, linoleyl group, etc.), aralkyl group having 7 to 22 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group,
2-naphthylmethyl group, 2- (2'-naphthyl) ethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group,
Methoxybenzyl group, dimethoxybenzyl group, butylbenzyl group, methoxycarbonylbenzyl group, etc.), alicyclic group having 4 to 12 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chloro) Cyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), carbon number 6 to
22 optionally substituted aromatic groups (eg, phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, anthranyl group, chlorophenyl group, bromophenyl group, butylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, Octyloxyphenyl group, ethoxycarbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N, N-dibutylaminophenyl group, N
-Methyl-N-dodecylphenyl group, thienyl group, hiranyl group, etc.) and the like.

[0169] c _1, c ₂ represents a b _1, b ₂ the same contents as in Formula (II), details are described in the description of the b _1, b ₂ of the formula (II).

As the polymer component in the dispersion stabilizing resin of the present invention, other polymer components may be contained in addition to the above-mentioned components.

The other polymer component may be any as long as it copolymerizes with the monomer corresponding to the component represented by the general formula (X). Examples of the corresponding monomer include:
α-olefins, acrylonitrile, methacrylonitrile, vinyl-containing heterocycles (as the heterocycle, for example, pyran ring, pyrrolidone ring, imidazole ring, pyridine ring, etc.), vinyl group-containing carboxylic acids (eg acrylic acid, methacrylic acid) , Crotonic acid, itaconic acid, maleic acid, etc.), vinyl group-containing carboxamides (eg, acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.) and the like.

In the dispersion stabilizing resin of the present invention, the polymer component represented by the general formula (X) is the total polymer 10 of the resin.
It is 30 parts by weight or more, preferably 50 parts by weight or more in 0 parts by weight.

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

One of the polymer components as the dispersion stabilizing resin
As a result, when a heat and / or photocurable group is contained, further elution can be further suppressed by further chemically bonding to the binder resin.

Further, it is preferable that the dispersion stabilizing resin of the present invention contains at least one polymerizable double bond group moiety represented by the general formula (II) in the polymer chain.

The polymerizable double bond group portion will be described below.

[0177]

[Chemical 49]

In the general formula (II), V ₀ is -O-, -C
OO -, - OCO -, - (CH 2) p -OCO -, -
_{(CH 2) p -COO -,} - SO 2 -, - CONR 1,
_{-SO 2 NR 1, -C 6 H} 4 -, - CONHCOO-,
Or represents -CONHCONH- (p represents an integer of 1 to 4).

In addition to hydrogen atom, R ₁ is preferably a hydrocarbon group which may be substituted and has 1 to 18 carbon atoms (eg, 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, 2-
Methoxyethyl group, 3-bromopropyl group, etc.), alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, Etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), An alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group,
Etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, Acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

[0180] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group) Group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

B ₁ and b ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg Methyl group, ethyl group, propyl group, butyl group, etc.)-COO-R ₂ or COOR ₂ via hydrocarbon (R ₂ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an oil) Represents a cyclic group or an aryl group, which may be substituted,
Specifically, it represents the same contents as those described for R ₁ ).

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

More preferably, in the general formula (II), V
_0, -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
-, - CONHCOO- or -C ₆ H ₄ - represents a, b
₁ and b ₂ may be the same or different from each other, a hydrogen atom,
Represents a methyl group, -COOR ₂ or -CH ₂ COOR ₂ , (R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Represents a hexyl group, etc.). Even more preferably, one of b ₁ and b ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group-containing moiety represented by the general formula (II), specifically, CH ₂ ═CH—CO
_{-O-, CH 2 = C (CH} 3) -CO-O-, CH (C
_{H 3) = CH-CO-} O-, CH 2 = C (CH 2 COO
_{CH 3) -CO-O-, CH} 2 = C (CH 2 COOH)
_{-CO-O-, CH 2 = CH} -CONH-, CH 2 = C
_{(CH 3) -CONH-, CH (} CH 3) = CH-CO
_{NH-, CH 2 = C (CH} 3) -CONHCOO-, C
_{H 2 = CH-O-CO-} , CH 2 = CH-CH 2 -O-
_{CO-, CH 2 = CH-O-} , CH 2 = C (COOH)
_{-CH 2 -CO-O-, CH 2} = C (COOCH 3) -
_{CH 2 -CO-O-, CH 2} = CH-C 6 H 4 - , and the like.

The polymerizable double bond group-containing moiety is directly bonded to the main chain of the polymer chain or bonded to any linking group. A divalent organic residue and specifically as linking to group, -O -, - S -, - N (d 1) -,
_{-SO -, - SO 2 -,} - COO -, - OCO -, - C
ONHCO -, - NHCONH -, - CON (d 2) -
SO ₂ (d ₃₎ - and _{-S i (d 4) (d} 5) the selected linking groups from may be interposed, a divalent aliphatic group or a divalent aromatic group or these two, Represents an organic residue composed of a combination of valent residues. Where d _{1 to} d ₅
Represents the same contents as R ₁ in formula (II).

As the divalent aliphatic group, for example,-(C (k
_{1) (k 2)) -} , - (C (k 1) = C (k 2)) -,
- (C≡C) -, - C 6 H 10 -,

[0187]

[Chemical 50]

{K ₁ and k ₂ may be the same or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or an alkyl group having 1 to 12 carbon atoms ( For example, methyl group, ethyl group,
(Propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.)
Represents. Q is -O -, - S- or -NR ₂₀ - represents, R ₂₀ represents an alkyl group having 1 to 4 carbon atoms, a -CH ₂ Cl or -CH ₂ Br}.

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

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

The above-mentioned polymerizable double bond group-containing moiety is specifically randomly bonded in the polymer chain,
Alternatively, it is bonded only to one end of the main chain of the polymer chain. Preferably, a polymer having a polymerizable double bond group-containing portion bonded to only one end of the main chain of the polymer chain (hereinafter, abbreviated as monofunctional polymer [M]) is used.

Specific examples of the polymerizable double bond group-containing moiety represented by the general formula (II) of the monofunctional polymer [M] and the moiety composed of the organic residue linked to the polymerizable double bond group-containing moiety are as follows. However, the present invention is not limited to these. However, in each of the following examples, P ₁ is —H, —CH ₃ —, —
CH ₂ COOCH _3, -Cl, shows -Br or -CN, P ₂ represents -H or -CH _3, X is -Cl or -
Represents Br, n represents an integer of 2 to 12, and m represents an integer of 1 to 4.

[0193]

[Chemical 51]

[0194]

[Chemical 52]

[0195]

[Chemical 53]

[0196]

[Chemical 54]

[0197]

[Chemical 55]

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

For example, a method of copolymerizing a monomer containing two polymerizable double bond groups having different polymerization reactivities in a molecule, a carboxyl group, a hydroxyl group, an amino group, an epoxy group and the like in a molecule. After polymerizing a monofunctional monomer containing a reactive group to obtain a polymer, a polymerizable double-chain containing another reactive group that can chemically bond with the reactive group in the side chain of the polymer. Reacting with an organic low-molecular compound containing a bonding group,
Examples of well-known methods include a method of introducing by so-called polymer reaction.

As the above method, for example, JP-A-60-
The method described in Japanese Patent No. 185962 may be used. As the above method, specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (Published in 1977), Ryohei Oda "Polymer Fine Chemical" Kodansha (Published in 1976), JP-A-6
It is described in detail in the specification etc. filed as Japanese Patent Application Laid-Open No. 1-43757 and Japanese Patent Application No. 1-149305.

For example, a polymer reaction resulting from the combination of the functional group of group A and the functional group of group B in Table 1 below is a well-known method. Note that R ₂₂ and R _{23 in} Table-1
Are each a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, a methyl group, an 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,
And a methylbenzyl group, N, N (dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group and the like.

[0202]

[Table 1]

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

Specifically, P. Dreyfuss &
R. P. Quirk, Bncycl. Polym. Sc
i. Eng. , 7 , 551 (1987), p. F. Re
mpp, E. Franta, Adv. Polym. Sc
i. , 58 , 1 (1984), V.I. Percec, Ap
pl. Poly. Sci. , 285 , 95 (198
4), R.A. Asami, M .; Takari, Macro
mol. Chem. Suppl. , 12 , 163 (19
85), P.I. Rempp. , Et al, Macrom
ol. Chem. Suppl. , 8 , 3 (1984),
Yusuke Kawakami, Kagaku Kogyo, 38 , 56 (1987), Yuya Yamashita, Kogaku, 31 , 988 (1982), Shiro Kobayashi, Kogaku, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Azuma, Takashi Tsuda,
Functional Materials, 1987 , No. It can be synthesized according to the methods described in the review articles such as 10, 5 and the like, and the literatures and patents cited therein.

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

As described above, the dispersed resin particle of the present invention comprises the polar group-containing monofunctional monomer (C) and the silicon atom and / or fluorine atom-containing monofunctional monomer (D). It is a copolymer resin particle obtained by dispersion polymerization in the presence of a dispersion stabilizing resin.

Further, when the dispersed resin particles of the present invention have a network structure, the above-mentioned polar group-containing monofunctional monomer (C) and silicon atom and / or fluorine atom-containing monofunctional monomer ( The polymer of D) as a polymerizable component [abbreviated as polymer component (C)] is bridged between polymers to form a high-order network structure.

That is, the dispersed resin particles of the present invention are a non-aqueous latex composed of a portion insoluble in the non-aqueous dispersion solvent composed of the polymer component (C) and a polymer soluble in the solvent. In the case of having a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged.

As a result, the network resin particles are sparingly soluble or insoluble in water. In particular,
The solubility of the resin in water is 80% by weight or less, preferably 5
It is 0% by weight or less.

The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, (a) a method of crosslinking a polymer containing the polymer component (C) with various crosslinking agents or curing agents, and (b) containing at least a monomer corresponding to the polymer component (C). When a polymerization reaction is carried out by using a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, a network structure is formed between the molecules, and (c) the polymer. It can be carried out by a method such as a method in which the combined component (C) and the polymers containing the component containing a reactive group are crosslinked by a polymerization reaction or a polymer reaction.

