JPH05210265A - Original 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 functional groups expressed by formula I and formula II 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 resin A has 1X10<3> to 2X10<4> weight average mol.wt. and is formed by bonding a polymer component of a specific repeating unit and a polar group in the side chain 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 an electrophotographic method, and more particularly to an improvement in the composition of a photoconductive layer and specific properties on the photoconductive layer. The present invention relates to a lithographic printing plate precursor having a surface layer having

[0002]

2. Description of the Related Art At present, various types of offset master 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 used on a conductive support. The photoconductor provided with a photoconductive layer containing as a main component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is desensitized liquid called an etchant. A technique for obtaining an offset original plate by subjecting the non-image portion to hydrophilic treatment selectively 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 particular, as an offset original plate, there is a big problem that scumming occurs due to insufficient desensitizing property, and in order to improve this, various studies have been made on development of a zinc oxide binder resin for improving desensitizing property. It has been done, for example, Japanese Patent Publication Sho 5
No. 0-31011, JP-A-53-54027, JP-A-54-20735, JP-A-57-202544, and JP-A-58-68046. However, even the resins that are said to be effective in improving the desensitizing property are still unsatisfactory in the background stain and the printing durability when actually evaluated. Further, it is essential to desensitize zinc oxide with a desensitizing treatment solution under acidic conditions and to use an aqueous solution containing a desensitizing agent under acidic conditions as the dampening water during printing. Therefore, when acidic paper is used as the printing paper, a problem occurs, but when neutral paper is used, the printing durability is significantly reduced. Depending on the printing ink used, dampening water interacts with the ink on the printing material to cause scumming on the printed matter or abnormal emulsification of the ink. It causes the problem of being lost.

On the other hand, it is also possible to use an organic photoconductive compound as the photoconductive particles and use an electrophotographic body provided with a binder resin and a photoconductive layer on a grained aluminum substrate.

In order to make an original plate of this kind, a toner image is formed on the photosensitive layer by a usual electrophotographic method, and then the non-image area is dissolved and removed with a processing liquid in the same manner as described above. As a result, the non-image portion becomes an aluminum substrate and becomes hydrophilic. For example, Japanese Patent Publication No. 37-17162
Japanese Patent Publication No. 46-39405, Japanese Patent Laid-Open No. 52-2437.
JP-A-56-107246 and the like, when using a photosensitive layer in which an oxadiazole compound or an oxazole compound is bound with an alkali-soluble resin such as a styrene-maleic anhydride copolymer, or 55
-105254, JP-A-55-16125, JP-A-58-150953, JP-A-58-162961 and the like, and a photosensitive material comprising a phthalocyanine pigment or azo pigment and an alkali-soluble phenol resin. The case of using layers is known.

However, this plate-making process requires a large-scale device because the photosensitive layer in the non-image area must be dissolved and removed. Furthermore, a large amount of the photosensitive layer composition is eluted and accumulated in the processing liquid. Therefore, the durability of the treatment liquid becomes a problem, and at the same time, the problem of disposal is left as a big problem, and it is hard to say that the method is versatile.

Further, a method of forming a hydrophilic plate of a non-image area surface hydrophilic treatment type by providing a specific resin layer on an ordinary electrophotographic photosensitive member is disclosed in JP-B-45-5606.
No. That is, a printing plate is disclosed in which a surface layer made of a vinyl ether-maleic anhydride copolymer and a hydrophobic resin compatible therewith is provided on an 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 when it is ring-opened and hydrophilized. Therefore, 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, in JP-A-60-90343, JP-A-60-159756, JP-A-61-217292 and the like, a silylated polyvinyl alcohol is used as a main component and a crosslinking agent is also used. A method of providing a surface layer (hydrophilizable layer) is shown. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. In order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual hydroxyl groups are crosslinked with a crosslinking agent. It is described that these improve the stain resistance of the printed matter and improve the number of printed sheets.

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 stably because it is a polymer reaction. Further, since the chemical structure of the hydrophilic polymer is limited, 1) chargeability, 2) quality of copied image (dot reproducibility / resolution of image area, There is a problem that it is difficult to prevent the surface layer from affecting the background fog in the image area), 3) 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 upon 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 liquid or immersion water used during 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.

[0016]

However, various recent O.I. A. As for images of copy originals obtained from a device, various kinds and images of high definition have come to be used. On the other hand, it has become clear that, in the case of the original plate, a copy image with good reproducibility cannot be obtained with respect to the original document.

Further, in the electrophotographic lithographic printing plate precursor as a digital direct lithographic printing plate, when a scanning exposure system using a semiconductor laser beam is adopted, the time becomes longer than that of the whole surface simultaneous exposure system using visible light. In addition, since there are restrictions on the exposure intensity, electrostatic characteristics,
In particular, higher performance is required for dark charge retention characteristics and photosensitivity.

On the other hand, in the above-mentioned known original plate, the electrophotographic characteristics are deteriorated, and the actual copy image is apt to cause the background fog, and the fine lines are skipped and the characters are blurred.
As a result, when printing as a lithographic printing plate precursor, the image quality of the printed matter deteriorates, and the effect of preventing scumming due to the hydrophilicity improvement of the non-image portion of the binder resin is lost.

That is, various O.V. A. A lithographic printing plate precursor that can be used in each case such as an image of a copy original obtained from an apparatus and an exposure method using a semiconductor laser beam is desired.

The present invention improves the above-mentioned problems of the conventional lithographic printing plate precursor. That is,
The first 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 have a uniform background stain as an offset original plate. An object of the present invention is to provide a lithographic printing plate precursor that is excellent in desensitizing property and does not generate a background stain.

The second object of the present invention is to provide a lithographic printing plate precursor that is not easily affected by the type of sensitizing dye that can be used in combination and has excellent electrostatic properties even in a scanning exposure system using a semiconductor laser beam.

[0022]

The object of the present invention is to provide a lithographic plate using an electrophotographic photosensitive member comprising a conductive support and at least one photoconductive layer on the conductive support, and a surface layer on the uppermost layer. In the printing plate precursor, the surface layer contains at least one of the following non-aqueous dispersion resin particles [L], and at least one of the following resins [A] is used as a binder resin for the photoconductive layer. Achieved by a lithographic printing plate precursor containing a seed.

The non-aqueous dispersion resin particles [L] are represented by the general formula (I) and / or the general formula (II), which are soluble in the non-aqueous solvent but are insolubilized by polymerization. And a monofunctional monomer (C) containing at least one functional group represented by the formula (1) and a monofunctional monomer (C) containing a substituent containing at least a silicon atom and / or a fluorine atom. Non-aqueous dispersion resin particles obtained by carrying out a dispersion polymerization reaction of a possible monofunctional monomer (D) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.

