JPH0561214A - Production of planographic printing original plate - Google Patents

Abstract

PURPOSE:To reproduce a copied image which has an excellent electrostatic characteristic and is faithful to an original picture and to prevent an offset stock soln. from generating not only the surface stain uniform over the entire surface but dotty surface stain as well by processing the non-image part of a photoconductive layer by a desensitizing liquid. CONSTITUTION:An electrophotographic sensitive body is formed by incorporating a resin [A] and nonaq. dispersion resin particles [L] as a binder resin into the photoconductive layer. The resin [A] consists of the polymer component of the repeating unit expressed by formula I and a polymer component contg. a polar group. In the formula I, a1, a2 denote a hydrogen atom, etc.; R03 denote a hydrocarbon group. The nonaq. dispersion resin particles [L] are obtd. by bringing a polymer contg. a formyl group and a monomer having a substituent contg. a silicon atom into a polymn. reaction in the presence of a resin for stabilizing dispersion soluble in a nonaq. solvent. A toner image is formed on this electrophotographic sensitive body by image exposing and thereafter, the nonconductive layer of the non-image part of the image exclusive of the toner image part is desensitized by a processing liquid contg. a hydrophilic compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lithographic printing plate precursor prepared by electrophotography, and particularly to a composition for forming a photoconductive layer and a desensitizing treatment for the lithographic printing plate precursor. Regarding the improvement of the method.

[0002]

2. Description of the Related Art At present, various types of offset original plates for direct plate making have been proposed and put into practical use. Above all, photoconductive particles such as zinc oxide and a binder resin are mainly used on a conductive support. The photoconductor provided with the photoconductive layer as a component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is treated with a desensitizing solution called an etchant. However, a technique for obtaining an offset original plate by selectively making the non-image portion hydrophilic 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 at the same time the non-image area is sufficiently hydrophilized. It has water resistance, and in printing, the surface conductive layer with the image does not separate, and it is well compatible with fountain solution, so that it does not stain even when the number of printed sheets increases, It is necessary to have such properties as maintaining hydrophilicity. It has been clarified that these performances are greatly influenced by the type of binder resin in the photoconductive layer, and as offset master plates, various zinc oxide binder resins that improve desensitization are studied in particular. Has been done. Especially, methacrylate (or acrylate)
Examples include multi-component copolymers containing at least a component,
For example, Japanese Patent Publication No. 50-31011 and Japanese Patent Laid-Open No. 53-402.
7, JP-A-57-202544, and JP-A-58-68.
No. 046 is known.

Further, a binder resin using a resin containing a functional group capable of generating a hydrophilic group by decomposition has been investigated. For example, a binder resin containing a functional group capable of generating a hydroxyl group by decomposition (Japanese Patent Application Laid-Open No. 2000-242242). Sho 62-195684
JP-A-62-210475, JP-A-62-210
No. 476) or those containing a functional group capable of generating a carboxyl group by decomposition (Japanese Patent Laid-Open No. 62-21269), or those containing a functional group capable of generating a hydroxyl group or a carboxyl group by decomposition and bridging between polymers. To prevent water stain and improve printing durability by imparting water solubility and water swelling property (JP-A 1-19
1157, JP-A-1-197765, JP-A 1-1
91860, JP-A-1-185667, JP-A-1-
190552, JP-A-1-191158, etc.) are known.

However, even if the above-mentioned resin, which is said to be effective in improving the desensitizing property, is actually evaluated,
The background stains and printing durability were still unsatisfactory.

Further, JP-A-1-232356 and 1-26.
In each of the 1657 publications, it is described that the addition of resin particles containing a hydrophilic group to the photoconductive layer is effective in improving water retention.

It has been confirmed that the water retention is remarkably improved by improving these photoconductive compositions.

[0008]

However, when evaluated in more detail as a lithographic printing original plate, environmental fluctuations (high temperature
At high humidity or low temperature / low humidity, electrophotographic characteristics (especially charge retention in the dark, photosensitivity, etc.) fluctuated, and stable and good copied images could not be obtained. As a result, as a result, the print image of the printed matter using this as a printing original plate is deteriorated or the background stain prevention effect is reduced.

Further, in the electrophotographic lithographic printing original plate as a digital direct lithographic printing original plate, when a scanning exposure method using a semiconductor laser beam is adopted, the time becomes longer than that of the whole surface simultaneous exposure method 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 or 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.

The present invention improves the above-mentioned problems of the conventional electrophotographic lithographic printing plate precursor.

That is, the first object of the present invention is to provide a copy image which is excellent in electrostatic characteristics (in particular, dark charge retention and photosensitivity), which is faithful to the original image, and which is a uniform surface as an offset original plate. This is a method for producing a lithographic printing plate precursor that is excellent in desensitization and does not cause stains or spot stains.

A second object of the present invention is a method for producing a lithographic printing plate precursor having a clear and high-quality image even when the environment for forming a copied image varies from low temperature and low humidity to high temperature and high humidity.

The third object of the present invention is a method for producing a lithographic printing original plate which is not easily affected by the types of sensitizing dyes which can be used in combination and which has excellent electrostatic characteristics even in the scanning exposure system using a semiconductor laser beam.