As the cross-linking agent in the above method (a), compounds usually used as cross-linking agents can be mentioned.
Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), edited by The Society of Polymer Science, Japan, etc. Can be used.

For example, an organic silane compound (eg, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and other silane coupling agents), polyisocyanate compounds (for example, toluylene diisocyanate, o-toluy) Diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), polyol-based compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (eg, ethylenediamine, γ-hydroxypropyl) Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
Kakiuchi Hiroshi's "New Epoxy Resins" Shokoido (1985), Kuniyuki Hashimoto's "Epoxy Resins", compounds described in Nikkan Kogyo Shimbun (1969), melamine resins (eg Ichiro Miwa, Hideo Matsunaga) Edited by "Uria Melamine Resin", compounds described in Nikkan Kogyo Shimbun (1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976) Annually), Eizo Omori "functional acrylic resin" Techno System (published in 1985) and the like, and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6- Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacryle Door, bisphenol A-
Examples include diglycidyl ether diacrylate, oligoester acrylate, and their methacrylates.

Polymerization of a polyfunctional monomer (also referred to as polyfunctional monomer (E)) or a polyfunctional oligomer containing two or more polymerizable functional groups which are coexistent in the method (b). As the functional group, specifically, CH ₂ ═CH—CH
_{2 -, CH 2 = CH-} CO-O-, CH 2 = CH-, C
_{H 2 = C (CH 3)} -CO-O-, CH (CH 3) = C
_{H-CO-O-, CH 2} = CH-CONH-, CH 2 =
_{C (CH 3) -CONH-, CH} (CH 3) = CH-C
_{ONH-, CH 2 = CH-O} -CO-, CH 2 = C (C
_{H 3) -O-CO-, CH} 2 = CH-CH 2 -O-CO
_{-, CH 2 = CH-NHCO-} , CH 2 = CH-CH 2
_{-NHCO-, CH 2 = CH-SO} 2 -, CH 2 = CH
_{-CO-, CH 2 = CH-O-} , may be mentioned CH ₂ = CH-S-, and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a styrene derivative such as divinylbenzene or trivinylbenzene as a monomer or oligomer having the same polymerizable functional group: a polyvalent monomer. Alcohol (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg, hydrinoquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg methacrylic acid, acryl) Acid, crotonic acid, allyl acetic acid, etc.) and the like.

Examples of the monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, arylloyl). Propionic acid, itaconiloylacetic acid, itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropione) Ester derivatives or amide derivatives containing vinyl groups such as acids) (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, methacryloyl) Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene ester, N- allyl acrylamide, N-
Allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group And a condensate with a carboxylic acid containing

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

Further, in the case of the above method (c), in the case of forming a chemical bond by the reaction of the reactive groups between the macromolecules to form a bridge between the macromolecules, the reaction with the usual organic low molecular weight compound is performed. You can do the same. Specifically, it can be synthesized according to the same method as described in the method of synthesizing the dispersion stabilizing resin.

In the dispersion polymerization, monodisperse particles having a uniform particle size can be obtained, and fine particles of 0.5 μm or less can be easily obtained. The method (b) using a monomer is preferable.

As described above, the network-dispersed resin particles of the present invention contain a repeating unit containing a polar group and a polymer component soluble in the non-aqueous solvent, and the molecular chains are highly crosslinked. It is a polymer particle having a different structure.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, which may be used alone or in combination of two or more. Good.

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, hexane, octane, decane, dodecane and tridecane. , 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, dichloropropane,
Examples thereof include halogenated hydrocarbons such as trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing the dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle diameter of the resin particles easily becomes 0.8 μm or less, and the distribution of the particle diameter is very narrow and monodispersed. Can be particles.

Specifically, K.K. B. J. Barrett
"Dispersion Polymerizatio
n in Organic Media "John W
iley (1975), Koichiro Murata, Polymer processing, 2
3, 20 (1974), Tsunetaka-Toyokichi Tange Matsumoto, Japan Journal of the Adhesion Society of 9, 183 (1973), Toyokichi Tange, Journal of the Adhesion Society of Japan 23, 26 (1987), D . J. Walbrid
ge, NATO. Adv. study. Inst. Se
r. B. No. 67, 40 (1983), British Patent No. 8
No. 93429, No. 934038, US Pat. No. 1
122397, 394012, and 4606989, JP-A-60-179751, and 60-185.
The method is disclosed in each of the 963 publications and the like.

The dispersed resin particles of the present invention contain at least 1 of each of the monomer (C) and the monomer (D) and the dispersion stabilizing resin.
In the case of forming a network structure, it is composed of more than one species and, if necessary, is made to coexist with a polyfunctional monomer (E). In any case, what is important is a resin synthesized from these monomers. If the particles are insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, one dispersion stabilizing resin is used for the insoluble monomer (C) and the monomer (D).
It is preferable to use -50% by weight, and more preferably 2-30% by weight. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 ×.
It is 10 ⁵ .

In order to produce the dispersed resin particles used in the present invention as described above, generally, the monomer (C), the monomer (D), the dispersion stabilizing resin, and the polyfunctional monomer ( E)
And may be heat-polymerized in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium in a non-aqueous solvent. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of the monomer (C), the monomer (D), the dispersion stabilizing resin and the polyfunctional monomer (E),
(ii) There are methods such as dropwise addition or optional addition of the mixture of the above-mentioned polymerizable compound and polymerization initiator into the non-aqueous solvent, and the method is not limited to these, and any method can be used for production.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight.

The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 30 to 180.
The temperature is about 0 ° C, preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours.

The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles having a uniform particle size distribution. The surface layer of the photoreceptor of the present invention comprises the above resin particles uniformly dispersed in the binder resin of the matrix, and the binder resin will be described in detail below.

As the binder resin for the surface layer of the present invention, any of the conventionally known binder resins can be used.
Typical examples are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, vinyl alkanoate resin, polyvinyl. Butyral, alkyd resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Kurita, Jiro Ishiwatari, High Polymer,
Volume 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) p. 9, Koichi Nakamura, "Practical Technology of Binders for Recording Materials", 10th
Chapter, C.I. H. C. Published (1985), D.M. D. Tat
t, S. C. Heidecker, Tappi, 49
(No. 10), 439 (1966), E.I. S. Bal
ttazzi, R .; G. Blancloette et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Electrophotographic Society Journal 18 (No. 2), 2
8 (1980), JP-B-50-31011, JP-A-53.
-54027, 54-20735, 57-2025.
44, 54-68046, and the like.

Further, the surface layer may contain a crosslinking compound and a crosslinking promoting compound. Specifically, the same compounds as the group of crosslinkable compounds used for forming the crosslinked structure with the resin particles of the present invention can be mentioned. However, when contained in the surface layer, do not inhibit the hydrophilicity after desensitization,
Also, it must be used within a range that does not adversely affect the electrophotographic characteristics of the electrophotographic photosensitive member (for example, initial potential, dark charge retention rate, photosensitivity, residual potential, etc.). Specifically, with respect to the total solid content of the surface layer forming composition, 0.0
It is preferably used in the range of 05 to 10 parts by weight.

By using these crosslinkable compounds in combination, the surface layer forms a crosslinked structure and is made to have a higher order structure, whereby the film strength after desensitization of the surface layer is improved and the water retention property of the entire surface is improved. It is controlled and the water retention is improved.

Furthermore, fine particles (for example, metal oxides) other than the resin particles of the present invention are contained in the surface layer within a range of 0.001 to 5 parts by weight based on the total amount of the surface layer forming composition. It may be contained. As a result, it is possible to improve the film strength or adjust the surface smoothness due to the filler effect of adding fine particles.

Examples thereof include fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina and clay, and polymer particles such as polymethylmethacrylate, polystyrene and phenol resin.

What is important in constructing the surface layer is that the non-image area becomes sufficiently hydrophilic after the desensitizing treatment, as described above. That is, this hydrophilicity can be confirmed, for example, by measuring the contact angle with water. The contact angle of water on the surface of the surface layer (hydrophilizable layer) before the desensitizing treatment is about 60 ° to 120 °, but it decreases to about 5 ° to 20 ° after the desensitizing treatment. And then get very wet with water. For this reason,
The printing plate has an image area made of lipophilic toner and a highly hydrophilic non-image area formed on its surface. Therefore, the surface layer after the desensitizing treatment may have a contact angle with water of 20 degrees or less.

The present invention is particularly excellent in that it is more hydrophilic than the conventional ones. That is, the resin particles in the present invention are decomposed by the treatment of the desensitizing solution or the soaking water at the time of printing to generate a hydroxyl group,
It develops hydrophilicity.

Therefore, the original plate of the present invention containing the resin particles in the surface layer, the lipophilicity of the image area and the hydrophilicity of the non-image area are improved by making the non-image area hydrophilic by the desensitizing solution. The property is clear, and the printing ink is prevented from adhering to the non-image area during printing. As a result, it becomes possible to print a large number of prints with clear image quality without background stains.

Further, in the case of the above-mentioned resin particles partially cross-linked, the solubility in water is remarkably lowered while maintaining the hydrophilicity, and the particles become hardly soluble or insoluble, and the particles themselves have a water swelling property. To have.

Therefore, the hydrophilic group produced in the resin particles causes the surface of the non-image area to exhibit hydrophilicity, and the entire surface layer contains controlled water. The effect of the present invention that the hydrophilicity (printing ink repulsion) is further enhanced is improved, and the durability is improved.

More specifically, even if the amount of the above functional groups in the above resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or the size of the printing machine can be increased or the printing can be performed. Even when printing conditions such as pressure fluctuations become strict, it is possible to print a large number of prints with clear image quality without background stains.

In the past, only one material such as zinc oxide could be used because it had to have the property that photoconductivity and hydrophilicity were possible in one layer, but in the printing original plate of the present invention, By forming a surface layer like this, the functions were separated into a photoconductive layer and a hydrophilizable layer (surface layer), so stricter control during printing compared to conventional systems that rely on the desensitizing reaction of zinc oxide. Is significantly reduced.