As the resin [A], 1 × 10 ³ to 2 × 1
Having a weight average molecular weight of 0 ⁴ and having a repeating unit represented by the following general formula (III) as a polymer component in an amount of 30% by weight or more, -PO ₃ H ₂ , -SO ₃ H, -COOH, -P.
(= O) (OH) R ₀₁ [R ₀₁ is a hydrocarbon group or -OR ₀₂
Group (R ₀₂ represents a hydrocarbon group)] and 0.5 to 15% by weight of a polymer component having at least one polar group selected from an acid anhydride group.

[0025]

[Chemical 4]

[However, in the above formula (II), a ₁ ,
a ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ₀₃ represents a hydrocarbon. ] [-P above
(= O) (OH) R ₀₁ is

[0027]

[Chemical 5]

Is shown. In the present invention, the non-aqueous solvent-based dispersed resin particles may have a crosslinked structure.

Further, as the above-mentioned dispersion stabilizing resin in the present invention, those containing at least one polymerizable double bond group moiety represented by the following general formula (IV) in the polymer chain are particularly preferable. It is mentioned as a thing.

[0030]

[Chemical 6]

[In the general formula (IV), V ₀ is -O
-, - COO -, - OCO -, - (CH 2) p OCO
_{-, - (CH 2) p} COO -, - SO 2 -, - CON
_{(R 1) -, SO 2} N (R 1) -, - C 6 H 4 -, - C
ONHCOO- or -CONHCONH- (where p represents an integer of 1 to 4 and R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b ₁ and b
_2, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₂ (R ₂ through -COO-R ₂ or a hydrocarbon radical is a hydrogen atom or a substituent The resin [A] is preferably represented by the following general formula (IIIa) and the following general formula (IIIb) as a copolymer component represented by the general formula (III). It is preferable to contain at least one of the aryl group-containing methacrylate components.

[0032]

[Chemical 7]

[However, the above formulas (IIIa) and (III
In b), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, or -COR.
₀₄ or -COOR ₀₅ (R ₀₄ and R ₀₅ each have 1 to 1 carbon atoms
0 represents a hydrocarbon group) and L ₁ and L ₂ are each-
It represents a single bond or a connecting group having 1 to 4 connecting atoms for connecting COO- and the benzene ring. The lithographic printing plate precursor of the known art as described above contains, in the surface layer thereof, a surface layer resin which generates a hydrophilic group (for example, a hydroxyl group, a carboxyl group, etc.) by decomposition, and a compound which crosslinks the resin is also used. Things to do are being tried.

On the other hand, the present invention is obtained in the presence of a dispersion stabilizing resin containing a photoconductive layer containing a resin [A] as a binder resin and further containing a silicon atom and / or a fluorine atom. This is a lithographic printing plate precursor for an electrophotographic plate making system using an electrophotographic photoreceptor provided with an uppermost layer (surface layer) containing non-aqueous dispersion resin particles.

That is, the non-image portion after the toner image is formed according to a usual electrophotographic process (plate making) is sometimes abbreviated as non-aqueous dispersion resin particles (hereinafter referred to as resin particles [L]) contained in the uppermost layer. ) Is subjected to a desensitizing treatment to improve the lipophilic surface to a hydrophilic surface to obtain a printing original plate. As a result, the conventional problems can be overcome.

The resin particles [L] used in the present invention have an average particle size of 1 μm or less and a narrow particle size distribution, and the resin particles [L] have at least important properties. It has two. One of them is the functional group [monofunctional monomer (C) represented by the above general formula (I) of resin particles when treated with a treatment liquid containing at least one nucleophilic hydrophilic compound. ] A nucleophilic reactive hydrophilic compound can be added to the end of the above], whereby the particles can exhibit hydrophilicity and, at the same time, when the resin particles have a crosslinked structure, It is insoluble or slightly soluble in water while having water swelling property.

On the other hand, in the case of the functional group [monofunctional monomer (C)] represented by the above general formula (II), the dehydrohalogenation reaction first proceeds rapidly by the alkaline treatment solution. The functional group represented by the formula (I) is generated, and thereafter, the functional group becomes hydrophilic by the same reaction as described above.

As another one, 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 is bound. It is presumed that the above phenomenon will cause a migration / concentration phenomenon on the surface portion of the surface layer. Further, the polymer as a dispersion stabilizing resin used in the synthesis of the resin particles [L] is formed by physicochemical adsorption with an insoluble component composed of at least the polymer of the monomer (C), or In the case of the dispersion-stabilizing resin containing the polymerizable double bond group portion represented by the formula (III), it is considered that both polymer components are chemically bonded.

As described above, due to both effects of concentrating the particles [L] on the surface portion and making the particles hydrophilic by desensitizing treatment, sufficient water retention of the non-image area of the surface layer is achieved. It is a thing.

Further, the present invention contains, as a binder resin for the photoconductive layer, a specific polymer component represented by the formula (III) and a polymer component containing at least one of the specific polar groups described above. And a low molecular weight polymer resin [A]. Generally, in an electrophotographic photosensitive member, if a further layer (for example, a surface layer) is provided on the photoconductive layer, electrostatic characteristics (especially photosensitivity, residual potential, etc.) are deteriorated and faithful image reproducibility is deteriorated. In addition, the effect is great as various improvements are tried.

In order to solve this problem, the present invention is one of them, in which the faithful reproducibility of the copied image is not impaired when the image is actually taken by improving the electrostatic characteristics of the photoconductive layer. It was made. Furthermore, although it is usually sensitized by using a spectral sensitizing dye, these dyes sufficiently interact with the photoconductor even when the type of the spectral sensitizing dye used in the photoconductive layer of the present invention is changed. be able to.

Particularly in the case of dyes used for spectral sensitization for semiconductor laser light, this interaction becomes insufficient in the system of known binder resin, but in the system of the present invention, such development is not very excellent. It is a thing.

Furthermore, the resin particles contain a polymer component containing a fluorine atom and / or a silicon atom, whereby the particles cause a phenomenon of migration / concentration on the surface portion of the photoconductive layer, and a desensitizing oil is not produced. In showing hydrophilicity by chemical treatment,
In order to produce the same effect (water retention) as that of the known technique, the addition amount thereof was very small, and thereby the adverse effect on the electrophotographic characteristics could be minimized.

That is, the original plate of the present invention solves the difficult problem of excellent electrophotographic characteristics for forming a copy image and excellent water retention in the non-image area after desensitizing treatment after the copy image is formed. I was able to.

As described above, the resin particles of the present invention [L]
Means that the functional groups represented by the general formulas (I) and / or (II) can express hydrophilicity, and the resin particles [L] of the present invention are hydrophilized with a hydrophilic compound having a nucleophilic reactivity. The reaction mechanism is shown in the following reaction formula (1) using a representative example of sulfite ion as a nucleophilic reactive hydrophilic compound.