[0015]

The present invention has at least the above-mentioned object of providing a photoconductive layer comprising at least photoconductive zinc oxide particles, a spectral sensitizing dye and a binder resin on a conductive support. In the electrophotographic lithographic printing plate precursor having one layer, at least one of the following resins [A] is contained as the binder resin, and the maximum particles of the photoconductive zinc oxide particles are contained in the photoconductive layer. The electrophotographic photosensitive member containing at least one kind of non-aqueous dispersion resin particles [L] having the average particle diameter equal to or smaller than the above diameter is subjected to image exposure to form a toner image. The photoconductive layer in the non-image area other than the toner image area is desensitized with a treatment liquid containing a hydrophilic compound having a nucleophilic constant n of at least a value of 5.5 or more to obtain a printing original plate. A lithographic stamp characterized by It is achieved by the manufacturing method of use original.

As the resin [A], 1 × 10 ³ to 2 × 10
Having a weight average molecular weight of ⁴ and containing a repeating unit represented by the following general formula (I) as a polymer component in an amount of 30% by weight or more,
_{-PO 3 H 2, -SO 3 H} , -COOH, -P (= O)
(OH) R ₀₁ [R ₀₁ is a hydrocarbon group or a -OR ₀₂ group (R ₀₂
Represents a hydrocarbon group)] [the above-P (= O) (O
H) R ₀₁ is

[0017]

[Chemical 5]

Is shown. ] And 0.5 to 15% by weight as a polymer component having at least one polar group selected from a cyclic acid anhydride-containing group,

[0019]

[Chemical 6]

[However, in the above formula (I), a ₁ , a
Each ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. The non-aqueous dispersion resin particles [L] contained in the photoconductive layer of the present invention are a formyl group and / or the following general formula, which are soluble in the non-aqueous solvent but are insolubilized by polymerization in the non-aqueous solvent. (I
Copolymerization with a monofunctional monomer (C) having at least one functional group represented by I) and a substituent containing a silicon atom and / or a fluorine atom, and the monofunctional monomer (C). Copolymer resin particles obtained by subjecting a possible monofunctional monomer (D) to a dispersion polymerization reaction in the presence of a dispersion-stabilizing resin soluble in the non-aqueous solvent.

[0021]

[Chemical 7]

[However, in the above formula (II), A ₁ ,
A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A ₂ represent an organic residue which is linked to each other to form a ring. That is, according to the present invention, an electrophotographic photosensitive member containing the resin [A] and the dispersed resin particles [L] is insensitive to a treatment liquid containing a hydrophilic compound having a person nucleophilic constant n of 5.5 or more. The drawbacks of the related art can be overcome by the method for producing a lithographic printing plate precursor that is subjected to an oiling treatment.

In the lithographic printing plate precursor of the present invention, the non-image area of the photoconductive layer containing at least the photoconductive zinc oxide particles, the spectral sensitizing dye and the binder resin in the uppermost photoconductive layer is insensitive. This is a printing original plate of a system in which the surface is made hydrophilic by treating with an emulsifying liquid to obtain a lithographic printing plate.

The photoconductive layer of the present invention comprises a low molecular weight resin [at least comprising photoconductive zinc oxide, a spectral sensitizing dye, a specific copolymer component and a specific polar group-containing polymer component]. A] and non-aqueous solvent-based dispersed resin particles (hereinafter,
Resin particles [L] may be abbreviated in some cases).

The resin particles [L] used in the present invention have an average particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles and a narrow particle size distribution and a uniform particle size. There is something.

Further, the resin particles [L] of the present invention have a nucleophilic constant n.
Has a value of 5.5 or more when treated with a treatment liquid containing at least one hydrophilic compound (which exhibits nucleophilic reactivity) (desensitizing treatment), and / or the formyl group of the resin particles described above. A nucleophilic reactive hydrophilic compound can be added to the terminal of the functional group [monofunctional monomer (C)] represented by the formula (II), whereby the particles can exhibit hydrophilicity.

Furthermore, the resin particle [L] of the present invention comprises a polymer component [monofunctional monomer (D having at least one repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom). )]
This is considered to indicate that the large lipophilicity of the substituent containing a fluorine atom and / or a silicon atom causes a migration / concentration phenomenon on the surface portion of the photoconductive layer.

That is, in the lithographic printing plate precursor of the present invention, the resin particles [L] concentrated and present on the surface portion of the photoconductive layer form a hydrophilic group by the desensitizing treatment of the present invention, and are hydrophilic. By expressing, the non-image portion is sufficiently modified to be hydrophilic, and sufficient water retention that does not cause scumming is exhibited.

Further, the resin particles [L] are used after forming the photoconductive layer.
It rapidly migrates to the surface portion and concentrates and exists in the portion near the surface.

The mechanism of the resin particles [L] of the present invention being hydrophilized by a 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).

[0031]

[Chemical 8]

The resin particles of the present invention have a nucleophilic reactivity hydrophilic property such that the nucleophilic constant n of the person in the processing liquid is 5.5 or more only when the non-image area is desensitized as a lithographic printing plate. It is characterized by adding a hydrophilic group to the terminal by reacting with a hydrophilic compound as described above, thereby expressing hydrophilicity, that is, hydrophilizing, and it does not react with moisture in the atmosphere, so it is storable. There is no problem of concern. 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.

On the other hand, 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, the general formula (II)
As shown in the reaction formula (1), the functional group represented by can be used in the same manner as the formyl group, because the deacetalization reaction can easily proceed by acid treatment and can be converted into a formyl group. It is possible.

In the lithographic printing plate precursor of the present invention, the zinc oxide particles uniformly dispersed in the resin [A] may be desensitized by a known method to make the non-image area hydrophilic. Can be used together.

On the other hand, the resin [A] of the present invention is a low molecular weight polymer containing the specific polymer component represented by the formula (I) and having the specific polar group bonded thereto.