That is, in the conventional system using zinc oxide, a ferrocyan-based compound is used as the main component of the desensitizing solution for desensitizing zinc oxide, and this compound requires special handling management for preventing environmental pollution. What you need, and
Since the desensitized hydrophilized substance adheres to the printed matter, the amount consumed by printing many sheets at the time of printing,
It is customary to use by adding the desensitizing main agent to the immersion water for printing, but as a side effect, the usable types of color inks are limited, or it is possible to use neutral paper as the printing paper. There were problems such as difficulties.

On the other hand, in the system of the present invention, since the principle of desensitization is completely different, these problems can be easily solved.

Next, the photoconductive layer of the electrophotographic photosensitive material of the present invention will be described. The photoconductive layer contains at least a photoconductor and a binder resin, and it is particularly preferable that the photoconductive layer contains at least one of the following resins [A] as the binder resin.

In the resin [A], the weight average molecular weight is 1
× 10 ^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 1
0 is ^4, the glass transition point of the resin (A) is preferably -
It is 30 ° C to 110 ° C, and more preferably -20 ° C to 90 ° C.

When the molecular weight of the resin [A] is less than 10 ³ , the film forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even the resin of the present invention, In particular, in the case of photoreceptors using near-infrared to infrared spectral sensitizing dye, fluctuations in dark decay retention rate and photosensitivity under severe conditions of high temperature / high humidity, low temperature / low humidity are somewhat large, and stable copying is possible. The effect of the present invention that an image is obtained is diminished.

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

The content of the polar group in the resin [A] is 0.5.
If it is less than wt%, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group is more than 15% by weight, dispersibility is lowered no matter how low molecular weight the compound is, and scumming is increased when it is used as an offset master.

The low molecular weight resin [A] is represented by the above-mentioned general formula (Ia) and general formula (Ib).
Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or a naphthalene ring having a specific substituent at the 2-position and / or the 2- and 6-positions
(Hereinafter, this low molecular weight compound is referred to as resin [A ']).

The proportion of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (Ia) and / or the formula (Ib) in the resin [A '] is 30% by weight or more, preferably 50 to 97% by weight. The proportion of the polar group-containing polymer component is 0.5 to 1 relative to 100 parts by weight of the resin [A '].
It is 5% by weight, preferably 1 to 10% by weight.

Next, the repeating unit represented by the general formula (I) contained in the resin [A] in an amount of 30% by weight or more will be further described. In the general formula (I), a ₁ and a ₂ are preferably hydrogen atom, cyano group, alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.),
COO-R ₀₆ or -COO-R via a hydrocarbon group
₀₆ (R ₀₆ represents a hydrogen atom or an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 1 to 18 carbon atoms, which may be substituted. _It represents the same content as that described for ₀₃ ).

Examples of the hydrocarbon in the —COO—R ₀₆ group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. R ₀₃ has 1 to 18 carbon atoms
An optionally substituted alkyl group (for example, a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group , 2-methoxyethyl group, 2-ethoxyethoxy group,
3-hydroxypropyl group and the like, alkenyl group having 2 to 18 carbon atoms and optionally substituted (for example, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group,
Heptenyl group, octenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (benzyl group having carbon atoms,
Phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, Cycloheptyl group etc.), optionally substituted aryl group (eg phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl) Group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.) and the like.

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

In formula (Ia), preferred T ₁ and T
_{As 2} , each independently of one another, a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3-
Phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group) and aryl groups (for example, phenyl group, tolyl group, xylyl group,
Bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₀₄ and-
COOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms) can be mentioned.

In the formulas (Ia) and (Ib), L ₁ and L ₂ each represent a direct bond connecting —COO— and the benzene ring or — (CH ₂ ) _n1 — (n ₁ represents an integer of ₁ to 3). _{), - CH 2 OCO -,} - CH 2 CH 2 OCO -, -
_{(CH 2 O) m1 - (} m 1 represents an integer of 1 or 2), -
A connecting group having 1 to 4 connecting atoms such as CH ₂ CH ₂ O-, and the like, more preferably a direct bond or 1 to 2 connecting atoms.
Can be mentioned.

Formula (I) used in the resin [A] of the present invention
Specific examples of the copolymerization component corresponding to the repeating unit represented by a) or (Ib) are shown below. However, the scope of the present invention is not limited to this. The following (a-1)
In (a-20), n is an integer of 1 to 4, m is an integer of 0 or 1 to 3, p is an integer of 1 to 3, and R _{10 to} R ₁₃ are all -C _n H _{2n + 1} or _{- (CH 2) m -C 6} H 5 ( except, n, m are as defined above), X ₁ and X ₂ may be the same or different, a hydrogen atom, -Cl, -Br, either -I Represents.

[0257]

[Chemical 56]

[0258]

[Chemical 57]

[0259]

[Chemical 58]

[0260]

[Chemical 59]

Next, the polar group bonded to one end of the polymer main chain of the low molecular weight resin [A] will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH, -P (=
It is preferable that at least one selected from O) (OH) R ₀₁ and a cyclic acid anhydride-containing group.

The --P (═O) (OH) R ₀₁ group means the above R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group), and specifically, R ₀₁ represents an aliphatic group having 1 to 22 carbon atoms (eg, 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 Group, fluorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aryl group (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro- A methyl-phenyl group,
Dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.), and R ₀₂ has the same content as R ₀₁ .

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned.

Examples of the aliphatic dicarboxylic acid anhydride include:
Succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid ring Acid anhydride ring,
2,3-bicyclo [2,2,2] octadicarboxylic acid anhydride ring and the like can be mentioned, and these rings are, for example, chlorine atom,
A halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group may be substituted.

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

These polar groups may be directly bonded to the ends of the polymer main chain or may be bonded via a linking group.
The linking group, but may be any binding group, for example, if specifically mentioned, - _{[C (d 1) (d 2} ) ]
-(D ₁ and d ₂ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group,
Cyano group, alkyl group, (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group,
Butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.),-(C
_{H (d 3) -CH (d} 4) ] - (d _3, d ₄ is d _1, d
Represents a ₂ same contents _{as), - C 6 H 10 -} , - C 6 H
_{5 -, - O -, -} S -, - N (d 5) - [d ₅ represents a hydrogen atom or a hydrocarbon group (hydrocarbon group, as specifically hydrocarbon group having 1 to 12 carbon atoms (For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-methoxyethyl group, 2
-Chloroethyl group, 2-cyanoethyl group, benzyl group,
Methylbenzyl group, phenethyl group, phenyl group, tolyl group, chlorofell group, methoxyphenyl group, butylphenyl group, etc.)), -CO-, -COO-,
_{-OCO -, - (d 5)} CON -, - SO 2 N (d 5)
_{-, - SO 2 -, -} NHCONH -, - NHCOO-,
_{-NHSO 2 -, - CONHCOO -,} - CONHCO
NH-, a heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom, or a condensed ring thereof may be used: for example, a thiophene ring, a pyridine ring, a furan ring, imidazole. ring, piperidine ring, morpholine ring and the like) or _{-Si (d 6) (d 7} ) -
(D ₆ and d ₇ may be the same or different and represent a hydrocarbon group or —Od ₈ (d ₈ is a hydrocarbon group). These hydrocarbon groups are the same as those listed for d _5. And the like) or a linking group constituted by a combination of these.

Further, preferably, in the binder resin [A], the copolymerization component represented by the above general formula (I) [the general formula (Ia)] is used.
Or together including] those represented by (Ib), as the polymer component to be copolymerized therewith, -PO ₃ H _2, -SO ₃
0.05 to 10% by weight of a copolymerization component containing at least one polar group selected from H, -COOH, -P (= O) (OH) R ₀₁ and a cyclic acid anhydride-containing group. However, it is preferable in terms of further improving the electrostatic characteristics.

These specific polar groups have the same contents as the polar groups bonded to one end of the polymer main chain described above.
In the resin [A], the abundance ratio of the polar group contained as a copolymer component and the polar group bonded to one end of the polymer main chain is determined by other binder resins constituting the photoconductive layer of the present invention. , The resin particles, the spectral sensitizing dye, the chemical sensitizer or other additives, and the ratio thereof is preferably adjusted arbitrarily. What is important is that the total amount of both polar groups be used within the range of 0.5 to 15% by weight.

The copolymerization component containing these polar groups is
For example, any vinyl compound containing the polar group, which is copolymerizable with the monomer corresponding to the repeating unit represented by the general formula (I) [including general formulas (Ia) and (Ib)], may be used. For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by Japan Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, 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, itacone Acid half-esters, itaconic half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-)
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Vinyl- or allyl-group half-ester derivatives, and their carboxylic or sulfonic acid ester dielectrics,
Examples thereof include compounds containing the polar group in the substituent of the amide derivative.

Examples of the polar group-containing copolymerization component are shown below. Here, e ₁ represents H or CH ₃ , e ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₅ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and c is 1 to
3 is an integer, d is an integer of 2 to 11, and e is 1 to
11 is an integer, f is an integer of 2 to 4, and g is 2 to
Indicates an integer of 10.

[0271]

[Chemical 60]

[0272]

[Chemical formula 61]

[0273]

[Chemical formula 62]

[0274]

[Chemical 63]

[0275]

[Chemical 64]

[0276]

[Chemical 65]

[0277]

[Chemical 66]

[0278]

[Chemical 67]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ′]) is represented by the general formula (I) or (I
In addition to the monomer of a) and / or (Ib) and the monomer containing the polar group, another monomer other than these may be contained as a copolymerization component.

Examples of such other copolymerization component include, in addition to methacrylic acid esters, acrylic acid esters and crotonic acid esters having a substituent other than those described in the general formula (I), α-olefins. , Vinyl carboxylates or acrylic acid esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (for example, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl chloride) Naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like.

It is desirable that these other monomers do not exceed 30% by weight in the resin [A]. In the resin [A], as a method of bonding the polar group to one end of the polymer main chain,
Conventionally known methods of reacting various reagents with the ends of living polymers obtained by anionic polymerization or cationic polymerization (methods by ionic polymerization method), polymerization initiators and / or chain transfer agents containing a specific polar group in the molecule Method of radical polymerization using (method of radical polymerization), or containing reactive group (eg amino group, halogen atom, epoxy group, acid halide, etc.) at the terminal obtained by ionic polymerization method or radical polymerization method as described above The polymer can be easily produced by a synthetic method such as a method of converting the polymer into a specific polar group of the present invention by a polymer reaction.