[0046]

[Chemical 8]

That is, the resin particles of the present invention have a nucleophilic reactivity such that the nucleophilic constant n of the person in the processing liquid is 5.5 or more only when the non-image area is desensitized as a lithographic printing original plate. By adding a hydrophilic group to the terminal by reacting with the hydrophilic compound as described above to develop hydrophilicity, that is, by being hydrophilized, it does not react with moisture in the atmosphere, and therefore storage stability is concerned. Is not a matter of concern at all.

More specifically, the resin particles of the present invention have a maximum particle diameter of 2 μm or less, preferably 0.5 μm.
m or less. The average particle size of the particles is preferably 0.8 μm or less, more preferably 0.5 μm or less.

The smaller the particle size of the resin particles is, the larger the specific surface area thereof is, which brings about a good effect on the electrophotographic characteristics described above. Colloid particles (0.01 μm or less) are sufficient, but they are too small. If it is too much, it will be similar to the case of molecular dispersion, and the effect of being particles for improving the water retention ability will be weakened. Therefore, it is preferable to use 0.001 μm or more.

Further, in the present invention, the resin particles are those obtained by binding a hydrophobic polymer component, that is, a polymer component corresponding to the dispersion stabilizing resin, and the hydrophobic portion is the binder resin of the photoconductive layer. Since they interact with each other, the anchor effect of this portion does not elute with dampening water during printing, and good printing characteristics can be maintained even when a large number of sheets are printed.

Further, when a heat and / or photocurable group is contained as one of the polymer components as the dispersion stabilizing resin, further elution is further suppressed by further chemically bonding with a binder resin. can do.

Further, in the present invention, the resin particles having a crosslinked structure can further suppress the elution property with water, while exhibiting the water swelling property and further improving the water retention. In the present invention, the resin particles that do not form a crosslinked structure as described above or the resin particles that form a crosslinked structure (hereinafter simply referred to as crosslinked resin particles) are 10 parts by weight per 100 parts by weight of the total composition of the surface layer. It is preferably used in an amount of -80% by weight. If the amount of resin particles or crosslinked resin particles is less than 10% by weight, the hydrophilicity of the non-image area will not be sufficient, and if it is more than 80% by weight, the hydrophilicity of the non-image area will be further improved, but under severe conditions. The electrophotographic characteristics of the image are deteriorated and the copied image is deteriorated.

Further, the resin [A] contains at least one of the aryl group-containing methacrylate components represented by the following general formulas (IIIa) and (IIIb) as the copolymer component represented by the general formula [III]. It is preferable that the resin [A] (hereinafter, this low molecular weight substance is referred to as a resin [A ']) containing one of them is used. Photographic characteristics (especially V
₁₀ , D.I. R. R. , E _1/10 ) can be improved.

The reason for this is unknown, but one reason is that the arrangement of these polymer molecular chains at the zinc oxide interface in the film is due to the planarity effect of the benzene ring or naphthalene ring which is the ester component of the methacrylate. 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 of the present invention contain at least one functional group capable of decomposing to produce a hydrophilic group, and a monofunctional monomer (insoluble in the non-aqueous solvent after polymerization) ( C) and a monofunctional monomer (D) containing a repeating unit containing a fluorine atom and / or a silicon atom as at least a substituent and copolymerizable with the monofunctional monomer (C). It is obtained by polymerizing in the presence of a dispersion stabilizing resin which becomes soluble in the non-aqueous solvent afterwards.

The molecular weight of the dispersed resin particles is 10 ⁴ to 10 ⁶ ,
It is preferably 10 ^{4 to} 5 × 10 ⁵ . As a polymerization component in the resin particles, the proportion of the monomer (C) present is 30% by weight or more, preferably 50% by weight or more, and the proportion of the monomer (D) present is 0.5% by weight to 30%. %, Preferably 1% 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 25 ° C.

The weight average molecular weight of the dispersion stabilizing resin is 1 × 10 ³ to 1 × 10 ⁵ , preferably 2 × 10 ^3.
˜1 × 10 ⁵ , particularly preferably 3 × 10 ^{3 to} 5 × 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 resin particles 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, more preferably in the whole amount. 60-1
It is at least 00% by weight.

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.

With respect to 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. The amount of the resin particles [L] of the present invention present in the surface layer is 1 to 80% by weight, preferably 5% by weight based on the total weight of the surface layer composition.
-60% by weight.

The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. First, the monofunctional monomer (C), which is soluble in a non-aqueous solvent but is insolubilized by polymerization, will be described.
It has a functional group represented by the general formula (I) or (II) in its molecular structure.

[0065] Formula _{(I) -W 1 - (CH} 2) n1 -CH = CH 2 Formula _{(II) -W 2 - (CH} 2) n2 -CH 2 CH 2 -X formula (I), (II ), -W _1- , -W ₂ -are each -S
Represents O ₂ —, —CO— or —OOC—, n ₁ and n ₂ each represent 0 or 1, and X represents a halogen atom.

In the above general formula (I) or (II),
More preferably, n ₁ and n ₂ are 0. Further, the halogen atom of X specifically represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Furthermore, the functional group of the general formula (II) can be easily converted into the corresponding functional group of the formula (I) by dehydrohalogenation by alkali treatment as shown in the reaction formula (1). It can be used in the same manner as in (I).

The monomer (C) constituting the main component of the resin particles [L] of the present invention contains at least one of the functional groups represented by the above general formula (I) and / or general formula (II). Any one may be contained as long as it contains a polymerizable double bond group in one molecule.

More specifically, an example of the monomer (C) is represented by the following general formula (V).

[0070]

[Chemical 9]

In the formula (V), Z is --COO--, --OCO.
-, - O -, - CO -, - CONr 1 -, - SO 2 Nr
_1- (r ₁ represents a hydrogen atom or a hydrocarbon group), -CO
NHCOO -, - CONHCONH -, - CH 2 COO
-, - CH ₂ OCO-, or -C ₆ H ₄ - represents a.

Y represents an organic residue which directly bonds or connects -Z- and -W ₀ . Furthermore - [- Z-Y -] - is [= C (d ₂₎ -] unit and -W ₀ may be connected directly.
W ₀ represents a functional group represented by the general formula (I) or the general formula (II).

D ₁ and d ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (V) will be described in more detail. Preferably Z is -C
OO -, - OCO -, - O -, - CO -, - CONr 1
-, - SO ₂ Nr ₁ - or -C ₆ H ₄ - represents a.

However, r ₁ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Octyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-
Hydroxyethyl group, 3-bromopropyl group, etc., and aralkyl group having 7 to 9 carbon atoms which may be substituted (eg, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group) ,
Methoxybenzyl group, chloro-methylbenzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (for example, phenyl group, tolyl group, xylyl group, mesityl group,
Methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.) and the like.