The photoconductive layer of the present invention is dispersed by the photoconductive zinc oxide particles, the spectral sensitizing dye, and the resin [A] containing at least the resin particles [L] as a binder resin. Conceivable.

From the above, the present invention provides a low molecular weight compound having a specific polar group bonded when the photoconductive zinc oxide particles, the spectral sensitizing dye, the resin particles [L] and the resin [A] are dispersed. The resin [A] is adsorbed to the stoichiometric defects of the photoconductive zinc oxide, and the coating property and the adsorbed state for the interaction of the zinc oxide and the dye are appropriately performed, whereby the photoconductive oxidation is performed. It is considered that this is because while the zinc trap is compensated and the humidity characteristic is dramatically improved, the photoconductive zinc oxide is sufficiently dispersed and the aggregation is suppressed.

In particular, in the case of the conventional binder resin, when the kind of the spectral sensitizing dye is changed, the interaction such as adsorption is harmed and it becomes impossible to obtain satisfactory electrophotographic characteristics. However, the resin of the present invention [A ], It is possible to satisfy remarkably excellent electrophotographic characteristics even with a dye used for spectral sensitization for semiconductor laser light.

That is, the lithographic printing plate precursor of the present invention uses the resin [A] and the resin particles [L] of the present invention to form a good copy image due to excellent electrophotographic characteristics and a desensitized oil after the copy image is formed. It was possible to solve the difficult problem of excellent water retention in the non-image area after the chemical treatment.

Further, in the lithographic printing plate precursor of the present invention, since the resin particles in the photoconductive layer contain a polymer component containing a fluorine atom and / or a silicon atom in the resin particles, the resin particles can be obtained. It is also possible to add a very small amount to cause a migration / concentration phenomenon in the surface portion of the photoconductive layer and to bring about the same effect (water retention) as that of the known technique.

As a result, the lithographic printing plate precursor produced according to the present invention reproduces a copied image faithful to the original image even when the environmental conditions are changed or a low output laser beam is used, and a non-image. Since the part has good hydrophilicity, it does not cause scumming, and the photoconductive layer has good smoothness and electrostatic properties, and further has excellent printing durability.

Further, the lithographic printing plate precursor according to the present invention is characterized in that it is not affected by the environment at the time of plate making process and is very excellent in preservability before the process. Furthermore, resin [A]
Preferably contains at least one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I) ( Hereinafter, the resin [A ′] is preferable.

[0043]

[Chemical 9]

[In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR ₀₄ or-
COOR ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ are each -COO-
Represents a single bond or a linking group having 1 to 4 connecting atoms for connecting a benzene ring with the resin] The resin [A ′] has more electrophotographic properties (especially V ₁₀ , D) than the resin [A]. RR, E _1/10 )
Can be improved.

The reason for this is not clear, 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.

In the present invention, in the above resin particles, it is preferable that the polymer component having a formyl group and / or the functional group represented by the general formula (II) has a crosslinked structure.

In the present invention, the resin particles having a crosslinked structure further suppress the elution property with water, while exhibiting the water swelling property and further improving the water retention. Further, as the dispersion stabilizing resin in the present invention, a resin containing at least one polymerizable double bond group moiety represented by the following general formula (III) in the polymer chain is particularly preferable. As.

[0048]

[Chemical 10]

[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 R} 1 -, - C 6 H 4 -, - CONHC
Represents OO- or -CONHCONH- (provided that p
Represents an integer of 1 to 4, and R ₁ is a hydrogen atom or has 1 carbon atom.
Represent to 18 hydrocarbon group), b _1, b ₂ is through one another may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₂ or a hydrocarbon group -COO-R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)].

It is considered that the dispersion stabilizing resin for stabilizing dispersion of the non-aqueous dispersion resin particles of the present invention is adsorbed to the insolubilized copolymer portion in the reaction process of polymerization granulation, and further, the above formula (III) In the case of the dispersion-stabilizing resin containing a polymerizable double bond group portion represented by, both polymer components are considered to be chemically bonded.

That is, in the present invention, the resin particles are those in which a hydrophobic polymer component and a dispersion stabilizing resin are bonded,
Since this hydrophobic part interacts with the binder resin of the photoconductive layer, it does not elute with dampening water during printing due to the anchoring effect of this part, and it is possible to print a large number of sheets. Printing characteristics can be maintained.

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

As described above, the resin particles of the present invention have an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, but larger than the zinc oxide particle diameter. When the resin particles having a particle size are present, electrophotographic characteristics are deteriorated (especially uniform charging properties cannot be obtained). As a result, density unevenness in the image portion, breakage of characters / fine lines, jumping, or background fog in the non-image portion occurs in the copied image.

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

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

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

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

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

The proportion of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (Ia) and / or the formula (Ib) in the resin [A '] is 30% by weight or more, preferably 50%.
The amount of the polymer component containing a specific polar group is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the resin [A '].

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

Examples of the hydrocarbon in the —COO—R ₀₆ group through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like.

R ₀₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, Tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-
Cyanoethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethoxy group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group,
Octenyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (benzyl group having carbon atoms, phenethyl group,
Naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group,
Cycloheptyl group etc.), optionally substituted aryl group (eg phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl) Group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.) and the like.

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

In formula (Ia), preferred T ₁ and T ₂
Independently of each other, in addition to a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group), aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl group) -Benzyl group) and aryl groups (for example, phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₀₄ and -C.
OOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms) can be mentioned.