Specifically, P. Dreyfuss, R.A.
P. Quirk, Encycl. Polym, Sci.
Eng, 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Drugs", 30 , 232 (1985), Akira Ueda,
It can be produced by the methods described in the review articles such as Susumu Nagai "Science and Industry" 60 , 57 (1986) and the references cited therein.

Specifically, as the chain transfer agent used,
For example, a mercapto compound containing the polar group or the reactive group (that is, a group capable of being induced to the polar group) (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-
[N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino]
Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-butanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, 4- (2-meethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic anhydride, 2
-Mercaptoethylphosphonoic anhydride monomethyl ester, or an iodinated alkyl compound containing the above polar group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropane) Sulfonic acid).

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

These chain transfer agents or polymerization initiators are used in amounts of 0.5 to 15 per 100 parts by weight of all the monomers.
Parts by weight, preferably 2 to 10 parts by weight. The low molecular weight resin [A] (including [A ′]) as described above is preferably used in combination with a known resin for a conventional photoconductive layer. The use ratio of the low molecular weight resin [A] and the other resin is preferably 5 to 50/95 to 50 (weight ratio).

Other resins to be used in combination include a weight average molecular weight of 3 × 10 ^{4 to} 1 to 10 ⁶ , preferably 5 × 10 ^{4 to} 5.
× 10 ^{5 is} a medium to high molecular weight substance. The glass transition point of the resin used in combination is -10 ° C to 120 ° C, preferably 0 ° C.
~ 90 ° C.

For example, Ryuji Shibata and Jiro Ishiwatari, Kobunshi, No.
Volume 17, pp. 278 (1968), Harumi Miyamoto, Hide Takei
Hiko, Imaging,1973(No.8) Page 9, Nakamura
Koichi, "Practical Technology of Binders for Recording Materials", 10th
Chapter, C.I. H. C. Published (1985), D.M. Tat
t, S. C. Heidecker, Tappi,49
(No. 10), 439 (1966), E.I. S. Bal
tazzi R .; G. Blanclotte eta
l, Photo. Sci. Eng. ，16(No.
5), 354 (1972), Nguyen Chan Kae, Kiyo
Yu Mizumizu, Eiichi Inoue, The Institute of Electrophotography18(No. 2),
22 (1980), JP-B-50-51011, JP-A-5
3-54027, 54-20735, 57-202.
The materials disclosed in each publication of 544 and the like are listed.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, amide resins,
Hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, copolymer containing nitrogen atom-free heterocycle (For example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, a 1,3-dioxetane ring, and the like), an epoxy resin, and the like can be given.

As the medium to high molecular weight resin to be further used in combination, the above-mentioned physical properties are satisfied, and the following general formula (I
A polymer containing 30 parts by weight or more of the polymer component of the repeating unit represented by II) is included.

[0290]

[Chemical 68]

[In the formula (III), V is —COO—, —O
_{CO -, - (CH 2)} h -OCO -, - (CH 2) h -
COO -, - O-or -SO ₂ - represents a. However, h is 1
In the general formula (III), f ₃ and f ₄ have the same contents as a ₁ and a ₂ in the formula (I).

R ₀₇ has the same _meaning as R ₀₃ in formula (I). A medium to high molecular weight binder resin containing a polymer component represented by the general formula (III) (hereinafter referred to as resin [B])
Examples of the resin include a random copolymer resin containing a polymer component represented by the formula (III) (JP-A-63-4981).
7, 63-220149, 63-220148, etc.), a resin in which the random copolymer and a crosslinkable resin are used in combination (JP-A-1-102573, etc.), and a polymer component represented by the formula (III). A partially functionalized cross-linked copolymer (Japanese Patent Laid-Open Nos. 34860/1990, 40660/1990, etc.) and a monofunctional macromonomer consisting of a polymer component of a specific repeating unit and the formula (V). Graft type block copolymer by polymerization with a monomer corresponding to the component (Japanese Patent Application Nos. 63-203933 and 63-207317, Japanese Patent Application Nos. 1-163796, 1-212994, 1-229379). As for each of the above-mentioned No. 1-189245, the specification etc. which the present inventors have already applied for are cited.

In the present invention, the resin [A] is a low molecular weight copolymer in which a methacrylate copolymer component having a specific substituent and a specific polar group are bonded to one end of the polymer main chain. Adsorbs on the stoichiometric defects of the photoconductor in the photoconductive layer and is a low molecular weight substance, and therefore, the trapping of the photoconductor is compensated by improving the coverage of the surface of the photoconductor. It was found that while the temperature characteristics were dramatically improved, the photoconductor was sufficiently dispersed and the aggregation was suppressed.

As a result, it has been found that the electrophotographic characteristics of the electrophotographic photosensitive member become excellent, and in particular, extremely excellent performance is exhibited even when a spectral sensitizing dye for semiconductor laser light is used. It was

When the resin [B] having a medium to high molecular weight is used in combination, the photoconductive property is higher than that of the resin [A] alone without impairing the high performance of the electrophotographic characteristics due to the use of the resin [A]. It was found that the mechanical strength of the layer can be sufficiently improved. That is, the interaction between the adsorption and coating of the photoconductor and the binder resin is appropriately performed, and the film strength of the coating conductive layer is maintained.

It is considered that this is due to the following actions of the binder resin according to the present invention. That is, in the present invention, the resin [A] and the resin [B] are used together as the binder resin, and the weight average molecular weight of each resin and the content of the polar group in the resin are specified to obtain the photoconductor and the resin. The strength of interaction with can be changed. As a result, the resin [A] having a stronger interaction is selectively and appropriately adsorbed to the photoconductor, and the resin [B] having a weaker interaction than the resin [A] is attached to the polymer main chain in the resin. Of the resin [B] having a long molecular chain length and a graft molecular chain length and having a long interaction with the photoconductor to the extent that the polar group bonded to a specific position does not hinder the electrophotographic characteristics. It is considered that the interaction also significantly improved the electrophotographic properties and the mechanical strength of the film as described above.

The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and lead sulfide. From a sex perspective
Zinc oxide and titanium oxide are preferred.

When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, 1 part of the above-mentioned binder resin is added to 100 parts by weight of the inorganic photoconductive compound.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 40 parts by weight.

On the other hand, the organic compound may be any of the conventionally known compounds, and specifically, the following two types are known as conventionally known examples of the electrophotographic lithographic printing plate precursor. Firstly, Japanese Patent Publications 37-17162 and 62-514.
62, JP-A Nos. 52-2437, 54-19803 and 5
No. 6-107246, No. 57-161863, etc., which has a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binder resin. 56-146145, 60-17751,
60-177752, 60-17760, 60-2
54142, 62-54266, etc., and has a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin. As a special case of the second example, JP-A-60-230147 and 60-23014.
A photoconductive layer having a two-layer structure in which a charge generating agent and a charge transporting agent are contained in separate layers as described in JP-A No. 60-238853 and No. 8, is also known.

The electrophotographic lithographic printing plate precursor according to the invention may take any form of the above-mentioned two photoconductive layers.
In the case of the second example, the organic photoconductive compound referred to in the present invention functions as a charge transport agent.

Examples of the organic photoconductive compound in the present invention include (a) triazole derivatives described in US Pat. No. 3,121,197 and (b) US Pat. No. 3,189,944.
Oxadiazole derivatives described in No. 7, etc., (c)
Imidazole derivatives described in JP-B-37-16096, (d) US Pat. Nos. 3,615,402 and 38,209.
89, No. 3542544, Japanese Patent Publication No. 45-55
5, JP-A-51-10983 and JP-A-51-932.
24, the same 55-108667, the same 55-156953,
Polyarylalkane derivatives described in JP-A-56-36656, (e) U.S. Pat. Nos. 3,180,729 and 4;
278746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537, and JP-A-55-5.
1086, 56-80051, 56-88141,
57-45545, 54-112637, 55-
Pyrazoline derivatives and pyrazolone derivatives described in JP-A-74546, (f) US Pat. No. 3,615,404, JP-B-51-10105, JP-A-46-3712, JP-A-47-28336, JP-A-54-83435. ,
Phenylenediamine derivatives described in JP-A-54-110836, JP-A-54-119925 and the like, (g) US Patent Nos. 3567450, 3180703 and 324059.
7, 3658520, 4232103, 4175
961, 4012376, Japanese Patent Publication No. 49-3
5702, West German Patent (DAS) 111051
No. 8, JP-B-39-27577, JP-A-55-1
44250, 56-119132, 56-2243.
7 arylamine derivatives described in each publication, (h) amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) US Patent 354.
2546, etc., N, N-bicarbazyl derivatives, (j) US Pat. No. 3,257,203, etc., oxazole derivatives, (k) JP-A-56-462.
34, styrylanthracene derivatives,
(L) Fluorenone derivatives described in JP-A-54-110837, (m) US Pat. No. 3,717,462, JP-A-54-59143 (US Pat. No. 41.
(Corresponding to the specification of 50987), JP-A-55-5206
3, ibid 55-52064, ibid 55-46760, ibid 55
-85495, 57-11350, 57-1487.
49, 57-104144, and the like, (n) US Patent No. 404794.
8, same 4047949, same 4265990, same 4273
Nos. 846, 4299897, 4306008 and the like, and (o) JP-A-58-
190953, 59-95540, 59-9714.
8, 59-195658, 62-36674, etc., stilbene derivatives, (p) polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18674, Polyvinyl pyrene, polyvinyl anthracene, and poly-2-vinyl-4- (4 ′) described in each of the same 43-19192 publications.
Of vinyl polymers such as -dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; and (r) polyacenaphthylene, polyindene, acenaphthylene and styrene described in JP-B-43-19193. Polymers such as copolymers, (s) Japanese Patent Publication No. 56-
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP 13940,
(T) JP-A-56-90833 and JP-A-56-161550
Various triphenylmethane polymers described in each publication,
and so on.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t),
All conventionally known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
It is possible to use more than one type.