Y represents a direct bond or an organic residue connecting -Z- and -W ₀ . When Y represents an organic residue to be linked, this linking group represents a carbon-carbon bond which may be through a hetero atom (as a hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is shown), for example, _{-C (r 2) (r 3} )
_{-, - C 6 H 11,} -C 6 H 4 -, - (CH = CH) -,
-O -, - S -, - Nr 4 -, - COO -, - CONH
_{-, - SO 2 -, -} SO 2 NH-, NHCOO -, - N
_{HCONH -, - Si (r 5} ) (r 6) - which has the constitution alone or in combination of binding units, such as (but _{r 2, r 3, r 4} , r 5, r 6 , each of the Represents the same contents as r _1. ).

D ₁ and d ₂ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group). , Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group,
An optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group, phenethyl group, phenyl group, tolyl group, xylyl group,
And an aryl group such as a chlorophenyl group).

Furthermore, in the-[Z-Y] -bonding residue in the formula (V), the [= C (d ₂ )-] moiety and -W ₀ may be linked. The above-mentioned monomer (C) is illustrated more specifically below, but the scope of the present invention is not limited thereto. Examples (a-1) ~ (a -25) in, a is represents -H or -CH _3, R ₃ is -CH = CH ₂ or -CH ₂
Represents CH ₂ X, and X represents —F, —Cl, —Br, or —I.

[0078]

[Chemical 10]

[0079]

[Chemical 11]

[0080]

[Chemical 12]

[0081]

[Chemical 13]

As described above, the monomer (C) containing a functional group of the general formula (I) and / or the general formula (II) which constitutes the insoluble resin portion by polymerization in the resin particle [L] of the present invention. May be polymerized with other monomers to form the insoluble portion.

When another monomer is used as described above, 30 to 99 parts by weight based on 100 parts by weight of all the monomers constituting the insolubilized portion is used.
It is preferably in the range of 50% by weight, particularly 50 to 95% by weight.
Other monomers copolymerizable with these monomers (C) include, for example, aliphatic vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, allyl propionate or allyl esters. Esters or amide chains 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-olefin chains , Vinyl group-substituted heterocyclic compounds such as acrylonitrile, methacrylonitrile, and N-vinylpyrrolidone.

The above-mentioned monomer (C) is synthesized by a conventionally known sulfonylation carbonylation or carboxylic acid esterification reaction. For example, New Chemical Chemistry, edited by The Chemical Society of Japan, Volume 14, “Synthesis and Reaction of Organic Compounds” 75
1 page, 1000 page, 1759 page (1978) Maruzen Co., Ltd. Patai, Z. Rapport
and C. Stirling, “The Chemi
try of Sulfones and Sulp
Hoxides ”p. 165 (1988), John
It can be performed according to the method described in a review article such as published by Willey & Sons.

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) and-(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 (R 3) (R 4} ) (R 5), - Si (R 6) (R 7) O k -R 8
(K represents an integer of 1 to 20), a polysiloxane structure, and the like.

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 above-mentioned hydrocarbon group for R ₃ .

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

Next, specific examples of the repeating unit having a substituent containing the above fluorine atom and / or silicon atom 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.

[0093]

[Chemical 14]

[0094]

[Chemical 15]

[0095]

[Chemical 16]

[0096]

[Chemical 17]

[0097]

[Chemical 18]

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.

Other monomers are represented by the general formula (V
Examples thereof include those copolymerized with a monomer corresponding to the repeating unit of I) or a monomer corresponding to the component represented by the formula (VI).

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 the above-mentioned 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, examples of the polymer component used as the repeating unit of the dispersion stabilizing resin of the present invention include components represented by the following general formula (VI).

[0104]

[Chemical 19]

[0105] formula (VI), X ₂ represents the same content as V ₀ which Formula (IV), details are given in the description of V ₀ which formula (IV).

In the general formula (VI), 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-ethoxycarbonyl Butyl group, etc.), alkenyl group having 3 to 22 carbon atoms which may be substituted (for example, allyl group, hexenyl group, octenyl group, docenyl group, dodecenyl group, tridecenyl group, octadecenyl group, oleyl group, linoleyl group, etc.), carbon An optionally substituted aralkyl group of the formulas 7 to 22 (eg, benzyl group, phenethyl group, 3-phenylpropyi group Group, a 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. (Eg, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group, chlorocyclohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), aromatic group having 6 to 22 carbon atoms which may be substituted (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, ethoxy Carbonylphenyl group, acetylphenyl group, butoxycarbonylphenyl group, butylmethylphenyl group, N, N
-Dibutylaminophenyl group, N-methyl-N-dodecylphenyl group, thienyl group, hiranyl group, etc.) and the like.

C ₁ and c ₂ in the formula (VI) have the same contents as b ₁ and b ₂ in the formula (IV), and the details are described in the formula (IV).
In the description of b ₁ and b ₂ .

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 in addition to the other polymer components.

As the other polymer component, general formula (VI) is used.
Any component may be used as long as it is copolymerized with a monomer corresponding to the component represented by, and examples of the corresponding monomer include α-olefins, acrylonitrile, methacrylonitrile, and vinyl-containing heterocycles (heterocycles). Examples of the ring include 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 carboxamide. Examples thereof include acrylamide, methacrylamide, crotonic acid amide, itaconic acid amide, itaconic acid half amide, and itaconic acid diamide.

In the dispersion stabilizing resin of the present invention, the polymer component represented by the general formula (VI) is the whole polymer 1 of the resin.
It is 30 parts by weight or more, preferably 50 parts by weight or more in 00 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.

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

The polymerizable double bond group portion will be described below.

[0115]

[Chemical 20]

General formula (IV), 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 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).

[0118] 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 as or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group and 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 through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (IV), V ₀ is -COO-, -OCO-, -CH ₂ OCO.
_{-, - CH 2 COO -,} - O -, - CONH -, - SO
₂ NH -, - CONHCOO- or -C ₆ H ₄ - and represents, b _1, b _2, which may be the same or different, a hydrogen atom, 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, a hexyl group or the like). Still more preferably, b ₁ and b _{One of the two} in ₂ always represents a hydrogen atom.

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

These polymerizable double bond group-containing moieties are those directly bonded to the main chain of the polymer chain or bonded by 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 (IV).

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

[0125]

[Chemical 21]

{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, etc.) 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.

The above-mentioned monofunctional polymer [M] represented by the general formula (I
Specific examples of the polymerizable double bond group-containing moiety represented by V) and the moiety composed of the organic residue linked thereto include, but are not limited to, the following. However, in each of the following examples, P ₁ is —H, —CH _{3
-, - CH 2 COOCH 3,} -Cl, -Br or -CN
, P ₂ represents —H or —CH ₃ , X represents —Cl or —Br, n represents an integer of 2 to 12, and m represents 1 to
Indicates an integer of 4.

[0131]

[Chemical formula 22]

[0132]

[Chemical formula 23]

[0133]

[Chemical formula 24]

[0134]

[Chemical 25]

[0135]

[Chemical formula 26]

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.