In the formulas (Ia) and (Ib), L ₁ and L
₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) n1 - (} n 1 represents an integer of 1 to 3), -
_{CH 2 OCO -, - CH 2} CH 2 OCO -, - (CH 2
O) _m1 - (m ₁ represents an integer of 1 or _2), - CH 2 C
A connecting group having 1 to 4 connecting atoms such as H ₂ O-,
More preferably, a direct bond or a linking group having 1 to 2 bonding atoms can be mentioned.

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

[0067]

[Chemical 11]

[0068]

[Chemical formula 12]

[0069]

[Chemical 13]

[0070]

[Chemical 14]

[0071]

[Chemical 15]

[0072]

[Chemical 16]

[0073]

[Chemical 17]

[0074]

[Chemical 18]

[0075]

[Chemical 19]

[0076]

[Chemical 20]

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

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

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

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

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

The copolymerizable component containing a polar group of the resin [A] is, for example, a monomer corresponding to the repeating unit represented by the general formula (I) [including general formulas (Ia) and (Ib)]. Any vinyl compound containing a polymerizable polar group may be used, and it is described, for example, in "Polymer Data Handbook [Basic Edition]", edited by The Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α -Fluoro compound, α-tributylsilyl compound, α-cyano compound, β-chloro compound, β-bromo compound, α
-Chloro-β-methoxy form, α, β-dichloro form, etc.),
Methacrylic acid, itaconic acid, itaconic acid half esters,
Itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-
Hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid,
Maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids, vinyl group or allyl group half-ester derivatives, and these carboxylic acids or sulfonic acids And the compound containing the polar group in the substituent of the amide derivative.

The polar group-containing copolymerization component will be illustrated 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, g is 2 to
Indicates an integer of 10.

[0084]

[Chemical 21]

[0085]

[Chemical formula 22]

[0086]

[Chemical formula 23]

[0087]

[Chemical formula 24]

[0088]

[Chemical 25]

[0089]

[Chemical formula 26]

[0090]

[Chemical 27]

[0091]

[Chemical 28]

[0092]

[Chemical 29]

[0093]

[Chemical 30]

[0094]

[Chemical 31]

[0095]

[Chemical 32]

[0096]

[Chemical 33]

[0097]

[Chemical 34]

[0098]

[Chemical 35]

[0099]

[Chemical 36]

[0100]

[Chemical 37]

[0101]

[Chemical 38]

[0102]

[Chemical Formula 39]

[0103]

[Chemical 40]

[0104]

[Chemical 41]

[0105]

[Chemical 42]

[0106]

[Chemical 43]

[0107]

[Chemical 44]

[0108]

[Chemical 45]

[0109]

[Chemical 46]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ']) means a monomer other than these together with the monomer of the general formula (I), (Ia) and / or (Ib) and the monomer containing the polar group. The body may be contained as a copolymerization component.

Examples of such other copolymerization component include, for example, methacrylic acid esters, acrylic acid esters and crotonic acid esters having a substituent other than those described in the general formula (I), and α-olefins. , Vinyl carboxylates or acrylic acid esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (for example, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphtha). Phthalene, etc.), vinyl sulfone-containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like. 30% by weight of these other monomers in the resin [A]
It is desirable not to exceed.

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

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

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

Low molecular weight resin [A] as described above
(Including [A ′]) is preferably used in combination with the above-mentioned known resin for photoconductive zinc oxide. The use ratio of the low molecular weight resin and the other resin is preferably 5 to 50/95 to 50 (weight ratio).

In the present invention, the use ratio of photoconductive zinc oxide, resin (total binder resin) and resin particles [L] is preferably 100/10 to 100 / 0.01 to 10 (weight ratio). Further, the resin [A] is preferably 5 to 50% by weight in all the binder resins 10 to 100.

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

Typical examples are vinyl chloride-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-methacrylate copolymers, methacrylate copolymers, acrylate copolymers, vinyl acetate copolymers, polyvinyls. Butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

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

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

[0121]

[Chemical 47]

[In the formula (III), V is -COO-,-
_{OCO -, - (CH 2)} q -OCO -, - (CH 2) q
-COO -, - O- or -SO ₂ - represents a. However, q represents an integer of 1 to 4] In the general formula (III), f ₃ and f ₄ are a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms. (For example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) is represented. R ₁₃
Is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group,
Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms which may be substituted (for example, vinyl group, allyl group, isopropenyl group) , Butenyl group, hexenyl group, heptenyl group, octenyl group, etc.),
Aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), 5 carbon atoms 8
Optionally substituted cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl group (eg, phenyl group, tolyl group, xyl group, mesityl group, naphthyl group, methoxyphenyl) Group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl group, chlorophenyl group, dichlorophenyl group, iodophenyl group,
Methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, nitrophenyl group and the like).

The medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (III) is, for example, a resin of a random copolymer containing the polymer component represented by the formula (III). (Japanese Patent Laid-Open Nos. 63-49817 and 63-22
No. 0149, 63-220148, etc.), a resin in which the random copolymer and a crosslinkable resin are used in combination (Japanese Patent Application Laid-Open No. 1-21).
No. 11766, No. 1-102573), Formula (II
A copolymer containing a polymer component represented by I) and partially cross-linked in advance (Japanese Patent Laid-Open Nos. 34860/1990 and 4066/1990).
No. 0), a graft-type block copolymer obtained by polymerizing a monofunctional macromonomer consisting of a polymer component of a specific repeating unit and a monomer corresponding to the component represented by the formula (III) -53064, the same 2-56558,
Same 3-29957, same 3-77954, same 3-9286
1, each of the same 3-53257 gazettes) etc. are mentioned.

Next, the non-aqueous solvent-based dispersed resin particles used in the present invention will be described in detail. 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.

The resin particles used in the present invention have an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and have a narrow particle diameter distribution and a uniform particle diameter. Is.

