JPH05216292A - Production for planographic printing plate - Google Patents

Abstract

PURPOSE:To produce a planographic printing plate excellent in water retention characteristic, having an excellent printing image and high printing durability even in a severe condition and effective in the scanning exposure system using semiconductor laser beam. CONSTITUTION:The planographic printing plate contains a nonaquaous solvent dispersion-type resin particle, obtained by allowing a monomer (C) having at least one kind of formyl group and/or a functional group converted to formyl group by acid treating to polymerize with a monomer (D) having a substituted group containing silicon atom and/or fluorine atom and copolymerizable with the monomer (C) in the presence of a resin for stably dispersing, in the surface layer and contains a low molecular weight resin (A), made by bonding a polymer component having a specific repeating unit and one of the terminal of the polymer main chain to a polar group, in a photoconductive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate produced by an electrophotographic method, and more particularly, to improving the composition of a photoconductive layer and a surface layer having specific properties on the photoconductive layer. To improve the desensitizing method.

[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 above-mentioned problems of the lithographic printing plate precursor, the present inventors have previously used a resin containing a functional group capable of generating a carboxyl group as a main component of the surface layer upon decomposition. The lithographic printing plate precursor used was 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. It is an object of the present invention to provide a lithographic printing plate 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 which is not easily affected by the type of sensitizing dye that can be used in combination and which has excellent electrostatic properties even in the 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 resin [A] as a binder resin for the photoconductive layer. The lithographic printing plate precursor containing the above is imagewise exposed to form a toner image.
It is achieved by a method for producing a lithographic printing plate, which comprises a printing original plate by desensitizing with a processing liquid containing a hydrophilic compound having a value of 5.5 or more.

The non-aqueous dispersion resin particles [L] contained in the surface layer of the present invention include a formyl group and / or a non-aqueous solvent which is soluble in the non-aqueous solvent but is insolubilized by polymerization.
Alternatively, at least one functional group represented by the following general formula (I)
Seed monofunctional monomer [C] and a monofunctional monomer (D) containing a substituent containing a silicon atom and / or a fluorine atom and copolymerizable with the monofunctional monomer (D). And) are copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.

[0024]

[Chemical 5]

[However, in the above formula (I), A ₁ ,
A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A ₂ represent organic residues which are linked to each other to form a ring]

The resin [A] is 1 × 10 ³ to 2 × 1.
Having a weight average molecular weight of 0 ⁴ , containing 30% by weight or more of the repeating unit represented by the following general formula (II) as a polymer component, and at one end of the polymer main chain, -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 resin formed by bonding at least one polar group selected from a cyclic acid anhydride-containing group. is there.

[0027]

[Chemical 6]

[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 (= O) (OH) R ₀₁ is

[0029]

[Chemical 7]

Is shown. In the present invention, the non-aqueous solvent-based dispersed resin particles may have a crosslinked structure. In addition, as the dispersion stabilizing resin in the present invention, those containing at least one polymerizable double bond group moiety represented by the following general formula (III) in the polymer chain are particularly preferable. Be done.

[0031]

[Chemical 8]

[In the general formula (III), 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 (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula (II). It is preferable to contain at least one of the aryl group-containing methacrylate components.

[0033]

[Chemical 9]

[However, the above formulas (IIa) and (IIb)
In, T ₁ and T ₂ are each independently a hydrogen atom,
Represents a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR ₀₄ or -COOR ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent -CO
A single bond connecting O- and a benzene ring or a connecting atom number 1 to
Represents 4 linking groups. 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 includes a photoconductive layer containing the resin [A] as a binder resin, and further contains a silicon atom and / or a fluorine atom obtained in the presence of the dispersion stabilizing resin. It is a lithographic printing plate 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, insensitivity of non-aqueous dispersed resin particles (hereinafter sometimes abbreviated as resin particles [L]) contained in the surface layer in the non-image area after forming a toner image (plate making) according to a usual electrophotographic process. A printing plate is obtained by modifying the lipophilic surface to a hydrophilic surface by an oiling treatment. 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 formyl group of the resin particles and / or the functional group represented by the above general formula (I) when treated with a treatment liquid containing at least one nucleophilic hydrophilic compound. The monomer (C)] is capable of undergoing an addition reaction with a hydrophilic compound having a nucleophilic reactivity, which allows the particles to exhibit hydrophilicity and, at the same time, has a crosslinked structure in the resin particles, At this time, it has hydrophilicity, is insoluble or slightly soluble in water, and has water swellability.

As another one, the resin component [L] of the present invention contains a polymer component [monofunctional monofunctional monomer] containing at least a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom. It is presumed that the combination of the monomer (D)] causes a migration / concentration phenomenon on the surface portion of the photoconductive layer. Further, the polymer as the dispersion stabilizing resin used in the synthesis of the resin particles [L] has a physicochemical property with an insoluble component composed of at least the polymer of the monomer (C) and the monomer (D). Or by the above formula (II
In the case of the dispersion-stabilizing resin containing the polymerizable double bond group portion represented by I), it is considered that both polymer components are chemically bonded.

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

The mechanism of the resin particles [L] of the present invention being hydrophilized by the nucleophilic reactive hydrophilic compound is represented by the following reaction formula using the sulfite ion as the nucleophilic reactive hydrophilic compound as a representative example. It is shown in 1).

[0040]

[Chemical 10]

That is, the resin particles of the present invention have a nucleophilic reactivity such that the nucleophilic constant n of the person in the treatment liquid is 5.5 or more only when the non-image area is desensitized as a lithographic printing original plate. A hydrophilic group is added to the terminal by reacting with the hydrophilic compound as described above to thereby develop hydrophilicity, that is, because it is hydrophilized during desensitizing treatment, it is hydrophilic by treatment. Since the functional group to be reacted does not react with moisture in the atmosphere, there is no problem of concern regarding storability. Since the formyl group according to the present invention is a functional group that reacts very quickly with a nucleophilic compound, it is possible to rapidly develop hydrophilicity.

When a nucleophilic reactive hydrophilic compound having a person nucleophilic constant n of less than 5.5 is used, the non-image area is insufficiently hydrophilized. Furthermore, since the functional group represented by the general formula (I) can be converted into a formyl group by the acid treatment, the deacetalization reaction easily proceeds by the acid treatment, as shown in the reaction formula (1). It can be used similarly to the formyl group.

Further, in the present invention, as a binder resin in the photoconductive layer, at least one of the specific polymer component represented by the formula (II) and the specific polar group is added to one end of the polymer main chain. It contains a low molecular weight polymer resin [A] formed by bonding. 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.

To solve this problem, the present invention makes it possible to improve the electrostatic characteristics of the photoconductive layer by using the resin [A], and when the image is actually taken, the faithful reproducibility of the copied image is ensured. It was something that could be avoided. 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.