[0140]

[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.I. 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 a 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 particles of the present invention contain the polar group-containing monofunctional monomer (C) and the silicon atom and / or fluorine atom-containing monofunctional monomer (D) as described above. 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 hardly 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 used 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 (for example, 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.

Further, the polymerizability to be coexisted by the above method (b)
Polyfunctional monomer containing two or more functional groups [polyfunctional monomer
Also referred to as a monomer (E)] or a polyfunctional oligomer
As the polymerizable functional group, specifically, CH₂= CH-CH
₂-, CH₂= CH-CO-O-, CH₂= CH-, C
H₂= C (CH₃) -CO-O-, CH (CH₃) = C
H-CO-O-, CH₂= CH-CONH-, CH₂=
C (CH₃) -CONH-, CH (CH₃) = CH-C
ONH-, CH₂= CH-O-CO-, CH₂= C (C
H₃) -O-CO-, CH₂= CH-CH₂-O-CO
-, CH₂= CH-NHCO-, CH₂= CH-CH₂
-NHCO-, CH₂= CH-SO₂-, CH₂= CH
-CO-, CH ₂= CH-O-, CH₂= CH-S-, etc.
Can be mentioned. Identical to these polymerizable functional groups
There are two or more different or different monomers
Or an oligomer.

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: polyvalent. 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 polymers to form a bridge between the polymers, the reaction with a usual organic low molecular 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 the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and 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 particle diameter distribution 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 include 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, relative to 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, all 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 and 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 since it has a higher order structure, 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 oxide) 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 hydrophilic groups and exhibit 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 hydrophilicity, and the particles become slightly soluble or insoluble, and the particles themselves have water swelling property. Like

Therefore, the hydrophilic groups produced in the resin particles allow the surface of the non-image area to exhibit hydrophilicity, and the entire surface layer can contain 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-mentioned functional groups in the resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or the printing machine can be made larger 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.

Conventionally, only one material such as zinc oxide can be used because it is necessary to have the property that photoconductivity and hydrophilicity can be obtained 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 ferrocyanine compound is used as the main agent 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.

The binder resin (A) used in the present invention is described below.
Will be described in detail. In the weight [A], the weight average molecular weight is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 1.
It is 0 ³ to 1 × 10 ⁴ , and the glass transition point of the resin [A] is preferably −30 ° C. to 110 ° C., more preferably −20.
C to 90C.

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 abundance ratio of the polymer component corresponding to the repeating unit of the general formula (III) of the resin [A] is 30% by weight or more, preferably 50 to 97% by weight. The abundance ratio is 0.5 to 15% by weight, preferably 1 to 10% by weight.

The content of polar groups 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] has a specific substituent at the 2-position and / or at the 2-position and the 6-position represented by the above-mentioned general formulas (IIIa) and (IIIb). Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring (hereinafter, this low molecular weight compound is referred to as resin [A '])
Is preferred.

The content of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (IIIa) and / or the formula (IIIb) 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 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the resin [A '].

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

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 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, Tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group,
Octenyl group), 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, in the copolymer component corresponding to the repeating unit of the general formula (III),
IIa) and / or a copolymer component (resin [A ']) represented by a methacrylate component containing a specific aryl group represented by the general formula (IIIb).

In formula (IIIa), preferred T ₁ and T ₂ are, independently of each other, a hydrogen atom, a chlorine atom and a bromine atom, respectively, and a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms. 4 alkyl groups (eg methyl, ethyl, propyl, butyl, etc.), 7 carbon atoms
~ 9 aralkyl groups (for example, 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 -C
OR ₀₄ and -COOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described above as the preferable hydrocarbon group having 1 to 10 carbon atoms).

[0193] formula (IIIa) and (IIIb), L ₁ and L ₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) m1 - (} m 1 represents an integer of 1 to 3 _{), - CH 2 OCO -,} - CH 2 CH 2 OCO
-, - (an integer of m ₂ is 1 or _{2), - - (CH 2} O) m2 is CH ₂ CH ₂ O-such as such linking atoms 1-4 linking groups, more preferably directly A bond or a linking group having 1 to 2 bond atoms can be mentioned.

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

[0195]

[Chemical 27]

[0196]

[Chemical 28]

[0197]

[Chemical 29]

[0198]

[Chemical 30]

Next, the polar group in the polar group-containing component of the characteristic 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 .

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.

The copolymerizable component containing a polar group of the resin [A] is, for example, one represented by the general formula (III) [the general formula (IIIa), (I
IIb)]], any vinyl compound containing the polar group that can be copolymerized with a monomer corresponding to the repeating unit represented by the formula (IIb) can be used. Basic]] Baifukan (1986
Annual publication) etc. 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 body, α-cyano body, β-chloro body,
β-bromo form, α-chloro-β-methoxy form, α, β-
Dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid,
2-alkenylcarboxylic acids (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, vinyl Benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, half-ester derivative of vinyl group or allyl group of dicarboxylic acids, and ester substituents of these carboxylic or sulfonic acid, substituents of amide derivative Examples thereof include compounds having a polar group.

Examples of the polar group-containing copolymer 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.

[0206]

[Chemical 31]

[0207]

[Chemical 32]

[0208]

[Chemical 33]

[0209]

[Chemical 34]

[0210]

[Chemical 35]

[0211]

[Chemical 36]

[0212]

[Chemical 37]

[0213]

[Chemical 38]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ′]) is represented by the general formula (III),
In addition to the monomer of (IIIa) and / or (IIIb) 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 containing a substituent other than those described in the general formula (III), 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, Sulfonyl naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine,
Vinyl imidazole, vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine etc.)
Etc. These other monomers are 30 in the resin [A].
It is desirable not to exceed the weight percent.

The resin [A] has a weight average molecular weight of 1 × 10.
These are low molecular weight random copolymers having a molecular weight of ^{3 to} 2 × 10 ⁴ , and these polymerization methods can be easily synthesized by radical polymerization, ionic polymerization or the like by selecting the polymerization conditions in the conventionally known method. be able to. Monomers that polymerize,
The radical polymerization reaction is advantageous from the setting temperature of the polymerization solvent reaction and the like, in view of purification, apparatus reaction method and the like.

Specific examples of the polymerization initiator include commonly known azobis type initiators and peroxides.
In particular, as a characteristic of synthesizing a low molecular weight substance, a known method such as increasing the amount of the initiator used or increasing the polymerization set temperature may be applied. Specifically, the amount of the initiator used is in the range of 0.1 to 20 parts by weight with respect to the total amount of the monomers, and the set polymerization temperature is in the range of 30 to 200 ° C.

Further, a method of using a chain transfer agent in combination is also known. For example, a desired weight average molecular weight can be adjusted by using a mercapto compound, a halogenated compound or the like in the range of 0.01 to 10 parts by weight with respect to the total amount of monomers.