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.

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. Therefore, it is preferable to use 0.001 μm or more.

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 photoconductive zinc oxide. It is preferable to use it in an amount of 0.05 to 30% by weight. If the amount of resin particles or crosslinked resin particles is less than 0.05% by weight, the hydrophilicity of the non-image area will not be sufficient, and conversely, if it is more than 30% by weight, the hydrophilicity of the non-image area will be further improved, but severe. The electrophotographic characteristics under the conditions deteriorate, and 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, specifically, 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 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 total amount. 60-1
It is 00% by weight.

When the content 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 [II].

[0140]

[Chemical 48]

In the above formula (II), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ ,
A ₂ represents an organic residue which is linked to each other to form a ring.
When A 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 (eg, an alkyl group having 1 to 12 carbon atoms which may be substituted). Groups: Specific examples are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, methoxymethyl, ethoxymethyl, 2-hydroxyethyl, 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, preferably a functional group represented by the general formula (IIa), that is, a cyclic acetal group can be mentioned.

[0143]

[Chemical 49]

In the formula (IIa), A ₃ and A ₄ may be the same or different from each other, and are each a hydrogen atom or a carbon number of 1 to 1.
2 optionally substituted hydrocarbon groups, or an -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 (II) and (II
In a), when A _{1 to} A ₅ are aliphatic groups, the number of carbon atoms is 1
Are preferably an alkyl group having 6 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, and an aralkyl group having 7 to 9 carbon atoms.

Further, n is more preferably an integer of 1 to 3. Examples of the copolymerizable component containing a formyl group and / or a functional group represented by (II) used in the present invention include those represented by the repeating unit of the following general formula (IV).

[0148]

[Chemical 50]

[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 represents an organic residue which directly bonds or connects -Z- and -W _0- . Furthermore,-[Z-Y]-

[0151]

[Chemical 51]

The part and -W ₀ may be directly connected. W ₀ represents a formyl group or a functional group represented by (II).
f ₁ and f ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (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

[0157]

[Chemical 52]

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

[0159]

[Chemical 53]

[0160]

[Chemical 54]

[0161]

[Chemical 55]

[0162]

[Chemical 56]

In addition, specific examples of the functional group represented by the general formula (IIa) of the present invention are also shown. Examples (c'-1) to (c'-)
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.

[0165]

[Chemical 57]

[0166]

[Chemical 58]

The polymer component containing the formyl group and / or the functional group of the general formula (II) in the resin particle [L] of the present invention is, when the resin particle [L] is a copolymer,
It is preferably 30 to 99% by weight, and particularly preferably 50 to 95% by weight, based on the total copolymer.

The molecular weight of the polymer of the resin particles is 10
It is preferably from ³ to 10 ⁶ , more preferably from 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 (II) of the present invention as described above 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.

As the polymerizable functional group in the above-mentioned monomer synthesis, 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 particles [L] of the present invention are composed of the monomer [C]
It may be polymerized together with other monomers. Any other monomer may be used as long as it can be copolymerized with the monomer [C] and the copolymer becomes an insoluble polymer in the non-aqueous solvent.

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

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

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

Examples of the substituent containing a silicon atom include:
_{-Si (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 symbols as R ₃ , R ₄ and R ₅ .

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

[0182]

[Chemical 59]

[0183]

[Chemical 60]

[0184]

[Chemical formula 61]

[0185]

[Chemical formula 62]

[0186]

[Chemical 63]

[0187]

[Chemical 64]

[0188]

[Chemical 65]

[0189]

[Chemical 66]

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.

The other monomer may be a compound represented by the general formula (X) described below.
Or a monomer corresponding to the formula (X)
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 distilled water described above can satisfy 50 degrees or less.

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

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

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

[0196]

[Chemical 67]

[0197] formula (X), X ₂ represents the same content as V ₀ which Formula (II), details are given in the description of V ₀ which formula (II).

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

[0199] c _1, c ₂ represents a b _1, b ₂ the same contents as in Formula (II), details are described in the description of the b _1, b ₂ of the formula (II).

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

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

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

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

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

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

The polymerizable double bond group portion will be described below.

[0207]

[Chemical 68]

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

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

[0210] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group) Group, ethoxy group, propoxy group, butoxy group, etc.) and the like.

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

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

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

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

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 contents as R ₁ in formula (II).

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

[0217]

[Chemical 69]

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

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

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

The 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.

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

[0223]

[Chemical 70]

[0224]

[Chemical 71]

[0225]

[Chemical 72]

[0226]

[Chemical 73]

[0227]

[Chemical 74]

[0228]

[Chemical 75]

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-61-43757, Japanese Patent Application No. 1-149030
It is described in detail in the specification etc. filed as No. 5.

For example, a polymer reaction by a combination of a functional group of group A and a 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.

[0233]

[Table 1]

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

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

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

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

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

Further, the polymerizability to be coexisted by the above method (b)
Polyfunctional monomer containing two or more functional groups [polyfunctional monomer
Also referred to as a monomer (E)] or a polyfunctional oligomer
As the polymerizable functional group, specifically, CH₂= CH-CH₂-, CH₂= CH-CO-O-,
CH₂= CH-, CH₂= C (CH₃) -CO-O-,
CH (CH₃) = CH-CO-O-, CH₂= CH-C
ONH-, CH₂= C (CH₃) -CONH-, CH
(CH₃) = CH-CONH-, CH₂= CH-O-C
O-, CH₂= C (CH₃) -O-CO-, CH₂= C
H-CH₂-O-CO-, CH₂= CH-NHCO-,
CH₂= CH-CH₂-NHCO-, CH₂= CH-S
O₂-, CH₂= CH-CO-, CH ₂= CH-O-,
CH₂= CH-S- and the like can be mentioned. these
Two polymerizable functional groups with the same or different
Any monomer or oligomer having the above may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a styrene derivative such as divinylbenzene or trivinylbenzene as a monomer or oligomer having the same polymerizable functional group: 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 (for example, 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 5 mol%, preferably less than 5 mol% to form a resin.