As the sensitizing dye contained in the photoconductive layer of the first example, conventionally known sensitizing dyes used in electrophotographic photoreceptors can be used. These are "electronic photographs" 12
9 , (1973), "Organic Synthetic Chemistry" 24 (11), 1
010, (1966) and the like. For example, U.S. Pat. Nos. 31-41770 and 4283475, JP-A-48-25658, and JP-A-62-71.
Pyrylium dyes described in Japanese Patent No. 965, etc., Appli
ed Optics Supplement 3 50
(1969), triarylmethane dyes described in JP-A No. 50-39548, US Pat. No. 3,579,719.
Cyanine dyes described in Japanese Patent No. 6 and the like, JP-A-60-1
63047, ibid. 59-164588, ibid. 60-2525
The styryl dyes described in each of the 17 publications and the like are advantageously used.

As the charge generating agent contained in the photoconductive layer of the second example, various organic and inorganic charge generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments shown in the following (1) to (9) can be used. (1) U.S. Pat. Nos. 4,436,800 and 44,395.
06 specifications, JP-A-47-37543 and JP-A-58-1
23541, 58-192042, 58-2192.
63, 59-78356, 60-179746, 61-148453, 61-238063.
Azo pigments such as monoazo, bisazo, and trisazo pigments described in JP-B Nos. 60-5941 and 60-45664, and (2) U.S. Pat.
66802 each specification, JP-A-51-90827, 5
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in JP-A-2-55643, (3) U.S. Pat. No. 3,371,884, JP-A-47-30330.
Perylene pigments described in Japanese Patent Publication No.

(4) Indigo and thioindigo derivatives described in British Patent No. 2237680, JP-A No. 47-30331, etc., (5) British Patent No. 22376.
No. 79, Japanese Patent Application Laid-Open No. 47-30332, etc., quinacridone pigment (6) British Patent No. 223767.
No. 8, JP-A-59-184348, JP-A-62-28.
738 and 47-18544, and the like, (7) JP-A-47-30331 and JP-A-47-
No. 18543, bisbenzimidazole-based pigments, and (8) U.S. Pat. Nos. 4,396,610 and 4,644.
082 Squalium salt-based pigments described in each specification,
(9) JP-A-59-53850 and JP-A-61-212542
Examples thereof include azurenium salt-based pigments described in each publication and the like. These may be used alone or in combination of two or more.

Further, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content rate of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin, and an amount exceeding this is added. Then, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight of the organic photoconductive compound, relative to 100 parts by weight of the binding resin. The organic photoconductive compounds may be used alone or in combination of two or more.

The lithographic printing plate precursor of the present invention contains 10 to 10 parts by weight of the above-mentioned binding resin to 100 parts by weight of the photoconductive compound.
It is used in a proportion of 0 parts by weight, preferably 15 to 50 parts by weight.

In the present invention, various dyes can be used in combination as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al .: RCA R
view 15 , p. 469 (1954), Kouhei Kiyota et al .: The Institute of Electrical Communication, J63-C (No. 2), 9
7 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6 , 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972), and other general references for carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes. , Polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes, and phthalein type dyes are described in JP-B-51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyanin
eDyes and Related Compound
The dyes described in "ds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110,591,
3121008, 3125447 and 312817
9, No. 3132942, No. 3622317,
British Patent Nos. 12268892, 1309274, 14
No. 05898, Japanese Patent Publications No. 48-7814, 55
The dyes described in each publication of 18892 are listed.

Furthermore, near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, ibid 49-5034, ibid 49-45122, ibid 5
7-46245, 56-351141, 57-157.
254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and "Research Disclosure".
e ", 1982, 216 , pages 117 to 118, and the like.

The photoconductor of the present invention is also excellent in that the performance thereof does not easily vary depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used in combination, if necessary.

These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film property, surfactants and the like.

Examples of the chemical sensitizers include halogen, benzoquinone, chloranil, fluoranyl, bromanil,
Electron-withdrawing compounds such as dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone and tetracyanoethylene , Hiroshi Komon et al. "Recent Development and Practical Use of Photoconductive Materials and Photoconductors" No. 4
Chapter-Chapter 6: Japan Science Information Publishing Co., Ltd. (1986)
The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc. Moreover, JP-A-58-65439 and 58-
102239, 58-129439, 62-719.
The compounds described in each of the 65 publications and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate and dimethyl. Glycol phthalate or the like can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
It is from 01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0 μ, particularly 10 to 50 μ is suitable.

When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01 to 1 μm, particularly 0.05 to 1 μm.
0.5μ is preferred.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance in the same manner as in the past. Those which have been subjected to a conductive treatment by, for example, those which are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further for preventing curling, the support Having a water-resistant adhesive layer on its surface, having at least one precoat layer on the surface layer of the support, if necessary, and laminating a substrate with a conductive electroconductive plastic such as Al deposited on paper Etc. can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), pp. 2-11 (published in 1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.S.
F. Hoover, J .; Macromol. Sci. C
hem. A-4 (6), pp. 1273-1417 (197).
The ones described in "0 years" etc. are used.

The thickness of the hydrophilizable surface layer of the present invention is 10
.mu.m or less, especially for the Carlson process.
It is preferably 1 to 5 μm. If it is thicker than 5 μm,
There may occur inconveniences such as a decrease in sensitivity of the lithographic printing original plate as an electrophotographic photoreceptor and an increase in residual potential.

In order to actually prepare the photoreceptor of the present invention (printing original plate), generally, an electrophotographic photosensitive layer (photoconductive layer) is first formed on a conductive support according to a conventional method. Then, on this layer, the resin particles of the present invention, the binder resin, and if necessary, the above-mentioned additives and the like are dissolved or dispersed in a volatile hydrocarbon solvent having a boiling point of 200 ° C. or less, and this is applied and dried. Thus, the surface layer can be formed and manufactured.

The organic solvent used is particularly preferably a halogenated hydrocarbon having 1 to 3 carbon atoms such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane. Other chlorobenzene, toluene,
Various solvents used in the coating composition such as aromatic hydrocarbons such as xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran and methylene chloride, and mixtures of the above solvents can also be used. Is.

A publicly known method can be applied to prepare a printing plate using the lithographic printing plate precursor of the present invention obtained as described above, and a copy image is formed on the electrophotographic plate having the above-mentioned structure by a conventional method. After formation, it is created by desensitizing the non-image area. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include scanning exposure using a semiconductor laser, a He-Ne laser, or the like, reflection image exposure using a xenon lamp, a Tigsten lamp, a fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and the like. Next, development is performed using the above electrostatic latent image toner. As the developing method, conventionally known methods, for example, various methods such as cascade development, porcelain brush development, powder cloud development and liquid development can be used. Among them, liquid development is capable of forming a fine image and is suitable for making a printing plate. The formed toner image can be fixed by a known fixing method such as heat fixing, pressure fixing, solvent fixing and the like.

With respect to the lithographic printing original plate having the toner image thus formed, the non-image portion is subjected to a desensitizing treatment to prepare a printing plate.

The desensitizing treatment used in the present invention is a method in which the resin particles of the present invention are hydrolyzed by passing them through a treatment liquid.
Examples thereof include a method of decomposing by a redox reaction, a method of decomposing by a light irradiation treatment, and the like to generate a hydrophilic group.

The method of desensitizing the resin particles, that is, the method of decomposing the protected hydrophilic group is arbitrarily selected depending on the decomposition reactivity of the protected hydrophilic group. One of them is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 and alkaline conditions of pH 8 to 12. Adjustment of these pHs can be easily adjusted by known compounds. Alternatively, a method by redox reaction with a reducing or oxidizing water-soluble compound is also possible, and known compounds can be used as these compounds, for example, hydrazine hydrate, zincate, lipoic acid, hydroquinones, formic acid. , Thiosulfates, hydrogen peroxide, persulfates, quinones and the like.

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

Further, as a compound used in combination for speeding up the hydrophilization reaction, a nucleophilic constant n [R. G. Pearson, H .; Sobe
1, J.I. Songstad, J.M. Amer. Chem.
Soc. , 90, 319 (1968)] containing a substituent having a value of 5.5 or more and having a solubility of 1 part by weight or more in 100 parts by weight of distilled water.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Examples thereof include hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenecarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylamineacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl-2 -Mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid The dicarboxylate benzene sulfinic acid, a hydrazide compound, 2- hydrazino ethanol sulfonic acid, 4-hydrazino butanoic acid,
Hydrazinobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid and the like as a primary or secondary amine compound, for example, N- (2-hydroxyethyl) amine,
N, N-di (2-hydroxyethyl) amine, N, N-
Di (2-hydroxyethyl) ethylenediamine, tri (2-hydroxyethyl) ethylenediamine, N-
(2,3-dihydroxypropyl) amine, N, N-di (2,3-dihydroxypropyl) amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2 -Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

The amount of the nucleophilic compound present in these treatment solutions is 0.05 mol / liter to 10 mol / liter, preferably 0.1 mol / liter to 5 mol / liter.

The surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (1980), etc. Can be used.

The scope of the present invention is not limited to the above specific compound examples. The processing condition is a temperature of 15 ° C.
The immersion time at -60 ° C is preferably 10 seconds to 5 minutes.

Further, as a method of decomposing a specific functional group by irradiation with light, a process of irradiating with "chemically active light" may be included between any of the steps after obtaining a toner image in plate making. Good. That is, after electrophotographic development, light irradiation may be performed for fixing the toner image at the time of fixing the toner image, or other conventionally known fixing methods such as heat fixing, pressure fixing,
After fixing by solvent fixing or the like, light irradiation is performed.

The "chemically active rays" used in the present invention include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays,
Either γ rays or α rays may be used, but ultraviolet rays are preferable. More preferably from wavelength 310 nm to wavelength 5
Those that can emit light in the range of 00 nm are preferable, and generally, a high-pressure or ultra-high-pressure mercury lamp or the like is used. The process of light irradiation is usually 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 to 10 seconds can be sufficiently performed.

[0336]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. The production examples of the dispersion stabilizing resin (monofunctional polymer) for resin particles and resin particles will be specifically exemplified.

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 1 of [M-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,2'-azobisisobutyronitrile (abbreviation AIBN)
1.0 g was added and the mixture was stirred for 4 hours. I. B. N.
0.5 g was added and stirred for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110 ° C. for 8 hours. After cooling, it was reprecipitated in 2 liters of methanol to collect a slightly brownish oily substance and then dried. Yield 73 g, weight average molecular weight 3.6
It was × 10 ⁴ .