Low molecular weight resin [A] as described above
(Including [A ′]) is preferably used in combination with the above-mentioned known resin for photoconductive zinc oxide. The use ratio of the low molecular weight resin 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 × 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, typical ones are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, polyvinyl. Butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata and Jiro Ishiwata, "Polymer", Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8), page 9, Koichi Nakamura, "Practical technology of binders for insulating materials"
Chapter 10, C.I. H. C. Published (1985), D.M.
D. Tatt, S.M. C. Heidecker, Tapp
i, 49 (No. 10), 439 (1966), E.I.
S. Baltazzi, R.A. G. Blanklotte
et al, Photo. Sci. Eng. 16 (N
o. 5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography, 18 (No.
2), 28 (1980), JP-B-50-31011, JP-A-53-54027, 54-20735, 57-57.
The materials disclosed in JP-A-202544 and JP-A-58-68046 are cited.

As a medium to high molecular weight resin, which is a preferable resin to be used in combination, the above-mentioned physical properties are satisfied, and preferably 30% by weight or more of a polymer component of a repeating unit represented by the following general formula (VII) is contained. Polymers may be mentioned.

[0224]

[Chemical Formula 39]

[In the formula (VII), V is -COO-,-
_{OCO -, - (CH 2)} q -OCO -, - (CH 2) q
-COO -, - O- or -SO ₂ - represents a. However, q represents an integer of 1 to 4] In the general formula (VII), f ₃
And f ₄ represent a hydrogen atom, a halogen atom (for example, chlorine atom, bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.).

R ₀₇ 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, Tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group). , Methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.),
Optionally substituted cycloalkyl group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl group (eg, phenyl group, tolyl group, xyl 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, nitrophenyl Groups and the like).

The medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (VII) is, for example, a resin of a random copolymer containing the polymer component represented by the formula (VII). (Japanese Patent Laid-Open Nos. 63-49817 and 63-22
No. 0149, 63-220148, etc.), a resin in which the random copolymer and a crosslinkable resin are used in combination (Japanese Patent Application Laid-Open No. 1-21).
No. 11766, No. 1-102573, and Formula (VI)
A copolymer containing a polymer component represented by I) and partially cross-linked in advance (Japanese Patent Laid-Open Nos. 34860/1990 and 4066/1990).
0 each gazette), a graft type block copolymer obtained by polymerizing a monofunctional macromonomer consisting of a polymer component of a specific repeating unit and a monomer corresponding to the component represented by the formula (VII) (Japanese Patent Application No. 63-203933, 63-207
317, Japanese Patent Application Nos. 1-163796, 1-212994,
Examples of the above-mentioned Nos. 1-229379 and 1-189245 include those already filed by the present inventors).

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 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 as 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), "Synthetic Organic 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.
(4) British Patent No. 2
237680, JP-A 47-30331, etc., indigo and thioindigo derivatives, (5) British Patent No. 2237679, JP-A 47-3033.
Quinacridone pigments (6) described in JP-B No. 2-23, etc., British Patent No. 2237678, JP-A-59-18434.
No. 8, No. 62-28738, No. 47-18544, and the like, and (7) JP-A-47-30.
331, 47-18543, etc., bisbenzimidazole pigments, (8) US Pat.
10, Squalium salt-based pigments described in JP-A Nos. 4644082 and (9) JP-A-59-53850, 61.
Azurenium salt-based pigments described in JP-A-212542 and the like. These may be used alone or in combination of two or more.

The mixing ratio of the organic photoconductive compound and the binder resin determines the upper limit of the content of the organic photoconductive compound due to the compatibility between the organic photoconductive compound and the binder resin. 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 per 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 as a spectral sensitizer depending on the type 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 disclosed in Japanese Examined Patent Publication No. 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, in the near-infrared region having 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, pp. 117-118.

The photoconductor of the present invention is also excellent in that its performance does not easily change 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 sensitizer include halogen, benzoquinone, chloranil,
Fluoranyl, bromanil, dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone, tetracyanoethylene, etc. Electron-withdrawing compounds, Hiroshi Komon et al. "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors" Chapters 4 to 6: Polyaryl, a review article by the Japan Science Information Co., Ltd. (1986) Examples thereof include alkane compounds, hindered phenol compounds, p-phenylenediamine compounds and the like. Further, JP-A-58-65439, JP-A-58-102239, and JP-A-58-1.
The compounds and the like described in JP-A No. 29439 and 62-71965 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, 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 original plate of the present invention obtained as described above, and a copy image is formed on the electrophotographic original plate having the above-mentioned constitution 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, the electrostatic latent image is developed with toner. As the developing method, conventionally known methods, for example, various methods such as cascade development, magnetic 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 to be used in the present invention includes a functional group-containing resin particle of the present invention represented by the general formula (I) containing a hydrophilic group-containing compound that easily nucleophilically reacts with the double bond. It is achieved by treating with a solution (aqueous solution or a mixed solution containing a water-soluble organic solvent).

As the hydrophilic compound which causes a nucleophilic substitution reaction on the double bond of the functional group represented by the general formula (I), the nucleophilic constant n [R. G. Pears
on, H.H. Sobel, J .; Songstad, J.M. A
mer. Chem. Soc. , 90 , 319 (196
8)] is a hydrophilic compound containing a substituent having a value of 5.5 or more and soluble in 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-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl-2 -Mercapto-1-aminoacetic acid and the like, as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinic acid, Carboxybenzenesulfinic acid and the like, 2-hydrazinoethanolsulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid and the like as hydrazide compounds, Examples of the primary or secondary amine compound include 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. Further, the pH of the treatment liquid is preferably 4 or more.

The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. For example, an organic solvent soluble in water is added to water 10
1 to 50 parts by weight may be contained in 0 parts by weight. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol 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 kinds.

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 method of desensitizing the resin particles of the present invention containing the functional group represented by the general formula (II) is as follows. After the dehydrohalogenation reaction is carried out as shown in the above reaction formula (1), It is characterized in that a nucleophilic compound nucleophilically reacts with the generated double bond to make it hydrophilic.

Since the dehydrohalogenation reaction easily proceeds in a treatment liquid having a pH of 6 or more, the pH of the etching treatment liquid containing at least the nucleophilic compound is 6
With the above settings, dehydrohalogenation and hydrophilization by nucleophilic reaction are achieved.

More preferably, the pH of the treatment liquid is 8 or higher. Further, the dehydrohalogenation reaction may be allowed to proceed in a solution having a pH of 6 or more and then desensitized with a treatment liquid of a hydrophilic group-containing compound which undergoes a nucleophilic reaction.

The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. Furthermore, the hydrophilic treatment containing the nucleophilic compound can obtain the same effect even when the immersing water at the time of printing is used by containing the nucleophilic compound.

As described above, according to the present invention, any conventionally known electrophotographic photosensitive member can be used as a high quality lithographic printing original plate. The surface layer in the present invention is a film having both high hydrophilicity and water resistance after hydrophilic treatment, and
The adhesiveness between the substrate and the toner image is also very good, and thus the lithographic printing plate precursor thus obtained is extremely suppressed in the occurrence of background stain and has high printing durability.