Further, as described above, the resin particles contain a polymer component containing a fluorine atom and / or a silicon atom, whereby the particles have a phenomenon of migration / concentration to the surface portion of the surface layer. The resin particles of the present invention exhibit hydrophilicity due to the desensitizing treatment, and by using the resin particles of the present invention, the addition amount thereof is extremely high in order to produce the same effect (water retention) as that of the known technique. It was a small amount and the adverse effect on the electrophotographic characteristics could be minimized.

As described above, according to the present invention, it is possible to solve the problem of excellent water retention in the non-image area after the formation of a good copy image due to the excellent electrophotographic characteristics and the desensitization treatment after the copy image formation. We were able to.

In the present invention, the resin particles are a hydrophobic polymer component, that is, a polymer component corresponding to the dispersion stabilizing resin, which is bound to the binder resin of the surface layer. Since it is working, it does not elute with dampening water during printing due to the anchor effect of this part,
Good printing characteristics can be maintained even after printing a considerably large number of sheets.

Further, a heat and / or photocurable group may be contained as one of the polymer components as the dispersion stabilizing resin. In this case, the binder resin in the surface layer is chemically bonded to the binder resin. By doing so, the elution can be further suppressed. Further, in the present invention, if the resin particles forming a crosslinked structure, the elution property in water is further suppressed, while the water swelling property is exhibited,
Further, the water retention becomes good.

Further, the resin [A] contains at least one of the aryl group-containing methacrylate components represented by the following general formula (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula [II]. Resin [A] containing one (hereinafter, this low molecular weight compound is referred to as resin [A '])
It is preferable that the resin [A ′] is used, and the electrophotographic characteristics (particularly V ₁₀ , DRR, E _1/10 ) can be further improved as compared with the case of the resin [A]. ..

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 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 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 comprise a polymer component [polymer] composed of a monofunctional monomer (C) containing at least one formyl group and / or a functional group represented by the following general formula (II). And a monofunctional monomer (D) containing at least a fluorine atom and / or a silicon atom as a substituent, and a dispersion-stabilizing resin which is soluble in the non-aqueous solvent. It is characterized by being obtained by polymerizing below.

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

It should be noted that the dispersed resin particles have a larger specific surface area as the particle diameter becomes smaller, which brings about a good effect on the electrophotographic characteristics, and colloid particles (0.01 μm or less) are sufficient, but they are too small. If it is too large, it becomes similar to the case of molecular dispersion, and the effect of being particles for improving the water retention ability is weakened.

The molecular weight of the dispersed resin particles is 10 ⁴ to 1
It is 0 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In the present invention, the resin particles that do not form the above-mentioned crosslinked structure or the resin particles that form the crosslinked structure (hereinafter simply referred to as crosslinked resin particles) are based on 100 parts by weight of the total composition of the surface layer. It is preferably used in an amount of 10 to 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 at
The copied image deteriorates.

As the polymerization component in the resin, the monomer (C) is used.
Is present in an amount of 30% by weight or more, preferably 50% by weight or more, and the amount of the monomer (D) present is 0.5% by weight to 3%.
It is 0% by weight, preferably 1% by weight to 20% by weight. When containing other copolymerizable monomers, the content is at most 20% 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} 5 × 10 ⁵ , preferably 2 × 10 ^3.
˜1 × 10 ⁴ , 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, if it exceeds 5 × 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 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 resin particles [L] of the present invention dispersed in the photoconductive layer will be described in more detail below. The monofunctional monomer [C] used in the resin particles [L] contains at least a formyl group and / or a functional group represented by the general formula [I].

[0065]

[Chemical 11]

In the above formula (I), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ , A 2.
₂ represents an organic residue which is linked to each other to form a ring. A
_{When 1} and A ₂ each represent a hydrocarbon group, A ₁ and A ₂ are preferably an aliphatic group having 1 to 12 carbon atoms which may be substituted (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted). : Specific examples are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, methoxymethyl group, ethoxymethyl group, 2-hydroxyethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
An alkenyl group having 2 to 12 carbon atoms which may be substituted, such as a methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group and a 3-methoxypropyl group:
Specific examples thereof include a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a docenyl group and a dodecenyl group, which may have a carbon number of 7 to 12 and may be substituted; a benzyl group, a phenethyl group, 3 -Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, dimethoxybenzyl group, chlorobenzyl group, bromobenzyl group, fluorobenzyl group, dichlorobenzyl group And the like, such as C 3-12 alicyclic groups that may be substituted: specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and the like).

When A ₁ and A ₂ represent an organic residue which is linked to each other to form a ring, a functional group represented by formula (Ia), that is, a cyclic acetal group is preferable.

[0068]

[Chemical 12]

In the formula (Ia), A ₃ and A ₄ may be the same or different from each other, and are a hydrogen atom or a carbon number of 1 to 12
Optionally substituted hydrocarbon group or —OA ₅ group (A ₅
Represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.

Preferred examples in which A ₃ , A ₄ and A ₅ are hydrocarbon groups of hydrocarbons 1 to 12 which may be substituted include:
Aliphatic group (specifically, the same contents as those exemplified for A ₁ and A ₂ ), aromatic group (for example, phenyl group, tolyl group,
Xylyl group, methoxyphenyl group, chlorophenyl group,
Bromophenyl group, methoxycarbonylphenyl group, dimethoxyphenyl group, chloromethylphenyl group, naphthyl group, etc.) and the like.

More preferably, the formulas (I) and (Ia) are
In the case where A _{1 to} A ₅ are aliphatic groups, the number of carbon atoms is 1 to 6
Alkyl group, alkenyl group having 3 to 6 carbon atoms, and 7 carbon atoms
An aralkyl group of 9 is preferred. Moreover, n more preferably represents an integer of 1 to 3. Examples of the copolymerization component containing a formyl group and / or a functional group represented by (I) used in the present invention include those represented by the repeating unit of the following general formula (IV).

[0072]

[Chemical 13]

[However, in the formula [IV], Z is --COO.
-, - OCO -, - O -, - CO -, - CONr 1 -,
-SO ₂ Nr ₁ - (r ₁ represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCONH- , C
H ₂ COO-, CH ₂ OCO- or -C ₆ H ₄ - represents a. Y is -Z- and -W ₀ - represents an organic residue or linked directly attached to. Furthermore,-[Z-Y]-

[0074]

[Chemical 14]

The part and -W ₀ may be directly connected. W ₀ represents a formyl group or a functional group represented by (I). f ₁ ,
f ₂ may be the same as or different from each other 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 (IV) will be described in more detail.

Preferably, Z is --COO--, --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 (for example, a methyl group, an ethyl group, a propyl group, a 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 and optionally substituted (for example, benzyl group, phenethyl group, 3
-Phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (e.g., phenyl group, tolyl group, xylyl group,
Mesityl group, methoxyphenyl group, chlorophenyl group,
Bromophenyl group, chloro-methoxy-phenyl group, etc.)
Etc.