Further, in the case of the above method (c), in the case of forming a chemical bond by the reaction of the reactive groups between the polymers to form a bridge between the polymers, the reaction with a usual organic low molecular compound is 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, since monodisperse particles having a uniform particle size can be obtained and fine particles of 0.5 μm or less can be easily obtained, polyfunctionality is used as a method for forming a network structure. The method (b) using a monomer is preferable.

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

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

Specific examples of this organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol and benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, hexane, octane, decane, dodecane and tridecane. , Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples thereof include halogenated hydrocarbons such as trichloroethane. However, it is not limited to the above-mentioned compound examples.

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

Specifically, K. B. J. Barrett
"Dispersion Polymerization
in Organic Media "John Wil
ey (1975), Koichiro Murata, Polymer processing, 23 ,
20 (1974), Tsunetaka Matsumoto / Toyoyoshi Tange, Japan Adhesive Association Magazine 9 , 183 (1973), Tokichi Tange, Adhesive Society of Japan
23 , 26 (1987), D.I. J. Walbridge
e, NATO. Adv. study. Inst. Se
r. B. No. 67, 40 (1983), British Patent No. 8
No. 93429, No. 934038, US Pat. No. 1
122397, 394012, and 4606989, JP-A-60-179751, and 60-185.
The method is disclosed in each of the 963 publications and the like.

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

In order to produce the dispersion 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, a method of adding a polymerization initiator to a mixed solution of (i) monomer (C), monomer (D), dispersion stabilizing resin and polyfunctional monomer (E),
(ii) There are methods such as dropwise addition or optional addition of the mixture of the above-mentioned polymerizable compound and polymerization initiator into the non-aqueous solvent, and the method is not limited to these, and any method can be used for production.

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

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

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

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide. Further, as another inorganic photoconductor, titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide or the like may be used in combination.

However, the content of these other photoconductive materials is 40% by weight or less, preferably 20% by weight or less of the photoconductive zinc oxide.

If the content of other photoconductive materials exceeds 40% by weight,
The effect of improving the hydrophilicity of the non-image area as the lithographic printing original plate is diminished.

As the photoconductive zinc oxide according to the present invention,
What is conventionally known in the technical field of this kind may be used,
Not only so-called zinc oxide, but also acid-treated zinc oxide, pigment-pretreated, kneaded and pulverized again (so-called press treatment), etc. are not particularly limited.

The total amount of the binder resin used for the inorganic photoconductive material is 1 part binder resin per 100 parts by weight of the photoconductor.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 50 parts by weight.

The spectral sensitizing dye used in the photoconductive layer of the present invention may be any conventionally known dye, and these may be used alone or in combination. 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 .: Transactions of the Institute of Electrical Communication, J63-C (No. 2) 97.
Page (1980), Yuji Harasaki et al., Journal of Industrial Chemistry 66 , 78.
And 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan 3
5 , carbon dioxide dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes,
Cyanine dye, rhodacyanine dye, cytylyl dye, etc.),
Examples thereof include phthalocyanine dye (which may contain a metal).

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

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyani
neDyes and Related Compou
The dyes described in "nds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,11059.
1, 3121008, 3125447, 3128
No. 179, No. 3132942, No. 3622317, British Patent Nos. 12268892, No. 1309274, No. 1405898, and Japanese Patent Publication Nos. 48-7814 and 55-18892.

[0268] Furthermore, in the near-infrared region 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, JP-A-49-5034, JP-A-49-45122,
57-46245, 56-34141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Pat.
Each issue, "Research Disclosure
e ", 1982, 216, pages 117 to 118, and the like. The photoconductor of the present invention is excellent in that the performance thereof does not fluctuate depending on the sensitizing dye even when various sensitizing dyes are used in combination.

Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers such as chemical sensitizers may be used in combination. For example, the review mentioned above: Imaging 19
73 (No. 8) page 12, etc., electron-accepting compounds (eg, halogen, benzoquinone, chloranil,
Acid anhydrides, organic carboxylic acids, etc.), Hiroshi Komon et al., "Recent Developments and Practical Uses of Photoconductive Materials and Photoconductors", Chapters 4 to 6: Japan Science Information Publishing Co., Ltd. (1986) The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc.

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

Examples of the charge transport material of the laminated type photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, triphenylmethane dyes and the like. The thickness of the charge transport layer is preferably 5 to 40 μ, particularly 10 to 30 μ.

As the resin used for forming the charge transport layer,
Typical examples are polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl chloride copolymer resin, polyacrylic resin, polyolefin resin, urethane resin, polyester resin, epoxy resin. Resins, melamine resins, thermoplastic resins such as silicone resins, and curable resins are appropriately used.

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, for example, 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 preventing curling, A body having a water-resistant adhesive layer on its surface, a body having at least one precoat layer as necessary on the surface layer of the support, and a base conductive plastic having vapor-deposited Al etc. laminated on paper. Things etc. can be used.