[0338]

[Chemical 69]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 2: [M-2] A mixed solution of 100 g of 2-etherhexyl methacrylate, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75 ° C while stirring under a nitrogen stream. 2,2 '
-Azobis (4-cyanovaleric acid) (abbreviation ACV)
2g and reacted for 4 hours. C. V. 0.8 g was added and reacted for 4 hours. After cooling, it was reprecipitated in 2 liters of methanol to collect an oily substance and dried.

50 g of the obtained oily substance, 6 g of 2-hydroxyethyl methacrylate, 150 g of tetrahydrofuran
Was dissolved, and a mixed solution of 8 g of dicyclohexyl carboxylic diimide (D.C.C.), 0.2 g of 4- (N, N-dimethylamino) pyridine and 20 g of methylene chloride was added dropwise at a temperature of 25 to 30C. Then, the mixture was stirred as it was for 4 hours. Next, 5 g of formic acid was added to this reaction mixture and stirred for 1 hour. After separating the precipitated insoluble matter by filtration, the filtrate was reprecipitated in 1 liter of methanol to collect an oily matter. Furthermore,
This oily substance was dissolved in 200 g of tetrahydrofuran, the insoluble substance was filtered off, and reprecipitated again in 1 liter of methanol, and the oily substance was collected and dried. The yield was 32 g and the weight average molecular weight was 4.2 × 10 ⁴ .

[0341]

[Chemical 70]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 3: [M-3] A mixed solution of 96 g of butyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. A. I. B. N. 1.
0 g was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, this reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of an oily substance. The weight average molecular weight was 8 × 10 ³ .

[0343]

[Chemical 71]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 4 of [M-4] A mixed solution of 100 g of n-butyl methacrylate, 4 g of β-mercaptopropionic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. A. I. B. N. 1 g was added and reacted for 6 hours. The reaction mixture was cooled and set to a temperature of 25 ° C., then 10 g of 2-hydroxyethyl methacrylate and 8 g of dicarboxylic carboxylic diimide (D.C.C.), 4- (N, N-).
Dimethylamino) pyridine 0.2 g and methylene chloride 2
0 g of the mixed solution was added dropwise at a temperature of 25 to 30 ° C., and the mixture was further stirred as it was for 4 hours. Next, 5 g of formic acid was added to this reaction mixture and stirred for 1 hour. The precipitated insoluble matter was filtered off, the filtrate was reprecipitated in 1 liter of methanol, and an oily matter was collected by filtration. Further, this oily substance was dissolved in 200 g of tetrahydrofuran, the insoluble substance was filtered off, and reprecipitated again in 2 liters of methanol, and the oily substance was collected and dried. The yield was 68 g and the weight average molecular weight was 6.6 × 10 ³ .

[0345]

[Chemical 72]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Examples 5 to 12: [M-5] to [M-12] In Production Example 4, 100 g of n-butyl methacrylate
Each resin was produced in the same manner as in Production Example 4, except that the monomer group corresponding to Table 2 below was used instead of. The weight average molecular weight of each resin was in the range of 5.5 × 10 ^{3 to} 7 × 10 ³ .

[0347]

[Table 2]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Examples 13 to 16 of [M-13] to [M-16] The same operation as in Production Example 4 was repeated except that the compounds corresponding to Table 3 were used in place of 2-hydroxymethacrylate in Production Example 4. To produce each resin. The weight average molecular weight of each resin was in the range of 6 × 10 ^{3 to} 7 × 10 ³ .

[0349]

[Table 3]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 17: [M-17] A mixed solution of 80 g of hexyl methacrylate, 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was heated to a temperature of 60 ° C while stirring under a nitrogen stream. In addition to this, 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN)
0.8 g was added and the reaction was carried out for 4 hours. I. V. N
0.4 g was added and reacted for 4 hours. Temperature 2 during this reaction
After cooling to 5 ° C., 4 g of methacrylic acid was added and D. C. C. 1 g of a mixed solution of 6 g, 4- (N, N-dimethylamino) pyridine 0.1 g and methylene chloride 15 g.
The mixture was added dropwise over time, and the mixture was stirred as it was for 3 hours. Next, 10 g of water was added, the mixture was stirred for 1 hour, and the precipitated insoluble matter was filtered off.
The filtrate was reprecipitated in 1 liter of methanol to collect an oily substance. Further, this oily substance was dissolved in 150 g of benzene, the insoluble substance was filtered off, and then reprecipitated again in 1 liter of methanol to collect the oily substance and dried. Yield 56g, weight average molecular weight 8x
It was 10 ³ .

[0351]

[Chemical formula 73]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Examples 18 to 22: [M-18] to [M-22] By carrying out the reaction as shown in Production Example 17, the following Table-4 is shown.
The respective dispersion stabilizing resins were synthesized. The weight average molecular weight of each resin was in the range of 6 × 10 ^{3 to} 9 × 10 ³ .

[0353]

[Table 4]

[0354]

[Table 5]

Production Example 1 of Resin Particles [L-1] A mixed solution of 10 g of the dispersion stabilizing resin [M-17] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. In addition, the following monomer [C-1] 47
g, the following monomer [D-1] 3 g, ethylene glycol dimethacrylate 5 g, A. I. V. N. A mixed solution of 0.5 g and 240 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was continued for 2 hours. Furthermore, A. I. V. N.
0.5 g was added and reacted for 2 hours. After cooling, a 200 mesh nylon cloth was passed through to obtain a white dispersion. The latex had an average particle size of 0.18 μm. {: CAPA-5
00 [HORIBA, Ltd.] particle size measurement}

[0356]

[Chemical 74]

Production Examples 2-12 of Resin Particles: [L-2]
[L-12] Same as Production Example 1 except that Monomers [C-1] and [D-1] in Production Example 1 of resin particles were replaced with the present monomer in Table 5 below. To produce resin particles. The average particle size of each particle was within the range of 0.65 to 0.30.

[0358]

[Table 6]

[0359]

[Table 7]

[0360]

[Table 8]

Production Example 13 of resin particles: [L-13] Dispersion stabilizing resin AA-6 [manufactured by Toagosei Co., Ltd. Macromonomer: Macromonomer having methyl methacrylate as a repeating unit: weight average molecular weight 1.5 × 10 5] ⁴ ] 7.5g
A mixed solution of and 133 g of methyl ethyl ketone was heated to 60 ° C. while stirring under a nitrogen stream. 20 g of the following monomer [C-13], 5 g of the following monomer [D-11] and 5 g of diethylene glycol dimethacrylate, A. I. V.
N. A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour, and A. I. V. N. 0.25 g was added and reacted for 2 hours. After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth is 0.25μ.
It was m.

[0362]

[Chemical 75]

Production Examples 14-24 of Resin Particles: [L-1
4] to [L-24] In the same manner as in Production Example 14, except that the polyfunctional compound shown in Table 6 below was used in place of 5 g of ethylene glycol dimethacrylate in Production Example 13 of resin particles, resin particles [L
-15] to [L-25] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0364]

[Table 9]

Production Examples 25-34 of Resin Particles: [L-2
5] to [L-34] 46 g of monomer [C-12], 4 g of monomer [D-7], 2 g of ethylene glycol diacrylate, and 8 g of each dispersion stabilizing resin [M] shown in Table 7 below. Then, 230 g of dipropyl ketone was added dropwise to a solution of 200 g of dipropyl ketone heated to a temperature of 60 ° C. under a nitrogen stream in 2 hours while stirring. After reacting for 1 hour as it is, A. I. V. N.
0.3 g was added and reacted for 2 hours. After cooling, the average particle size of each dispersion obtained through a 200-mesh nylon cloth was 0.
It was 18 to 0.25 μm.

[0366]

[Table 10]

Production Examples 35-40 of Resin Particles: [L-3
5] to [L-40] Dispersion stabilizing resin AA-6 7 g, monomer {D-4] 4
g, a mixture of each monomer shown in Table 8 below and 340 g of a reaction solvent shown in Table 9 below was heated to a temperature of 60 ° C. under a nitrogen stream. In addition to this, I. V. N. Add 0.3g 2
Reacts for a time, and further I. V. N. 0.1 g was added and reacted for 2 hours. The average particle size of the dispersion obtained after passing through a 200 mesh nylon cloth after cooling is 0.15 μm to 0.3
It was in the range of 0 μm.

[0368]

[Table 11]

[0369]

[Table 12]

Next, a synthesis example of the binder resin [A] will be specifically exemplified. Synthesis Example of Resin [A] 1: [A-1] A mixed solution of 96 g of benzyl methacrylate, 4 g of thiosalicylic acid and 200 g of toluene was heated under a nitrogen stream at a temperature of 75.
Warmed to ° C. 1.0 g of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 0.4 g was added for 2 hours, and then A. I. B. N. 0.2 g was added and stirred for 3 hours. The obtained copolymer [A-1] has the following structure,
Its weight average molecular weight was 6.8 × 10 ³ .

[0371]

[Chemical 76]

Synthesis Examples 2 to 13 of Resin [A]: [A-2]
~ [A-13] In Synthesis Example 1 of Resin [A], the monomers shown in Table 9 below were used in place of 96 g of benzyl methacrylate, and the other operations were performed in the same manner as in Synthesis Example 1 to obtain resins [A-13]. -2] ~ [A
-13] was synthesized. The weight average molecular weight of each resin is 6.0.
× was 10 ³ ~8 × 10 ^3.

[0373]

[Table 13]

[0374]

[Table 14]

[0375]

[Table 15]

Synthesis Examples 14 to 24 of Resin [A]: [A-1
4] to [A-24] In Synthesis Example 1 of Resin [A], instead of 96 g of benzyl methacrylate and 4 g of thiosalicylic acid, the following Table-10 is used.
Each of the resins [A-14] to [A-24] was synthesized by the same reaction as in Synthesis Example 1 except that the methacrylate and mercapto compound shown in 1 were used, and that 150 g of toluene and 50 g of isopropanol were used instead of 200 g of toluene. .. The weight average molecular weight of each obtained copolymer was 6.8 × 10 ³ .