Y represents a direct bond or an organic residue connecting -Z- and -W ₀ . When Y represents an organic residue to be linked,
The linking group, carbon atoms which may have through a heteroatom - represents a carbon bond (the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom), for example - [C (r ₂₎
(R _{3)] -, - C 6 H 10 -} , - C 6 H 4 -, - (CH
= CH) -, - O - , - S -, - Nr 4 -, - COO
-, - CONH -, - SO 2 -, - SO 2 NH -, - N
HCOO -, - NHCONH -, - Si (r 5)
(R ₆ )-or the like, or a combination of bonding units. (However, r ₂ , r ₃ , r ₄ , r ₅ , r
₆ represents the same content as r ₁ above).

F ₁ and f 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, butoxycarbonylmethyl group, ethoxycarbonylmethyl group,
Represents an optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group and phenethyl group, phenyl group, tolyl group, xylyl group, aryl group such as chlorophenyl group, etc.) ..

Furthermore,-[Z-Y]-in the formula (IV)
The binding residue is

[0080]

[Chemical 15]

The part and the -W ₀ part may be directly connected. Specific examples of the polymer component containing the formyl group and / or the functional group represented by the general formula (I) of the present invention are shown below. In Examples (a-1) to (a-15), a is -H or -C.
Represents H ₃ . However, the present invention is not limited to this.

[0082]

[Chemical 16]

[0083]

[Chemical 17]

[0084]

[Chemical 18]

Specific examples of the functional group represented by the general formula (Ia) of the present invention are also shown. Examples (a'-1) to (a'-)
9), R ₁₀ and R ₁₁ represent an alkyl group having 1 to 4 carbon atoms or —CH ₂ C ₆ H ₅ , and R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, —CH ₂ C ₆ H ₅ or phenyl. Represents a group. However, the scope of the present invention is not limited to these specific examples.

[0086]

[Chemical 19]

The polymer component containing the formyl group and / or the functional group of the general formula (I) in the resin particle [L] of the present invention is not limited to a total amount when the resin particle [L] is a copolymer. 30-99% by weight, especially 50-95% by weight in the copolymer
Is preferred. The molecular weight of the polymer of the resin particles is preferably 10 ³ to 10 ⁶ , particularly 5 × 10 ^{3 to} 5 × 10 ⁵ .

The monofunctional monomer [C] having the formyl group and / or the functional group represented by the general formula (I) of the present invention can be synthesized by a conventionally known synthesis method. ..

For example, as a method for synthesizing a compound containing a formyl group, the New Chemical Chemistry Course, Volume 14, edited by The Chemical Society of Japan,
Pp. 636 (1978) published by Maruzen Co., Ltd. Mulle
r, "Methoden der Organisehe
n Chemie ", p. 13 (1954), Georg.
Methods described in Theme Verlag, edited by The Chemical Society of Japan, New Experimental Chemistry Lecture, Volume 19, 231 (1957) Maruzen Co., Ltd., etc.

The polymerizable functional group in the above-mentioned monomer synthesis is an ordinary polymerizable double bond group, specifically CH.
_{2 = CH-CH 2 -,} CH 2 = CH-CO-O-, CH
_{2 = CH (CH 3) -CO} -O-, CH (CH 3) = C
_{H-CO-O-, CH 2} = CH-CONH-, CH 2 =
_{C (CH 3) -CONH-, CH} 2 = C (CH 3) -C
_{ONHCOO-, CH 2 = C (CH} 3) -CONHCO
_{NH-, CH (CH 3) =} CH-CONH-, CH 2 =
_{CH-O-CO-, CH 2} = CH-C 6 H 4 -, CH 2
_{= C (CH 3) -O-} CO-, CH 2 = CH-CH 2 -
_{O-CO-, CH 2 = CH} -NHCO-, CH 2 = CH
_{-CH 2 -NHCO-, CH 2 = CH} -SO 2 -, CH
_{2 = CH-CO-, CH 2} = CH-O-, CH 2 = CH
-S- and the like can be mentioned.

The resin particle [L] of the present invention comprises the monomer [C]
It may be polymerized together with other monomers. Any other monomer may be used as long as it can be copolymerized with the monomer [C] and the copolymer becomes an insoluble polymer in the non-aqueous solvent. Other monomers copolymerizable with these monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, aliphatic vinyl carboxylates such as allyl propionate or allyl esters, acrylic acid. , Esters or amides of unsaturated carboxylic acids such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, α-olefins, acrylonitrile, Examples include vinyl group-substituted heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone.

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

It contains a substituent containing at least two fluorine atoms and / or silicon atoms, which can be copolymerized 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 hydrocarbon group for R ₃ above.

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

[0101]

[Chemical 20]

[0102]

[Chemical 21]

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

[0105]

[Chemical formula 24]

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

Examples of other monomers include those represented by the general formula (V) described below.
Or a monomer corresponding to the repeating unit of the formula (V)
Examples thereof include those copolymerized with a monomer corresponding to the component shown in.

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

The dispersion stabilizing resin of the present invention may be any polymer as long as it is a polymer soluble in the non-aqueous solvent. 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), Toyoyoshi Tange, Journal of Japan Adhesion Society 23
(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
Each polymer referred to in the review article of echnol, 10, 263 (1984) and the like.

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 (V).

[0112]

[Chemical 25]

[0113] formula (V), X ₂ represents the same content as V ₀ which formula (III), details are given in the description of V ₀ which formula (III).

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

[0115] c _1, c ₂ represents a b _1, b ₂ the same content as the In the formula (III), the details are described in the description of the b _1, b ₂ of the formula (III).

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.

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

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

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

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

Further, the dispersion stabilizing resin of the present invention preferably contains at least one polymerizable double bond group moiety represented by the above general formula (III) in the polymer chain.

The polymerizable double bond group portion will be described below.

[0123]

[Chemical formula 26]

In the general formula (III), V ₀ is -O.
-, - COO -, - OCO -, - (CH 2) p -OCO
_{-, - (CH 2) p} -COO -, - SO 2 -, - CON
_{R 1, -SO 2 NR 1,} -C 6 H 4 -, - CONHCO
Represents O- or -CONHCONH- (p is 1 to 4)
Represents the integer).

In addition to hydrogen atom, R ₁ is preferably a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (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).

[0126] 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, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg Methyl group, ethyl group, propyl group, butyl group, etc.)-COO-R ₂ or COOR ₂ via hydrocarbon (R ₂ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an oil Represents a cyclic group or an aryl group, which may be substituted,
Specifically, it represents the same contents as those described for R ₁ ).

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

More preferably, in the general formula (III), 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 (III), specifically, CH ₂ ═CH
_{-CO-O-, CH 2 = C} (CH 3) -CO-O-, C
_{H (CH 3) = CH-} CO-O-, CH 2 = C (CH 2
_{COOCH 3) -CO-O-, CH} 2 = C (CH 2 CO
_{OH) -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 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 content as R ₁ in formula (III).

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

[0133]

[Chemical 27]

{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 and 1,3-oxazoline ring.