Specifically, as examples of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), p2-11 (1975), Hiroyuki Moriga, "Science of Introductory Special Paper", Polymer Publishing (1975), M.S. F. Hoo
ver., J. Macromol. Sci. Chem. A
-4 (6), pages 1327 to 1417 (1970) and the like are used.

In order to actually prepare the lithographic printing plate precursor of the present invention, the resin of the present invention and, if necessary, the above-mentioned additives and the like are volatile carbonized at a boiling point of 200 ° C. or lower according to a conventional method. The electrophotographic photosensitive layer (photoconductive layer) can be formed by dissolving or dispersing in a hydrogen solvent, and coating and drying the solution. As the organic solvent used,
Specifically, especially dichloromethane, chloroform, 1,2
1 to 3 carbon atoms, such as dichloroethane, tetrachloroethane, dichloropropane or trichloroethane
The halogenated hydrocarbons of are preferred. Other aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran and methylene chloride, and various solvents used in the coating composition and the above solvents. Mixtures of can also be used.

The production of a printed matter using the electrophotographic printing original plate of the present invention is carried out by forming a copy image on the electrophotographic original plate having the above-mentioned constitution by a conventional method and then desensitizing the non-image area. Created.

The printing original plate of the present invention is prepared by desensitizing the non-image portion of the lithographic printing original plate thus formed. The desensitizing treatment used in the present invention is, as described above, desensitizing the resin particles of the present invention containing a functional group represented by the formyl group and / or the general formula (II), that is, imparting hydrophilicity, And by desensitizing the zinc oxide particles.

The formyl group-containing resin particles of the present invention can be desensitized (hydrophilicity imparted) by a solution (aqueous solution or water solution) containing a hydrophilic group-containing compound which easily undergoes a nucleophilic reaction with the formyl group. It is achieved by treatment with a mixed solution containing an organic solvent.

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 a desensitizing solution for zinc oxide photoconductor, or
The binder resin is used by being contained in a treatment liquid for separate treatment. The amount of the nucleophilic compound present in these treatment solutions was 0.1.
The amount is 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.

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 for desensitizing the functional group-containing resin of the present invention represented by the general formula (II) 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 solution having a pH of 5 or less, it is treated with the above-mentioned treatment solution for desensitizing zinc oxide (usually adjusted to pH 5 or less) or nucleophilic. PH before treatment to carry out reaction
A formyl group can be easily produced by treatment in a treatment liquid of 5 or less, and subsequently, hydrophilicity is obtained by a nucleophilic reaction.

Desensitization of zinc oxide has hitherto been carried out as a desensitizing treatment liquid of this type by using a ferrocyanine salt, a cyanide-containing treatment liquid containing a ferricyanate as a main component, an amminecobalt complex, phytic acid and Known are cyanide-free treatment liquids containing their derivatives, guanidine derivatives as main components, treatment liquids containing inorganic or organic acids that form chelates with zinc ions as main components, or treatment liquids containing water-soluble polymers. ..

For example, as a cyanide-containing treatment liquid,
JP-B-44-9045, JP-B-46-39403, JP-A-5-39
2-76101, ibid 57-107889, ibid 54-11.
Examples thereof include those described in each of the 7201 publications.

As the phytic acid compound-containing treatment liquid,
JP-A-53-83807, 53-83805, 53
-102102, 53-109701, 53-12
7003, 54-2803, and 54-44901 each are mentioned.

Treatment solutions containing a metal complex compound such as a cobalt complex are disclosed in JP-A-53-104301 and JP-A-53-1.
40103, 54-18304, and JP-B-43-284.
04 The thing described in each gazette is mentioned.

As the treatment liquid containing an inorganic or organic acid, JP-B-39-13702, 40-10308 and 43-2 are available.
8408, 40-26124, JP-A-51-1185.
No. 01, etc. are mentioned.

Examples of the guanidine compound-containing treatment liquid include those described in JP-A-56-111695. A treatment liquid containing a water-soluble polymer is disclosed in Japanese Patent Application Laid-Open No.
2-126302, 52-134501, 53-4
9506, 53-59502, 53-10430
2, JP-B-38-9665, 39-22263, 4
0-763, 40-2202, JP-A-49-3640.
2 The thing described in each gazette etc. is mentioned.

In any of the above desensitizing treatments,
Zinc oxide in the surface layer, which is the photoconductive layer, is ionized into zinc ions, and this ion causes a chelation reaction with the compound forming a chelate in the desensitizing solution, forming a zinc chelate, which is the surface. It is believed to be deposited in the layer and made hydrophilic.

Therefore, the printing original 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 at the time of printing contains the nucleophilic compound.

[0296]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. Synthesis Example of Binder Resin [A] 1: [A-1] A mixed solution of 95 g of benzyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to a temperature of 90 ° C. under a nitrogen stream, and then 2,2′-azobis. 6.0 g of isobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 2 g was added and reacted for 2 hours. The weight average molecular weight of the obtained copolymer [A-1] was 8,500. Synthesis Example 2/28 of Binder Resin [A]: [A-2] to [A-
28] Resins [A-2] to [A-28] shown in Table 2 below were synthesized in the same manner as in the polymerization conditions of Synthesis Example 1 of resin [A].

[0297]

[Table 2]

[0298]

[Table 3]

[0299]

[Table 4]

[0300]

[Table 5]

[0301]

[Table 6]

[0302]

[Table 7]

[0303]

[Table 8]

Synthesis Example 29 of Binder Resin [A]: [A-2
9] A mixed solution of 95 g of 2,6-dichlorophenyl methacrylate, 5 g of acrylic acid, 2 g of n-dodecyl mercaptan and 200 g of toluene was heated to a temperature of 80 ° C. under a nitrogen stream, and then A. I. B. N. Add 2g and react for 4 hours,
Then A. I. B. N. 0.5 g was added for 2 hours, and A. I. B. N. 0.5 g was added and reacted for 3 hours. After cooling, it was reprecipitated in 2 liters of a mixed solution of methanol / water (9/1), the precipitate was collected by decantation, and dried under reduced pressure. The yield of the obtained waxy copolymer is 78.
The weight average molecular weight in g was 6.3 × 10 ³ .