[0377]

[Table 16]

[0378]

[Table 17]

[0379]

[Table 18]

Synthesis Example 25 of resin [A]: [A-25] 1-naphthyl methacrylate 95.5 g, methacrylic acid 0.5 g, toluene 150 g and isopropanol 50.
The mixed solution of g was heated to a temperature of 80 ° C. under a nitrogen stream.
4,4'-azobis (4-cyano) valeric acid (abbreviation A.
C. V. ) 5.0 g was added and stirred for 5 hours. Furthermore, A.
C. V. 1 g was added for 2 hours, and then A. C. V. 1 g was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5 × 10 ³ .

[0380]

[Chemical 77]

Synthesis Example 26 of Resin [A]: [A-26] 50 g of methyl methacrylate and 150 g of methylene chloride.
The mixed solution of was cooled to -20 ° C under a nitrogen stream. 1.0 g of 10% 1,1-diphenylhexyllithium hexane solution adjusted immediately before was added, and the mixture was stirred for 5 hours. Carbon dioxide was passed under stirring at a flow rate of 10 ml / cc for 10 minutes, cooling was stopped, and the reaction mixture was allowed to stir until it reached room temperature. Next, the reaction mixture was reprecipitated in a solution of 50 cc of 1N hydrochloric acid dissolved in 1 liter of methanol, and a white powder was collected by filtration. The powder was washed with water until it became neutral, and then dried under reduced pressure. Yield 18 g, weight average molecular weight 6.
It was 5 × 10 ³ .

[0383]

[Chemical 78]

Synthesis Example 27 of Resin [A]: [A-27] 95 g of benzyl methacrylate, 4 g of thioglycolic acid
And a mixed solution of 200 g of toluene under a nitrogen stream at a temperature of 7
Warmed to 5 ° C.

A. C. V. 1.0 g was added and reacted for 6 hours, and then A. C. V. 0.4 g was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 7.8 × 10.
^{Was 3} .

[0386]

[Chemical 79]

Example 1 and Comparative Examples AB (Example 1) 8 g (as solid content) of resin [A-5],
34 g of resin [B-1] having the following structure (as solid content),
A mixture of 200 g of photoconductive zinc oxide, 0.017 g of methine dye [I] having the following structure, 0.18 g of phthalic anhydride and 300 g of toluene was mixed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 9 × 10 ³ r.p. p. m. At 10 rpm
Dispersed for minutes. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 100 ° C. for 30 seconds.

[0388]

[Chemical 80]

A toluene dispersion having the following formulation was coated on the surface of this photoreceptor with a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour to form a surface layer of about 2 μm.

Toluene Dispersion for Surface Layer Resin [B′-1] having the following structure 3 g Resin particles [L-1] 5 g (as solid content) Phthalic anhydride 0.02 g O-chlorophenol 0.001 g was added to toluene. The total amount was 100 g.

[0391]

[Chemical 81]

Then, an electrophotographic light-sensitive material was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. (Comparative Example A) The same operation as in Example 1 was carried out except that only 42 g of the resin [B-1] was used in place of 8 g of the resin [A-5] and 33 g of the resin [B-1] in Example 1. An electrophotographic photosensitive material was produced. (Comparative Example B) Comparative Dispersion Resin Particles: LR-1 Production Example 1 of Resin Particles: In L-1, except that the resin having the following structure was used in place of 10 g of the dispersion stabilizing resin [M-32], It was synthesized in the same manner as in Production Example 1. The average particle size of the obtained latex was 0.17 μm.

[0393]

[Chemical formula 82]

Comparative Photoreceptor In Example 1, 3 g of resin particles [LR-1] were used instead of 3 g of resin particles [L-1] of the toluene dispersion for the surface layer.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that (as the solid content) was used.

Film formation (smoothness of the surface), electrostatic characteristics, desensitizing property of the photoconductive layer (represented by contact angle of water of the photoconductive layer after desensitizing treatment) and printing of these light-sensitive materials. I investigated the sex. As for printability, a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) was used as a developer, and a developer LD-1 having the following content was used to perform exposure / development processing to form an image and desensitization treatment. It investigated using the lithographic printing plate obtained by doing. (Note that the printing machine used was a Hamada Star 800SX type manufactured by Hamada Star Co., Ltd.)

Liquid developer: LD-1 ・ Synthesis of toner particles Methyl methacrylate 60 g, methyl acrylate 40
g, 20 g of a dispersion polymer having the following structure and Isopar H6
While stirring 80 g of the mixed solution under a nitrogen stream, a temperature of 65
Warmed to ° C. To this, 1.2 g of 2,2'-azobis (isovaleronitrile) (AIVN) was added and reacted for 2 hours. I. V. N. 0.5 g was added and the mixture was reacted for 2 hours. I. V. N. 0.5 g was added and reacted for 2 hours.

Next, the reaction temperature was raised to 90 ° C. and the temperature was raised to 30 mm.
The mixture was stirred under reduced pressure of Hg for 1 hour to remove unreacted monomers. After cooling to room temperature, it was filtered through a 200-mesh nylon cloth to obtain a white dispersion. The reaction rate of the monomers of the obtained dispersion was 95% by weight, and the average particle size of the resin particles was 0.25.
The particle size was μm and the monodispersity was good. (The particle size is C
APA-500: used by Baba Seisakusho).

[0398]

[Chemical 83]

Production of colored particles: 10 g of tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 1 nigrosine
0 g and 30 g of Isopar G were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine. -Production of liquid developer 45 g of the resin dispersion of the toner particles, 25 g of the nigrosine dispersion, 0.06 g of hexadecene / semi-maleic acid octadecylamide copolymer and 15 g of FOC-1800 were diluted to 1 liter of Isopar G. By doing so, a liquid developer for electrostatic photography was prepared.

The above results are summarized in Table-11.

[0401]

[Table 19]

Note 1) Smoothness of surface layer:
Using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.), the smoothness (sec / cc) under the condition of an air capacity of 1 cc
Was measured. Note 2) Electrostatic characteristics: Corona discharge at -6 kV for 20 seconds using a paper analyzer (Kawaguchi Electric Co., Ltd. paper analyzer SP-428 type) on each light-sensitive material in a dark room at a temperature of 20 ° C and 65% RH. After that, it was left for 10 seconds and the surface potential V ₁₀ at this time was measured. Then, the potential V ₁₀₀ after standing still in the dark for 100 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [D. R. R. The (%)], (V ₁₀₀ /
It was determined by V ₁₀ ) × 100 (%).

Further, the surface of the photoconductive layer was-
After being charged to 400 V, irradiation with monochromatic light having a wavelength of 780 nm is performed, and the time until the surface potential V ₁₀ is attenuated to 1/10 is obtained, and the exposure amount E _1/10 (erg / cm ² ) is calculated from this. The condition of temperature 20 ° C. and 65% RH was set to I, and the same evaluation was performed under the environmental conditions of temperature 30 ° C. and 80% RH, and this was set to II. Note 3) Imaging: Each light-sensitive material was left for one day under the following environmental conditions. Next, it is charged at -5kV and 2.0m as a light source.
Using a W output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm), on the surface of the photosensitive material,
After exposure under a dose of 45 erg / cm ² with a pitch of 25 μm and a scanning speed of 330 m / sec, the above-mentioned LD-1 was used as a liquid developer to develop and fix the copy image (fog, fog, The image quality) was visually evaluated. Note 4) Raw plate water retentivity: Each light-sensitive material itself was immersed for 3 minutes in a desensitizing solution E-1 having the following formulation (original plate not made into a plate: abbreviated as raw plate). These plates were printed on a Hamada Star 8005X type manufactured by Hamada Star Co., Ltd. using distilled water as dampening water, and the presence or absence of background stains on the 50th printed sheet after printing was visually evaluated. Desensitizing treatment liquid: E-1 Diethanolamine 75 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 3 g Benzyl alcohol 100 g was diluted with distilled water to a total volume of 1.0 liter and then adjusted to pH 13.5 with potassium hydroxide. . Note 5) Background stain of printed matter: After making each photosensitive material by the same operation as in Note 3) above, immersing it in the processing liquid of E-1 used for Note 4) for 3 minutes, and then using E as fountain solution. A solution obtained by diluting -1 with water three times was also printed using a neutral paper as a printing paper, and the number of printed sheets until the background stain of the printed matter was visually discriminated was examined.

The surface smoothness of each photosensitive material was good. The electrostatic characteristics of the present invention and Comparative Example B were good, and the actual image pickup properties and the copied images were clear. However, Comparative Example A is D.I. R. R. In addition, the photosensitivity was remarkably lowered, and the image pickup property was not usable for practical use due to the lack of fine lines and characters, and the fog in the non-image area. These facts show that by using the resin [A] of the present invention as the binder resin of the photoconductive layer, excellent electrophotographic characteristics can be obtained even in the semiconductor laser light scanning exposure method.

When each of these photoreceptors was subjected to a desensitizing treatment to evaluate the degree of hydrophilicity of the non-image area (water-holding capacity of the original plate), Comparative Example B showed significant background stain due to the adhesion of printing ink, The part was not sufficiently hydrophilized.

Further, after the plate was actually made and then desensitized, the planographic printing plate of the present invention showed no scumming even when neutral paper was used as a printing paper, and showed a clear print quality of an image. 5,000 prints were obtained. On the other hand, in Comparative Example A, since the reproducibility of the image after plate making was insufficient, the image of the printed matter was also unsatisfactory after printing. Further, in Comparative Example B, the image after plate making was good, but the non-image area was not sufficiently desensitized, so that the printed matter had background stains from the imprinting.

This means that only the resin particles [L] of the present invention in the surface layer develop sufficient hydrophilicity and ink adhesion to non-image areas does not occur. As described above, the electrophotographic lithographic printing plate precursor in which the hydrophilicity of the non-image area was sufficiently advanced and the background fog did not occur was the only one of the present invention. Example 2 In Example 1, 8 g of resin [A-5], resin [B-
1] 34 g, methine dye [I] 0.017 g and resin particles [L-1] 5.0 g, instead of resin [A-19] 6
g, resin [B-2] having the following structure 35.0 g, methine dye [II] having the following structure 0.020 g, and resin particles [L-3
7] An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 5.5 g was used.