The polymerizable double bond group-containing moiety as described above 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 (II
Specific examples of the polymerizable double bond group-containing moiety represented by I) 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.

[0139]

[Chemical 28]

[0140]

[Chemical 29]

[0141]

[Chemical 30]

[0142]

[Chemical 31]

[0143]

[Chemical 32]

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.

[0148]

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

As described above, the dispersed resin particles of the present invention contain the monofunctional monomer (C) containing a polar group and the monofunctional monomer (D) containing a silicon atom and / or a fluorine atom. 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 crosslinked 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 crosslinked 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 cross-linked structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged.

As a result, the crosslinked 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 having two or more polymerizable functional groups, a crosslinked 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.

Examples of the cross-linking agent in the above method (a) include compounds that are usually used as cross-linking agents.
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 coexist 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 the bridge between the polymers, the reaction of the usual organic low molecular compound is 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 dispersion polymerization, monodisperse particles having a uniform particle size are obtained, and fine particles of 0.5 μm or less are easily obtained. Therefore, as a method for forming a network structure, polyfunctionality is used. 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, 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 contain at least 1 of each of the monomer (C) and the monomer (D) and the dispersion stabilizing resin.
In the case of forming a network structure, it is composed of more than one species and, if necessary, is made to coexist with a polyfunctional monomer (E). In any case, what is important is a resin synthesized from these monomers. If the particles are insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, one dispersion stabilizing resin is used for the insoluble monomer (C) and the monomer (D).
It is preferable to use -50% by weight, and more preferably 2-30% by weight. The molecular weight of the dispersed resin particles of the present invention is 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 ×.
It is 10 ⁵ .

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

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

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

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

The surface layer of the photoreceptor of the present invention comprises the above resin particles uniformly dispersed in the binder resin of the matrix, and the binder resin will be described in detail below.
As the binder resin for the surface layer of the present invention, all those conventionally known as 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, a metal oxide) other than the resin particles of the present invention are contained in the surface layer in an amount of 0.0 with respect to the total amount of the composition for forming the surface layer.
You may contain in the range of 01-5 weight part. 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 forming the surface layer is that the non-image area is sufficiently hydrophilic after the desensitizing treatment, as described above.

That is, this hydrophilicity can be confirmed by, for example, 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. Therefore, the printing plate has an image portion made of lipophilic toner and a highly hydrophilic non-image portion 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 one. 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, in 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 clear due to the hydrophilicity of the non-image area which is hydrophilized by the desensitizing solution. Therefore, the printing ink is prevented from adhering to the non-image portion during printing. As a result, it becomes possible to print a large number of prints with clear image quality without background stains.

Further, in the case of the above-mentioned resin particles partially cross-linked, the solubility in water is remarkably lowered while maintaining the hydrophilicity, and the particles become hardly soluble or insoluble, and the particles themselves have water swelling property. Like Therefore, the hydrophilic group generated in the resin particles causes the surface of the non-image area to have hydrophilicity, and the entire surface layer contains controlled water. The effect of the present invention that the (printing ink repulsion) is further enhanced is improved, and the sustainability is improved.

More specifically, even if the amount of the above-mentioned functional groups in the above resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or the size of the printing machine can be increased or printing can be performed. Even when printing conditions such as pressure fluctuations become strict, it is possible to print a large number of prints with clear image quality without background stains. In the past, only one material, such as zinc oxide, could be used because it had to have the property that photoconductivity and hydrophilization were possible in one layer, but in the printing original plate of the present invention, as described above. By forming the surface layer, the functions are separated into the photoconductive layer and the hydrophilizable layer (surface layer), so strict control during printing is significantly eased compared to the conventional system that relies on the desensitizing reaction of zinc oxide. To be done.

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

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

Next, the binder resin [A] used in the present invention.
Will be described in more detail. In the weight [A], the weight average molecular weight is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3
The glass transition point of the resin [A] is preferably −30 ° C. to 110 ° C., more preferably −10 ³ to 1 × 10 ^4.
It is 20 ° C to 90 ° C. When the molecular weight of the resin [A] is less than 10 ³ , the film-forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight of the resin [A] is more than 2 × 10 ⁴ , even the resin of the present invention has a near red color. In the photoconductor using the outside-infrared spectral sensitizing dye, the variation of dark decay retention rate and photosensitivity under severe conditions of high temperature / high humidity, low temperature / low humidity becomes a little large, and stable copy image can be obtained. That is, the effect of the present invention that it is obtained is diminished.

The content of the polymer component corresponding to the repeating unit of the general formula (II) of the resin [A] is 30% by weight or more,
The proportion of the polymer component containing the specific polar group is preferably 0.5 to 15% by weight, and preferably 0.5 to 15% by weight, preferably 1 to 10% by weight. When the content of the polar group in the resin [A] is less than 0.5% by weight, 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 general formula (IIa) and the general formula (IIb). 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 formula (IIa) in the resin [A '] and /
Alternatively, the proportion of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (IIb) is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the polymer component containing a specific polar group is the resin [A ' ] 0.5 to 100 parts by weight
-15% by weight, preferably 1-10% by weight.

Next, the repeating unit represented by the general formula (II), which is contained in the resin [A] in an amount of 30% by weight or more, will be further described. In the general formula (II), a ₁ and a ₂ are preferably a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), —COO—R _06. Or -COO via a hydrocarbon group
—R ₀₆ (R ₀₆ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically, The same content as that described for R ₀₃ below is represented).

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

More preferably, in the copolymer component corresponding to the repeating unit of formula (II),
a) and / or a copolymer component (resin [A ']) represented by a methacrylate component containing a specific aryl group represented by the general formula (IIb). In formula (IIa), preferable T ₁ and T ₂ are, independently of each other, a hydrogen atom, a chlorine atom, and a bromine atom, respectively, and a carbon number of 1 to 1.
As the hydrocarbon group having 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3 -Phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-
Methyl-benzyl group) and aryl groups (eg phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₀₄ and -COOR ₀₅ (preferred R
Examples of ₀₄ and R ₀₅ include those described above as the preferable hydrocarbon group having 1 to 10 carbon atoms).

In formulas (IIa) and (IIb), L
₁ and L ₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) n1 - (} n 1 represents an integer of _{1~3), - CH 2 OCO -} , - CH 2 CH 2 OCO -,-
_{(CH 2 O) m1 - (} m 1 represents an integer of 1 or 2), -
A connecting group having 1 to 4 connecting atoms such as CH ₂ CH ₂ O-, and the like, more preferably a direct bond or 1 to 2 connecting atoms.
Can be mentioned.

Formula (II) used in the resin [A] of the present invention
Specific examples of the copolymerization component corresponding to the repeating unit represented by a) or (IIb) are shown below. However, the scope of the present invention is not limited to this. The following (d-
In 1) ~ (d-20) , n is an integer of 1 to 4, m is 0 or an integer of 1 to 3, p is an integer of 1-3, R ₁₀ ~R ₁₃ -C Both _n H _{2n + 1} or _{- (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,-
Represents one of I.