Further, since the printing plate of the present invention can maintain the original sensitivity of the electrophotographic photosensitive layer almost as it is, a printing plate plate having dramatically higher sensitivity than the conventional printing plate plate for electrophotographic plate making can be obtained. ..

Further, conventionally, only one material such as zinc oxide can be used because one layer must have a property that it can be made hydrophilic with the photoconductive layer. However, in the printing original plate of the present invention, only a limited material can be used. Since the functions are separated into the conductive layer and the hydrophilizable layer, the selection range of the photoconductive layer is expanded, and therefore, for example, if a material having high sensitivity in the long wavelength light region is selected,
Writing using a He-Ne laser or a semiconductor laser, which has been impossible in the past, is possible.

Further, in the printing original plate of the present invention, the non-image area can be made hydrophilic by only immersing it in the hydrophilic treatment liquid for at least several seconds, so that the plate can be made by a small and simple apparatus. Furthermore, even when neutral paper is used as the printing paper and various printing inks are used, it is possible to print a large number of sheets.

[0268]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Next, production examples of the resin particles [L] and the dispersion stabilizing resin (monofunctional polymer [M]) will be specifically exemplified. Production Example of Dispersion Stabilizing Resin (Monofunctional Polymer [M]) 1:
[M-1] A mixed solution of 97 g of dodecyl methacrylate, 3 g of glycidyl methacrylate and 200 g of toluene was heated to 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 .

[0270]

[Chemical 40]

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 .

[0273]

[Chemical 41]

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 .

[0275]

[Chemical 42]

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 .

[0277]

[Chemical 43]

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 .

[0279]

[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 .

[0281]

[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 .

[0283]

[Chemical 44]

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 .

[0285]

[Table 4]

[0286]

[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. with 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}

[0288]

[Chemical 45]

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.

[0290]

[Table 6]

[0291]

[Table 7]

[0292]

[Table 8]

[0293]

[Table 9]

[0294]

[Table 10]

Production Example 18 of resin particles: [L-18] 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. In addition to this, the monomer [C
-1] 20 g, monomer [D-4] 5 g diethylene glycol dimethacrylate 5 g, A. I. V. N. 0.5 g
A mixed solution of 150 g of methyl ethyl ketone and 1 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 was 0.25 μm.

Production Examples 19-28 of resin particles: [L-1
9] to [L-28] Resin particles [L-28] were prepared in the same manner as in Production Example 18 except that polyfunctional compounds shown in Table 6 below were used instead of ethylene glycol dimethacrylate 2 g in Production Example 18 of resin particles.
-19] to [L-28] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0297]

[Table 11]

Production Examples 29-38 of resin particles: [L-2
9] to [L-38] Monomer [C-8] 47.5 g, Monomer [D-11] 2.
5 g, 2 g of ethylene glycol diacrylate, 8 g of each dispersion stabilizing resin [M] listed in Table 7 below, and 230 g of dipropyl ketone were stirred in a solution of 200 g of dipropyl ketone heated to 60 ° C. under a nitrogen stream. While being dropped for 2 hours. After reacting for 1 hour as it is, A. I.
V. N. 0.3 g was added and reacted for 2 hours. After cooling 200
The average particle size of each dispersion obtained through the mesh nylon cloth was 0.18 to 0.25 μm.

[0299]

[Table 12]

The following is a specific example of the synthesis of the binder resin [A]. Synthesis Example of Binder Resin [A] 1: [A-1] A mixed solution of 95 g of benzyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to a temperature of 90 ° C. under a nitrogen stream, and then 2,2′-azobis. 6.0 g of isobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 2 g was added and reacted for 2 hours. The weight average molecular weight of the obtained copolymer [A-1] was 8
It was 500.

[0301]

[Chemical 46]

Synthesis Examples 2 to 28 of Binder Resin [A]: [A-
2] to [A-28] Resins [A-2] to [A-28] shown in Table 8 below were synthesized in the same manner as in the polymerization conditions of Synthesis Example 1 of Resin [A].

[0303]

[Table 13]

[0304]

[Table 14]

[0305]

[Table 15]

[0306]

[Table 16]

[0307]

[Table 17]

[0308]

[Table 18]

[0309]

[Table 19]

Example 1 and Comparative Examples AB Example 1 6 g of resin [A-3] (as solid content), 34 g of resin [B-1] having the following structure (as solid content), 200 g of photoconductive zinc oxide. A methine dye [I] 0.017 having the following structure
g, a mixture of 0.18 g of phthalic anhydride and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) 9 ×
10 ³ r. p. m. It was dispersed for 15 minutes at the rotation speed of. The amount of dry adhesion of this photosensitive layer-forming dispersion on a conductively treated paper is 2
Apply 2g / m ² with a wire bar and apply 100
It was dried at 30 ° C. for 30 seconds.

[0311]

[Chemical 47]

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] 2 g having the following structure Resin particles [L-1] 4 g (as solid content) Phthalic anhydride 0.01 g o-Chlorophenol 0.002 g was added to toluene. The total amount was 100 g.

Then, an electrophotographic light-sensitive material was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0315]

[Chemical 48]

Comparative Example A In Example 1, 6 g of resin [A-4] and resin [B-
1] An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 40 g of the resin [B-1] was used instead of 34 g. Comparative Example B Comparative Dispersion Resin Particles: [LR-1] In Production Example 1: [L-1] of resin particles, a resin having the following structure was used instead of 10 g of the dispersion stabilizing resin [P-32]. Was synthesized in the same manner as in Production Example 1. The average particle size of the obtained latex was 0.17 μm.

[0317]

[Chemical 49]

Comparative Photoreceptor In Example 1, instead of 4 g of resin particles [L-1] in the toluene dispersion for the surface layer, resin particles [LR-1] 4 were used.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that g (as solid content) was used.

Film formation (smoothness of the surface), electrostatic characteristics, desensitizing property of the photoconductive layer (expressed by the contact angle of the photoconductive layer after desensitizing treatment with water) and printing of these photosensitive 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 liquid developer LD-1 having the following formulation was used to perform exposure / development processing to form an image and desensitization. It investigated using the lithographic printing plate obtained by processing. (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 60 g of methyl methacrylate, 40 of methyl acrylate
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).

[0322]

[Chemical 50]

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-9.

[0325]

[Table 20]

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 90 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 is changed to -4 by corona discharge.
After charging to 00 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 (temperature 20 ° C., 65% RH) was set to I, and the same evaluation was conducted 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 E-1: a desensitizing solution having the following formulation at a temperature of 40 ° C. (original plate not made into a plate: abbreviated as raw plate). These versions are Hamada Star 8005X type manufactured by Hamada Star Co., Ltd.
Print using distilled water as dampening water and print 50 times after printing.
The presence or absence of background stains on the first printed matter was visually evaluated. Desensitizing treatment liquid: E-1 Serine 80 g Monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to make the total volume 1.0 liter, and then pH 13. Adjusted to 0. Note 5) Background stain of printed matter: After making each light-sensitive material by the same operation as in Note 3) above, immersing it in the processing liquid of E-1 used in Note 4) for 3 minutes, and then using E as fountain solution. A solution obtained by diluting -1 with water by a factor of 4 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 could be visually discriminated was examined.