[0408]

[Chemical 84]

Each characteristic was measured in the same manner as in Example 1.
The following are particularly severe environmental conditions (30 ° C, 80% R
H) shows the measurement results under. Electrostatic properties V _10: -770V D. R. R. : 78% E _1/10 : 42 erg / cm ² Imaging property: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No background stain up to 5,000 sheets E-1 used in 1
In place of the above, the desensitizing treatment liquid E-2 having the following formulation was used.

Desensitizing treatment liquid: E-2 Serine 60 g N, N-dimethylmonoethanolamine 60 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8 g Methyl ethyl ketone 100 g was dissolved in distilled water to a total volume of 1.0 liter and water. The pH was adjusted to 13.0 with potassium oxide.

Each of the light-sensitive materials of the present invention has a charging property,
The dark charge retention rate and photosensitivity were excellent, and clear images without actual fog were obtained even under severe conditions of high temperature and high humidity (30 ° C., 80% RH) in actual copied images and printed matter. Examples 3 to 14 In place of the resin particles [L], resin [A] and resin [B] used in Example 1, 5.0 g of resin particles [L] of the present invention shown in Table 12 below (solid content) Each) and each of the photosensitive materials were prepared in the same manner as in Example 1 except that 5 g of the resin [A] and 34 g of the resin [B-3] having the following structure were used.

The electrostatic characteristics and the printing characteristics were evaluated by operating in the same manner as in Example 1.

[0413]

[Chemical 85]

[0414]

[Table 20]

With respect to each of the light-sensitive materials, the electrostatic property and the printing property were measured by operating in the same manner as in Example 1. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high at high temperature. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image was obtained with no background fog or fine line skipping.

When the performance of the offset lithographic original plate was evaluated after desensitization, the water retention of the original plate was good and it was possible to print 3,000 sheets even in the actual printing results after plate making. Examples 15 to 18 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 13 below were used instead of the methine dye [I].

[0417]

[Table 21]

[0418]

[Table 22]

Each of the light-sensitive materials exhibited almost the same characteristics as those in Example 1 in terms of image pick-up property and printing property, showing good results. Examples 19-21 6.0 g of resin [A] shown in Table 13 below, 34.0 g of binder resin [B-4] having the following structure, 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranin, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was dispersed in a ball mill for 4 hours. The electrophotographic photosensitive material was prepared by applying the dispersion for forming a photosensitive layer to a conductive-treated paper with a wire bar so that the dry adhesion amount was 20 g / m ^2, and drying at 100 ° C. for 3 minutes.

[0420]

[Chemical formula 86]

A toluene dispersion having the following formulation was applied on the surface of this photoreceptor by a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour to form a surface layer of about 2 μm. Toluene Dispersion for Surface Layer 2 g of resin [B′-2] having the following structure: 5 g of resin particles [L] shown in Table 13 below (as solid content) 1,2,4,5-benzenetetracarboxylic dianhydride 0.0015 g of 02 g phenol was added to toluene to make the total amount 100 g.

[0422]

[Chemical 87]

Then, an electrophotographic light-sensitive material was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. The film properties (surface smoothness) of the light-sensitive material, the imaging property, the desensitizing property of the photoconductive layer (expressed by the contact angle of the photoconductive layer after the desensitizing treatment with water) and the printability were examined.

The above results are summarized in Table-14.

[0425]

[Table 23]

In the mode for carrying out the evaluation items shown in Table 14, the image pick-up performance was performed as follows, and otherwise the same as in Example 1. Note) Imaging: Each photosensitive material and fully automatic plate-making machine ELP40
After leaving 4V (manufactured by Fuji Photo Film Co., Ltd.) at room temperature and humidity (20 ° C., 65%) for one day, plate making is performed to form a copy image, and the obtained copy original image (fog, image Visually observe (image quality) (this is referred to as I). The image quality II of the copied image is tested by the same method as the above I except that the platemaking is performed at high temperature and high humidity (30 ° C., 80%).

As shown in Table 14 for each light-sensitive material, all the performances were good, and the number of printable sheets was 3,000. Example 22 5 g of bisazo pigment having the following structural formula, and tetrahydrofuran 9
5 g and resin [A-1] 0.8% by weight and resin [B-
4] A mixture of 30 g of a 4.2 wt% tetrahydrofuran solution was thoroughly pulverized with a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 1 by using a wire round rod to give a dispersion of about 0.
A 7 μm charge generation layer was formed.

[0428]

[Chemical 88]

Next, the hydrazone compound 20 of the following structural formula
g, 20 g of polycarbonate resin (manufactured by GE Corporation, trade name Lexan 121) and 160 g of tetrahydrofuran are applied on the charge generation layer using a wire round rod to form a charge transport amount of about 18 μm, and two layers are formed. An electrophotographic photosensitive member having a photosensitive layer composed of was obtained.

[0430]

[Chemical 89]

Resin particles [L-13] were formed on the surface of this photoreceptor.
% By weight (as solid content), 2% by weight of resin [B′-3] having the following structure, 0.01% by weight of phthalic anhydride,
And a toluene solution containing 0.005% by weight of 2-chlorophenol were coated with a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 130 ° C. for 1 hour to about 2
A μm surface layer was formed. Then in the dark at 20 ℃, 65%
An electrophotographic photosensitive material was produced by leaving it for 24 hours under the condition of RH.

[0432]

[Chemical 90]

This light-sensitive material was immersed in the desensitizing solution (E-3) prepared according to the following formulation for 3 minutes to be desensitized. Desensitizing treatment solution (E-3) Monoethanolamine 52 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 10 g Methylethylketone 80 g These were dissolved in distilled water to pH 13.
The total amount was adjusted to 0 to make 1.0 liter. Distilled water 2
It was 10 ° or less when a contact angle with the formed water was measured with a goniometer by placing μ liter of water droplets.
The contact angle before the desensitizing treatment was 95 °, which clearly shows that the surface layer of the present light-sensitive material was very favorably hydrophilized.

As in the first embodiment, this is a fully automatic plate making machine E.
When plate making was carried out by using the developer LD-1 with LP404V, the density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear.

[0435] Furthermore, the master plate for master making after the plate making was added to the desensitizing solution (E-3) prepared by the above-mentioned formulation at a temperature of 40.
Desensitizing treatment was carried out by treating at 0 ° C. for 2 minutes. When this offset printing original plate was printed by a printing machine, the printed matter after printing 3,000 sheets had no fog in the non-image area and the image was clear. Examples 23 to 27 Resin particles used in the surface layer in Example 19 [L-1
6] Resin particles [L] shown in Table 15 below instead of 5.5 g
Each photosensitive material was prepared in the same manner as in Example 19 except that 6 g was used in total.

[0436]

[Table 24]

After each plate was made in the same manner as in Example 19, it was desensitized with the following desensitizing solution E-4 at a temperature of 35 ° C. for 3 minutes. Desensitizing treatment liquid (E-4) Boric acid 55 g Sodium sulfite 40 g Benzyl alcohol 80 g Dissolve these in distilled water to make a total volume of 1.0 liter, and prepare with sodium hydroxide so that this liquid has a pH of 13.0. did.

When each of the obtained master plates for offset master was printed, the printed material after 3,000 sheets had no background stain on the non-image area and the image was clear.

[0439]

According to the present invention, it is possible to obtain a lithographic printing plate precursor having an excellent printed image and high printing durability even under severe conditions. Further, the lithographic printing plate precursor of the present invention is effective for a scanning exposure method using a semiconductor laser beam.

Claims (4)

[Claims] 1. A lithographic printing plate precursor using an electrophotographic photosensitive member comprising a photoconductive layer of at least one layer provided on a conductive support, and a surface layer provided on the uppermost layer of the photoconductive layer. A lithographic printing plate containing at least one kind of the following non-aqueous dispersion resin particles [L] and at least one kind of the following resin [A] as a binder resin for the photoconductive layer. Original version. Non-aqueous dispersion resin particles [L]: In a non-aqueous solvent, it is soluble in the non-aqueous solvent, but is insolubilized by polymerization.
Decomposed by thiol group, sulfo group, amino group and -P
_{(= Z 0) (- Z} 0 -H) R '1 group [Z ₀ represents an oxygen atom or a sulfur atom. R _'1 is -Z ₀ -H, a hydrocarbon or _{-Z 0 -R' 2 (R '} 2 represents a hydrocarbon group) at least one functional group for generating at least one of the radicals represents a] A monofunctional monomer (C) contained and a monofunctional monomer (D) containing a substituent containing a silicon atom and / or a fluorine atom and copolymerizable with the monofunctional monomer (D). And) in the presence of a dispersion-stabilizing resin soluble in the non-aqueous solvent, the copolymer resin particles obtained by a dispersion polymerization reaction. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing a repeating unit represented by the following general formula (I) in an amount of 30% by weight or more as a polymer component, and polymer main at one end of the _{chain, -PO 3 H 2, -SO 3} H, -COO
H, -P (= O) (OH) R ₀₁ [R ₀₁ represents a hydrocarbon group or -OR ₀₂ (R ₀₂ represents a hydrocarbon group)] and at least one selected from a cyclic acid anhydride-containing group. A resin formed by combining two polar groups. [Chemical 1] [However, in the above formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. ] 2. The lithographic printing plate precursor as claimed in claim 1, wherein the non-aqueous solvent-based dispersed resin particles have a crosslinked structure. 3. The dispersion stabilizing resin comprises a polymer chain in the polymer chain,
The composition comprises at least one polymerizable double bond group moiety represented by the following general formula (II).
And the lithographic printing plate precursor as described in 2 above. [Chemical 2] [In the general formula (II), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CONR 1 -, - S
_{O 2 NR 1 -, - C} 6 H 5 -, - CONHCOO-, or -CONHCONH- a represents (wherein, p represents an integer of 1 to 4, R ₁ is a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms Represents a group), b ₁ and b ₂ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or —C via a hydrocarbon group.
OO-R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)] 4. The aryl group-containing methacrylate component represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I), The lithographic printing plate precursor as claimed in any one of claims 1 to 3, comprising at least one. [Chemical 3] [In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ₀₄ or —COOR.
₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent a single bond or a connecting atom number of 1 to 4 which connects —COO— and the benzene ring. Represents a linking group of. ]