[0195]

[Chemical 33]

[0196]

[Chemical 34]

[0197]

[Chemical 35]

[0198]

[Chemical 36]

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

The --P (═O) (OH) R ₀₁ group means the above R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group), and specifically, R ₀₁ represents an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group Group, fluorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aryl group (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro- A methyl-phenyl group,
Dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.), and R ₀₂ has the same content as R ₀₁ .

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 anhydride ring, 2,3-bicyclo [2,2,2]
2] octadicarboxylic acid anhydride rings and the like, and these rings are, for example, halogen atoms such as chlorine atom and bromine atom,
An alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group may be substituted.

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

These polar groups may be directly bonded to the ends of the polymer main chain or may be bonded via a linking group.
The linking group, but may be any binding group, for example, if specifically mentioned, - _{[C (d 1) (d 2} ) ]
-(D ₁ and d ₂ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group,
Cyano group, alkyl group, (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group,
Butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.),-(C
_{H (d 3) -CH (d} 4) ] - (d _3, d ₄ is d _1, d
Represents a ₂ same contents _{as), - C 6 H 10 -} , - C 6 H 5,
-O -, - S -, - N (d 5) - [d ₅ represents a hydrogen atom or a hydrocarbon group (hydrocarbon group, as specifically having 1 to 12 carbon atoms hydrocarbon group (e.g., methyl Group, ethyl group, propyl group, butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group,
A chlorofer group, a methoxyphenyl group, a butylphenyl group, etc.)], -CO-, -COO-, -O.
_{CO -, - (d 5)} CON -, - SO 2 N (d 5) -,
_{-SO 2 -, - NHCONH -,} - NHCOO -, - N
HSO _2- , -CONHCOO-, -CONHCONH
-, A heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom, or a condensed ring thereof: a thiophene ring, a pyridine ring,
A furan ring, an imidazole ring, piperidine ring, morpholine ring and the like) or _{-Si (d 6) (d 7} ) - (d
₆ , d ₇ may be the same or different, and are a hydrocarbon group or-
It represents Od ₈ (d ₈ is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones as those mentioned for d ₅ ) or the like, or a linking group constituted by a combination of these.

Further, preferably, in the binder resin [A], the copolymerization component represented by the general formula (II) [the general formula (II
a) or (IIb) is also included],
This and the polymer component to be copolymerized, -PO ₃ H _2, -
Containing 0.05 to 10% by weight of a copolymerization component containing at least one polar group selected from SO ₃ H, —COOH, —P (═O) (OH) R ₀₁ and cyclic acid anhydride-containing group. It is preferable to improve the electrostatic properties.

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

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ′]) is represented by the general formula (II) or (I
In addition to the monomer of Ia) and / or (IIb), a monomer other than these may be contained as a copolymerization component. Furthermore,
Preferably, in the binder resin [A], the copolymerization component [general formula (IIa) and / or (I
Together including] those represented by ib), as the polymer component to be copolymerized _{therewith, -PO 3 H 2, -SO 3} H, -
0.5 to 10% by weight of a copolymerization component containing at least one polar group selected from COOH, -P (= O) (OH) -R ₀₁ and a cyclic acid anhydride-containing group,
It is preferable for improving the electrostatic characteristics.

What is important in the resin [A] of the present invention is that the proportion of the specific polar group-containing substitution component in the total amount of 100 parts by weight of the resin [A] is 0.5 to 0.5% as described above.
It is within the range of 10% by weight, and the resin [A]
In the case where it exists in both the main chain component of the polymer of the resin [A] and one end of the main chain, it is arbitrarily divided within the above proportion.

Preferably, the abundance ratio in the main chain component is 0.1 to 1.0, where 1.0 is the terminal component. These specific polar groups have the same contents as the polar groups bonded to one end of the polymer main chain described above.

In the resin [A], the abundance ratio of the polar group contained as the copolymer component and the polar group bonded to one end of the main chain of the polymer is different from that of the other components constituting the photoconductive layer of the present invention. The binder resin, the resin particles, the spectral sensitizing dye, the chemical sensitizer, and other additives differ depending on the kind and amount thereof, and the ratio is preferably adjusted arbitrarily. What is important is that the total amount of both polar groups be used within the range of 0.5 to 15% by weight.

The copolymerization component containing these polar groups is
For example, general formula (II) [general formulas (IIa), (IIb)
Also include] a vinyl-based compound containing the polar group that can be copolymerized with the monomer corresponding to the repeating unit represented by, for example, "Polymer Data Handbook ] Baifukan (published in 1986) and the like. 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 compound, α-bromo compound, α-fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α-chloro-β-methoxy compound, α, β-dichloro compound Etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2
-Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Vinyl group or allyl group half-ester derivative, and their carboxylic or sulfonic acid ester dielectrics,
Examples thereof include compounds containing the polar group in the substituent of the amide derivative.

Examples of the polar group-containing 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.

[0212]

[Chemical 37]

[0213]

[Chemical 38]

[0214]

[Chemical Formula 39]

[0215]

[Chemical 40]

[0216]

[Chemical 41]

[0217]

[Chemical 42]

[0218]

[Chemical 43]

[0219]

[Chemical 44]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ']) is represented by the general formula (II) or (I
In addition to the monomer of Ia) and / or (IIb) 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 (II), α-olefins, carvone Acid vinyl 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 (eg styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like). However, it is not limited to these.

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

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

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

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

Each of these chain transfer agents or polymerization initiators is added in an amount of 0.5 to 15 with respect to 100 parts by weight of all monomers.
Parts by weight, preferably 2 to 10 parts by weight. The low molecular weight resin [A] (including [A ′]) as described above is preferably used in combination with a known resin for a conventional photoconductive layer. The use ratio of the low molecular weight resin [A] and the other resin is preferably 5 to 90/95 to 5 (weight ratio).

Other resins to be used in combination include a weight average molecular weight of 3 × 10 ^{4 to} 1 to 10 ⁶ , preferably 5 × 10 ^{4 to} 5.
× 10 ^{5 is} a medium to high molecular weight substance. The glass transition point of the resin used in combination is -10 ° C to 120 ° C, preferably 0 ° C.
~ 90 ° C. For example, Ryuji Shibata and Jiro Ishiwata, Kobun, Vol. 17, p. 278 (1968), Harumi Miyamoto,
Hidehiko Takei, Imaging, 1973 (No.8) No.9
Page, edited by Koichi Nakamura, "Practical technology of binders for recording materials"
Chapter 10, C.I. H. C. Published (1985), D.M. T
att, S.A. C. Heidecker, Tappi, 4
9 (No. 10), 439 (1966), E.I. S. Ba
ltazzi R.D. G. Blanclotte eta
l, Photo. Sci. Eng. , 16 (No.
5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography, 18 (No. 2),
22 (1980), JP-B-50-51011, JP-A-5
3-54027, 54-20735, 57-202.
The materials disclosed in each publication of 544 and the like are listed.