The surface smoothness of each photographic 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.

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 and 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 exhibit 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, 6 g of resin [A-3], resin [B-
1] 34 g, methine dye [I] 0.017 g and resin particles [L-1] 4 g, instead of resin [A-19] 4 g,
35.0 g of resin [B-2] having the following structure 0.020 g of methine dye [II] having the following structure and 4 g of resin particles [L-2]
An electrophotographic light-sensitive material was produced in the same manner as in Example 1 except that was used.

[0332]

[Chemical 51]

The respective characteristics were 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: -630V D. R. R. : 78% E _1/10 : 45 erg / cm ² Imaging: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No scum up to 3,000 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 Sodium sulfite 80 g N-methylmonoethanolamine 70 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 hydroxylated. The pH was adjusted to 13.5 with potassium.

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 Instead of the resin particles [L], resin [A], and resin [B] used in Example 1, 4.5 g (solid content) of resin particles [L] of the present invention shown in Table 10 below. 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 printing characteristics were evaluated by operating in the same manner as in Example 1.

[0337]

[Chemical 52]

[0338]

[Table 21]

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 copy 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 after the actual printing. Examples 15 to 18 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 11 below were used instead of the methine dye [I].

[0341]

[Table 22]

Each of the light-sensitive materials exhibited substantially 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 12 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.

[0343]

[Chemical 53]

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′-2] having the following structure 2 g Resin particle [L] in Table 12 below 5 g (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.

[0345]

[Chemical 54]

Then, an electrophotographic photosensitive 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-12.

[0348]

[Table 23]

In the mode of carrying out the evaluation items shown in Table-12, 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 normal humidity (20 ° C., 65%) for one day, a plate is made 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 12 for each light-sensitive material, all the performances were good, and the number of printable sheets was 5,000. 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.

[0351]

[Chemical 55]

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.

[0353]

[Chemical 56]

Resin particles [L-27] were formed on the surface of this photoreceptor.
% By weight (as solid content), 1% 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.

[0355]

[Chemical 57]

This light-sensitive material was immersed in a desensitizing solution (E-3) prepared according to the following formulation at a temperature of 40 ° C. for 2 minutes to desensitize it. Desensitizing treatment solution (E-3) Thiomalic acid 80 g Monoethanolamine 52 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 10 g Methyl ethyl ketone 80 g These were dissolved in distilled water to pH 13.
It was adjusted to 5 and the total volume was 1.0 liter. Distilled water 2
When a microliter of water droplets was placed and the contact angle with the formed water was measured with a goniometer, it was 10 ° or less. 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.

This is a fully automatic plate making machine E as in the first embodiment.
When the above LD-1 was used for plate making with LP404V, the density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear.

Further, the master plate after master making was soaked in the desensitizing solution (E-4) prepared by the following formulation at 40 ° C. for 1 minute and then washed with water to desensitize it. .. Desensitizing treatment liquid (E-4) 2-mercaptoethanesulfonic acid 85 g Boric acid 55 g Benzyl alcohol 80 g These were dissolved in distilled water to a total volume of 1.0 liter, and the pH was adjusted to 13.0 with sodium hydroxide. Was prepared. The contact angle of the non-image area with distilled water was 10 ° or less, and the area was sufficiently hydrophilized.

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 22 to 33 Using each of the photosensitive materials prepared in Examples 1 to 21, etching treatment was performed as follows to prepare an offset printing original plate.

0.5 mol of the nucleophilic compound shown in Table 13 below,
Distilled water was added to 100 g of the organic solvent and 6 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter, and then the pH of each mixture was adjusted to 13.0. Each light-sensitive material was dipped in each processing solution at 35 ° C. for 3 minutes.

The obtained plate was printed under the same printing conditions as in Example 1. Each of the light-sensitive materials had good water retention and printing durability of 3,000 sheets.

[0362]

[Table 24]

[0363]

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 comprising at least one photoconductive layer provided on a conductive support, and a surface layer provided on the uppermost layer of the photoconductive layer. A lithographic printing plate precursor comprising at least one kind of dispersed resin particles [L] and at least one kind of resin [A] having the following content as a binder resin in the photoconductive layer. Non-aqueous dispersion resin particles [L]: a function represented by the following general formula (I) and / or general formula (II), which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the non-aqueous solvent Monofunctional monomer (C) containing at least one group and monofunctional copolymerizable with the monofunctional monomer (C) containing a substituent containing at least a silicon atom and / or a fluorine atom. Non-aqueous dispersion resin particles obtained by subjecting a polymerizable monomer (D) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. General formula _{(I) -W 1 - (CH} 2) n1 -CH = CH 2 Formula _{(II) -W 2 - (CH} 2) n2 -CH 2 CH 2 -X [where the above-mentioned formula (I) or ( In II), -W ₁
-, - W ₂ - are each -SO ₂ -, - CO- or -OOC
-, N ₁ and n ₂ each represent 0 or 1, and X represents a halogen atom.] Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , and having the following general formula ( and 30 wt% or more repeating units as the polymer component represented by III), -PO ₃ H _{2,
-SO 3 H, -COOH, -P (} = O) (OH) R
₀₁ [R ₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group)] and a polymer component having at least one polar group selected from cyclic acid anhydride-containing groups. 5
Resin containing about 15% by weight. [Chemical 1] [However, in the above formula (III), 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. ] 2. The lithographic printing plate precursor as claimed in claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a crosslinked structure. 3. The dispersion stabilizing resin comprises a polymer chain in the polymer chain,
The lithographic printing plate precursor as claimed in any one of claims (1) and (2), which contains at least one polymerizable double bond group moiety represented by the following general formula (IV). [Chemical 2] [In the general formula (IV), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CON (R 1) -,
_{-SO 2 N (R 1) -} , - C 6 H 4 -, - CONHCO
Represents O- or -CONHCONH- (provided that p represents an integer of 1 to 4, R ₁ represents a hydrogen atom or a carbon number of 1 to
18 hydrocarbon groups), b ₁ and b ₂ may be the same as or different from each other, and may be 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 an optionally substituted hydrocarbon group) 4. The aryl group-containing methacrylate component represented by the following general formula (IIIa) and the following general formula (IIIb) as a copolymer component represented by the general formula (III), wherein the resin [A] is The lithographic printing plate precursor as claimed in any one of claims (1) to (3), which comprises at least one. [Chemical 3] [In the above formulas (IIIa) and (IIIb), 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. ]