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

As the medium to high molecular weight resin to be used in combination, the above-mentioned physical properties are preferably satisfied, and the following general formula (V
Examples thereof include polymers containing 30 parts by weight or more of the polymer component of the repeating unit represented by I).

[0229]

[Chemical 45]

[In the formula (VI), V is -COO-, -OC.
_{O -, - (CH 2)} h -OCO -, - (CH 2) h -C
OO -, - O- or -SO ₂ - represents a. However, h is 1
Represents an integer of 4] In the general formula (VI), d ₁ and d
₂ represents the same contents as a ₁ and a ₂ in the formula (II).

R ₀₇ has the same _meaning as R ₀₃ in formula (II). Binder resin of medium to high molecular weight containing the polymer component represented by the general formula (VI) (hereinafter referred to as resin [B])
Examples of the resin include a random copolymer resin containing a polymer component represented by the formula (VI) (JP-A-63-49817,
63-220149, 63-220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-102573, etc.), and a polymer component represented by formula (VI). In addition, a partially cross-linked copolymer (Japanese Patent Laid-Open Nos. 34860/1990 and 40660/1990, etc.) is a monofunctional macromonomer consisting of a polymer component of a specific repeating unit and a component represented by the formula (VI). Graft-type block copolymers obtained by polymerization with a monomer corresponding to (JP-A-2-53064, JP-A-2-56558 and JP-A-3-299).
57, same 3-77954, same 3-92861, same 3-5
3257 each specification) etc. are mentioned.

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

As a result, it has been found that the electrophotographic characteristics of the electrophotographic photosensitive member are excellent, and in particular, even when a spectral sensitizing dye for semiconductor laser light is used, extremely excellent performance is exhibited. It was When the resin [B] having a medium to high molecular weight is used in combination, the mechanical performance of the photoconductive layer is improved as compared with the case where only the resin [A] is used, without impairing the high performance of the electrophotographic characteristics due to the use of the resin [A]. It was found that the target strength can be sufficiently improved. That is, the interaction between the adsorption and coating of the photoconductor and the binder resin is appropriately performed, and the film strength of the coating conductive layer is maintained.

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

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

When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, 1 part of the above 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, as the organic compound, any of conventionally known compounds may be used, and specifically, the following two types are known as conventionally known examples as the electrophotographic lithographic printing plate precursor. First, Japanese Patent Publications 37-17162 and 6
2-51462, JP-A-52-1437, 54-198.
No. 03, No. 56-107246, No. 57-161863, etc., having a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin. JP-A-56-146145 and 60-17.
751, No. 60-17752, No. 60-17760, No. 60-254142, No. 62-54266, etc., having a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin. Is. As a special case of the second example, JP-A-60-230147 and 60-23
There is also known a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers as described in JP-A No. 0148 and 60-238853.

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, etc., 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 4,439,506, JP-A-47-37543 and JP-A-58-1235.
41, the same 58-192042, the same 58-219263,
59-78356, 60-179746, 61-
Azo pigments such as monoazo, bisazo and trisazo pigments described in JP-B Nos. 148453, 61-238063, JP-B-60-5941 and JP-B No. 60-45664, and (2) US Pat.
02 each specification, JP-A-51-90827, 52-5
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in Japanese Patent Publication No. 5643, (3) US Pat.
No. 371884, Japanese Patent Laid-Open No. 47-30330, and the like, (4) British Patent No. 2237.
680, indigo and thioindigo derivatives described in JP-A-47-30331, (5) British Patent No. 2237679, JP-A-47-30332, and other quinacridone-based pigments ( 6) British Patent No. 2
237678, JP-A-59-184348, JP-A-62-28738, JP-A-47-18544 and the like, and (7) JP-A-47-3033.
1, bisbenzimidazole pigments described in JP-A-47-18543 and (8) US Pat. No. 4,396,661.
No. 0, No. 4644082, etc., Squalium salt-based pigments, (9) JP-A-59-53850, No. 61-
And the azurenium salt-based pigments described in JP-A-212542 and the like. These may be used alone or in combination of two or more.

Further, regarding the mixing ratio of the organic photoconductive compound and the binding resin, the upper limit of the content rate of the organic photoconductive compound is determined by the compatibility between the organic photoconductive compound and the binding resin. 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 invention contains 10 to 10 parts by weight of the above-mentioned binding resin to 100 parts by weight of the photoconductive compound.
It is used in a proportion of 0 parts by weight, preferably 15 to 50 parts by weight. In the present invention, various dyes may be used together 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, the near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, ibid 49-5034, ibid 49-45122, ibid 5
7-46245, 56-351141, 57-157.
254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and "Research Disclosure".
e ”, 1982, 216, pp. 117-118.

The photoconductor of the present invention (lithographic printing plate precursor) is excellent in that its performance is hardly changed by 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. As these additives,
A chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties, a surfactant and the like are included.

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

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate, 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.
˜1 μ, particularly 0.05 to 0.5 μ is preferable.

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.

As the organic solvent to be used, specifically, a halogenated hydrocarbon having 1 to 3 carbon atoms such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane is particularly preferable. 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 known method can be applied to prepare a printing plate using the lithographic printing plate precursor of the present invention obtained as described above, and a copy image can be formed on the electrophotographic plate having the above-mentioned structure by a conventional method. After formation, it is created by desensitizing the non-image area. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include scanning exposure using a semiconductor laser, a He-Ne laser, or the like, reflection image exposure using a xenon lamp, a Tigsten lamp, a fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and the like. Next, 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 form a printing plate.

The desensitizing treatment used in the present invention is, as described above, the desensitizing of the resin particles of the present invention containing the formyl group and / or the functional group represented by the general formula (I), that is, hydrophilicity. It is achieved by the addition of. The method for desensitizing (conferring hydrophilicity) the formyl group-containing resin particles of the present invention includes a solution containing a hydrophilic group-containing compound that easily nucleophilically reacts with the formyl group (aqueous solution or water-soluble organic solvent). It is achieved by treating with a mixed solution containing).

As a hydrophilic compound which causes a nucleophilic substitution reaction on a formyl group, a nucleophilic constant n [R. G. Person, H .; Sobel,
J. Songstad, J.M. Amer. Chem. So
c. , 90 , 319 (1968)] containing a substituent having a value of 5.5 or more, and 1 in 100 parts by weight of distilled water.
A hydrophilic compound which can dissolve by weight or more can be used.

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, mercaptobenzenedicarboxylic 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 or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinate , Dicarboxybenzenesulfinic acid and the like as a hydrazide compound, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid Etc. as primary or secondary amine compounds such as 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.

These nucleophilic compounds are used by being contained in the desensitizing solution. The amount of the nucleophilic compound present in these treatment liquids is 0.1 mol / liter to 10 mol / liter, preferably 0.5 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, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, 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.

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

The scope of the present invention is not limited to the above specific compound examples. The method of desensitizing the functional group-containing resin of the present invention represented by the general formula (I) is, as shown in the above reaction formula (1), a formyl group produced after a dealcoholization reaction by acid decomposition. In addition, the nucleophile is hydrophilized by nucleophilic reaction.

Since the dealcoholization reaction easily proceeds in a treatment liquid having a pH of 5 or less, it is possible to easily form a formyl group by treatment in the treatment liquid having a pH of 5 or less before the treatment for carrying out the nucleophilic reaction. And then hydrophilized by a nucleophilic reaction. Therefore, the planographic printing plate produced by the present invention is prepared by the desensitizing treatment as described above.

Further, the hydrophilic treatment with the treatment liquid containing the nucleophilic compound can obtain the same effect even when the fountain solution for printing contains the nucleophilic compound.

[0268]

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

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

[0270]

[Chemical 46]

Production Example 2 of dispersion stabilizing resin: [M-2] A mixed solution of 100 g of 2-ethylhexyl 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 47]

Production Example 3 of Dispersion Stabilizing Resin: [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. with 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 48]

Production Example 4 of Dispersion Stabilizing Resin: [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 49]

Production Examples 5 to 12 of dispersion stabilizing resin: [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]

Production Examples 13 to 16 of dispersion stabilizing resin: [M
-13] to [M-16] Each resin was produced in the same manner as in Production Example 4 except that the compound corresponding to Table 3 was used instead of 2-hydroxymethacrylate in Production Example 4. The weight average molecular weight of each resin was in the range of 6 × 10 ^{3 to} 7 × 10 ³ .

[0281]

[Table 3]

Production Example 17 of dispersion stabilizing resin: [M-1
7] 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 50]

Production Examples 18 to 22 of dispersion stabilizing resin: [M
-18] to [M-22] By carrying out the reaction as shown in Production Example 17, the following Table-4.
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 [P-17] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. Acrolein [C-1] 4
7 g, the following monomer [D-1] 3 g, ethylene glycol dimethacrylate 5 g, A.I. 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 0.15 μm. {: CAPA-5
00 [HORIBA, Ltd.] particle size measurement}

[0288]

[Chemical 51]

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 0.10 to 0.30 μm.

[0290]

[Table 6]

[0291]

[Table 7]

[0292]

[Table 8]

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

[0294]

[Chemical 52]

Production Examples 14-24 of Resin Particles: [L-1
4] to [L-24] Resin particles [L-24] were produced in the same manner as in Production Example 14 except that the polyfunctional compound shown in Table 6 below was used instead of 5 g of ethylene glycol dimethacrylate in Production Example 12 of resin particles.
-15] to [L-25] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0296]

[Table 9]

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

[0298]

[Table 10]

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

[0300]

[Table 11]

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

[0302]

[Chemical 53]

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

[0304]

[Table 12]

[0305]

[Table 13]

[0306]

[Table 14]

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

[0308]

[Table 15]

[0309]

[Table 16]

[0310]

[Table 17]

Synthesis Example 25 of Resin [A]: [A-25] 98 g of 1-naphthyl methacrylate, methacrylic acid 2
g, 150 g of toluene and 50 g of isopropanol were heated to a temperature of 80 ° C. under a nitrogen stream. 4,4 '
-Azobis (4-cyano) valeric acid (abbreviation ACV)
5.0 g was added and stirred for 5 hours. Furthermore, A. C. V. 1
g for 2 hours, and then A. C. V. 1 g was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5.
It was × 10 ³ .

[0312]

[Chemical 54]

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

[0314]

[Chemical 55]

Example 1 and Comparative Examples AB Example 1 Resin [A-4] 8 g (as solid content), Resin [B-1] having the following structure 32 g (as solid content), Photoconductive zinc oxide 200 g 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.) 1 ×
10 ⁴ 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 with a wire bar to give 5g / m ² and 100
It was dried at 30 ° C. for 30 seconds.

[0316]

[Chemical 56]

A toluene dispersion having the following formulation was applied on the surface of this photoreceptor by a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour to form a surface layer of about 2 μm. Toluene Dispersion for Surface Layer Resin [B′-1] 2 g having the following structure: Resin particle [L-1] 4.5 g (as solid content) Phthalic anhydride 0.01 g o-Chlorophenol 0.002 g was added to toluene to make the total amount. It 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.

[0319]

[Chemical 57]

Comparative Example A In Example 1, 8 g of resin [A-4] and resin [B-
1] An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 40 g of the resin [B-1] was used instead of 32 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.

[0321]

[Chemical 58]

Comparative Photoreceptor In Example 1, instead of 4.5 g of the resin particles [L-1] in the toluene dispersion for the surface layer, resin particles [LR-
1] An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 4.5 g (as solid content) was used. Examine the film properties (surface smoothness), electrostatic properties, desensitizing properties of the photoconductive layer (expressed by the contact angle of water of the photoconductive layer after desensitizing treatment) and printability of these photosensitive materials. It was 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 contents was used for exposure and development 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 Methyl methacrylate 60 g, methyl acrylate 40
g, 20 g of a dispersion polymer having the following structure and Isopar H6
While stirring 80 g of the mixed solution under a nitrogen stream, a temperature of 65
Warmed to ° C. To this, 1.2 g of 2,2'-azobis (isovaleronitrile) (AIVN) was added and reacted for 2 hours. I. V. N. 0.5 g was added and the mixture was reacted for 2 hours. I. V. N. 0.5 g was added and reacted for 2 hours.

Then, 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).

[0325]

[Chemical 59]

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

The above results are summarized in Table-11.

[0328]

[Table 18]

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 2 minutes in an E-1 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 Sodium sulfite 80 g Monoethanolamine 45 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to a total volume of 1.0 liter and then pH 13 with potassium hydroxide. Adjusted to .5. Note 5) Background stain of printed matter: After making each photosensitive material by the same operation as in Note 3) above, immersing it in the processing liquid of E-1 used in Note 4) at a temperature of 35 ° C. for 3 minutes, and then wetting it. E-as water
A solution obtained by diluting 1 with water four times was also printed using a neutral paper as a printing paper, and the number of printed sheets until the background stain of the printed matter 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.

When each of these photoreceptors was subjected to a desensitizing treatment to evaluate the degree of hydrophilicity of the non-image area (water-holding capacity of the original plate), Comparative Example B showed significant background stain due to the adhesion of printing ink 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 background stain even when neutral paper was used as the printing paper, and a printed image of clear image quality of 5 was obtained. I got a thousand.
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, 8 g of resin [A-4] and resin [B-
1] 32 g, methine dye [I] 0.017 g and resin particles [L-1] 4.0 g, instead of resin [A-19] 6
g, resin [B-2] having the following structure 34.0 g, methine dye [II] having the following structure 0.020 g, and resin particles [L-2]
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 4.5 g was used.

[0335]

[Chemical 60]

Each property was measured in the same manner as in Example 1.
The following are particularly severe environmental conditions (30 ° C, 80% R
H) shows the measurement results under. Electrostatic properties V _10: -740V D. R. R. : 77% E _1/10 : 48 erg / cm ² Imaging property: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No scumming 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 2-mercaptoethanesulfonic acid 85 g Morpholine 40 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 1 g Methyl ethyl ketone 100 g was dissolved in distilled water to a total volume of 1.0 liter and potassium hydroxide. The pH was adjusted to 13.0.

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 20 Instead of the resin particles [L], resin [A] and resin [B] used in Example 1, 5.0 g of the resin particles [L] of the present invention shown in Table 12 below. Each photographic material was prepared in the same manner as in Example 1 except that (as the solid content) and 7 g of the resin [A] or 33 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.

[0341]

[Chemical formula 61]

[0342]

[Table 19]

With respect to each of the light-sensitive materials, the electrostatic characteristics and the printing characteristics were measured in the same manner as in Example 13. As a result, the chargeability, the dark charge retention rate, and the photosensitivity were all excellent, and the actual copied image was high at high temperature. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image was obtained with no background fog or fine line skipping. When the performance of the offset lithographic original plate was evaluated after desensitization, the water retention of the original plate was good in all cases, and 3,000 sheets could be printed even in the printing result after the actual plate making.

Examples 21 to 24 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 13 below were used instead of the methine dye [I].

[0345]

[Table 20]

Each of the light-sensitive materials exhibited almost the same image pick-up property and printing property as those of Example 1, and it was a good result. Examples 25 to 27 7.0 g of resin [A] shown in Table 13 below, 34.0 g of binder resin [B-4] having the following structure, 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was added in a homogenizer at a rotation speed of 1 × 10 ⁴ r.p.m. p. m. Dispersed for 15 minutes. This electrophotographic photosensitive material was prepared by applying the photosensitive layer-forming dispersion to a conductive-treated paper with a wire bar so that the dry adhesion amount was 22 g / m ² and drying at 100 ° C. for 3 minutes.

[0347]

[Chemical formula 62]

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 1 g Resin particles [L] in Table 14 below 4.5 g (as solid content) 1,2,4,5-benzenetetracarboxylic dianhydride 0.02 g Phenol 0.0015 g was added to toluene to make the total amount 100 g.

[0349]

[Chemical 63]

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-14.

[0351]

[Table 21]

In the mode of carrying out the evaluation items shown in Table 14, the image pick-up performance was carried out 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 14 for each light-sensitive material, all the performances were good, and the number of printable sheets was 3,000.

Example 28 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.

[0355]

[Chemical 64]

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.

[0357]

[Chemical 65]

Resin particles [L-29] were formed on the surface of this photoreceptor.
3.3% 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.

[0359]

[Chemical 66]

This photosensitive material was immersed in a desensitizing solution (E-3) prepared according to the following formulation at a temperature of 40 ° C. for 1 minute to desensitize it. Desensitizing treatment liquid (E-3) Serine 75 g Monoethanolamine 30 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 1.5 g Methyl ethyl ketone 80 g These are 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.

As in the first embodiment, this is a fully automatic plate-making machine E.
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. Furthermore, temperature 40 ℃
The master plate after plate making was soaked in the desensitizing solution (E-4) prepared by the following formulation, for 1.5 minutes, and then washed with water for desensitizing treatment.

Desensitizing Treatment Liquid (E-4) Sodium Sulfite 85 g Boric Acid 55 g Benzyl Alcohol 80 g These are dissolved in distilled water to a total volume of 1.0 liter, and the pH of this liquid is adjusted to 13.0 with sodium hydroxide. Was prepared in the same manner. 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 5,000 sheets had no fog in the non-image area and the image was clear.

Examples 29 to 40 Using each of the photosensitive materials prepared in Examples 1 to 28, an etching process was carried out as follows to prepare an offset printing original plate. After adding distilled water to 0.5 mol of the nucleophilic compound shown in Table 14 below, 100 g of an organic solvent and 6 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter,
The pH of each mixture was adjusted to 11.0. Each light-sensitive material was dipped in the above processing solution at 45 ° C. for 1 minute.

The plate thus obtained 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.

[0366]

[Table 22]

[0367]

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

Claims (4)

[Claims] 1. At least one layer of light on a conductive support.
A flat layer with a conductive layer and a surface layer on top of it.
In the original plate for plate printing, the following
Contain at least one aqueous dispersion resin particle [L]
And a resin having the following content as a binder resin in the photoconductive layer.
A lithographic printing plate precursor containing at least one of [A]
Image exposure to form a toner image, and then
-At least the photoconductive layer in the non-image area other than the image area
Hydrophilic compound having a nucleophilic constant n of 5.5 or more
Printing by desensitizing with a treatment liquid containing
A method for producing a lithographic printing plate, which comprises using an original plate. Non-aqueous dispersion resin particles [L]: in the non-aqueous solvent, the non-water-soluble
A solvent that is soluble in the medium but becomes insoluble by polymerization.
A mil group and / or a functional group represented by the following general formula (I)
Monofunctional monomer [C] having at least one kind, and silicon
An atom and / or a fluorine atom-containing substituent,
Monofunctional monomer copolymerizable with functional monomer (C)
(D) represents the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent.
Copolymerization obtained by carrying out dispersion polymerization reaction in the presence of
Body resin particles. [Chemical 1][However, in the above formula (I), A₁, A₂Are the same
Same or different, and represents a hydrocarbon group, or
A₁, A₂Is an organic residue that connects to each other to form a ring
Representation] Resin [A]: 1 × 10³~ 2 x 10^FourWeight average molecular weight of
And having a repeating unit represented by the following general formula (II)
Polymer containing 30% by weight or more as a polymer component
At one end of the main chain, -PO₃H₂, -SO₃H, -COO
H, -P (= O) (OH) R ₀₁[R₀₁Is a hydrocarbon group or
-OR₀₂Group (R₀₂Represents a hydrocarbon group) and a ring
At least one type of polarity selected from the group containing acid anhydride
A resin formed by combining groups. [Chemical 2][However, in the above formula (II), a₁, A₂Are each
Represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group.
You R₀₃Represents hydrocarbon. ] 2. The method for producing a lithographic printing plate 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 method for producing a lithographic printing plate according to Claims (1) and (2), which comprises at least one polymerizable double bond group moiety represented by the following general formula (III). [Chemical 3] [In the general formula (III), 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 (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula (II), At least one is contained, The manufacturing method of the lithographic printing plate in any one of Claims (1)-(3) characterized by the above-mentioned. [Chemical 4] [However, in the above formulas (IIa) and (IIb),
T ₁ and T ₂ are each independently a hydrogen atom and a carbon number of 1 to
10 hydrocarbon groups, chlorine atom, -COR ₀₄ or -COO
R ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ each represent a single bond or a connecting atom number 1 to 4 which connects —COO— and the benzene ring. Represents a linking group. ]