Next, specific examples of production of the dispersion stabilizing resin for resin particles and resin particles will be described.

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

[0307]

[Chemical 76]

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

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

[0310]

[Chemical 77]

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

[0312]

[Chemical 78]

Production Example 4 of Resin for Dispersion Stabilization: P-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. with 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 .

[0314]

[Chemical 79]

Production Examples 5 to 12 of dispersion stabilizing resin: P-5
~ P-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 3 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 .

[0316]

[Table 9]

Production Examples 13 to 16 of dispersion stabilizing resin: P-
13 to P-16 Each resin was produced in the same manner as in Production Example 4 except that the compound corresponding to Table 4 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 .

[0318]

[Table 10]

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

[0320]

[Chemical 80]

Production Examples 18 to 22 of dispersion stabilizing resin: P-
18 to P-22 By carrying out the reaction as shown in Production Example 17, the following Table-5.
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 .

[0322]

[Table 11]

[0323]

[Table 12]

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. with 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}

[0325]

[Chemical 81]

Production Examples 2-12 of Resin Particles: [L-2]
[L-12] Same as Production Example 1 except that in Production Example 1 of resin particles, the monomers [C-1] and [D-1] were replaced with the main monomer shown in Table 6 below. To produce resin particles. The average particle size of each particle was within the range of 0.10 to 0.30 μm.

[0327]

[Table 13]

[0328]

[Table 14]

[0329]

[Table 15]

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

[0331]

[Chemical formula 82]

Production Examples 14-24 of Resin Particles: [L-1
4] to [L-24] In the same manner as in Production Example 14, except that the polyfunctional compound shown in Table 7 below was used in place 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.

[0333]

[Table 16]

Production Examples 25-34 of Resin Particles: [L-2
5] to [L-34] Monomer [C-12] 46 g, Monomer [D-7] 4 g, Ethylene glycol diacrylate 2 g, Each dispersion stabilizing resin [P] 8 g described in Table 8 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.

[0335]

[Table 17]

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.

[0337]

[Table 18]

Example 1 and Comparative Examples AB Example 1 6 g of resin [A-3] (as solid content), 33 g of resin [B-1] having the following structure (as solid content), 200 g of photoconductive zinc oxide. Methine dye [I] 0.018 having the following structure
g, a mixture of 0.15 g of salicylic acid and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
10 ³ r. p. m. Was dispersed for 10 minutes at the rotation speed of. To this, 1.0 g (as solid content) of dispersed resin particles [L-1] and 0.01 g of phthalic anhydride were added, and the rotation speed was 1 × 1.
0 ³ r. p. m. Dispersed for 1 minute. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 100 ° C. for 30 seconds, and further heated at 120 ° C. for 1 hour. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

[0339]

[Chemical 83]

[0340]

[Chemical 84]

Comparative Example A In Example 1, 6 g of resin [A-4] and resin [B-
1] An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 39 g of the resin [B-1] was used instead of 33 g. Comparative Example B Comparative Dispersed Resin Particles: [LR-1] In Production Example 1: [L-1] of resin particles, the monomer [D
-1] was synthesized in the same manner as in Production Example 1 except that 3 g was removed. The average particle size of the obtained latex was 0.17 μm.

Comparative Photoreceptor Same as Example 1 except that 1 g of resin particles [LR-1] (as solid content) was used in place of 1 g of resin particles [L-1] in Example 1. An electrophotographic photosensitive material was produced.

Film formation (smoothness of the surface), electrostatic characteristics, desensitizing property of the photoconductive layer (represented by contact angle of water of the photoconductive layer after desensitizing treatment) and printing of these photosensitive materials. I investigated the sex. The printing property is a lithographic plate obtained by exposing and developing an image on a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) using a developer ELP-T to form an image and desensitizing the image. It examined using the printing plate. (Incidentally, Hamada Star 800SX manufactured by Hamada Star Co., Ltd. was used as the printing machine.) The above results are summarized in Table-10.

[0344]

[Table 19]

Embodiments of the evaluation items shown in Table-10 are as follows. Note 1) Smoothness of photoconductive layer: Using the Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.), the smoothness (sec / cc) of the obtained photosensitive material was measured under the condition of an air capacity of 1 cc. It was measured. Note 2) Electrostatic characteristics: Corona discharge at −6 kV for 20 seconds using a paper analyzer (Paper Analyzer-SP-428 type manufactured by Kawaguchi Electric Co., Ltd.) on each photosensitive 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 the dark decay for 90 seconds, that is, the dark decay retention rate [DR (%)] was measured. [(V ₁₀₀ /
V ₁₀ ) × 100 (%)].

The surface of the photoconductive layer was-
After charging to 500 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. Environmental conditions at the time of imaging are I (20 ° C, 65% RH)
And II (30 ° C., 80% RH). 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 speed exposure under a dose of 45 erg / cm ² at a pitch of 25 μm and a scanning speed of 330 m / sec, ELP-T (Fuji Photo Film Co., Ltd.) was used as a liquid developer.
The copied image (fog, image quality of the image) obtained by developing and fixing was visually evaluated.

Note 4) Raw plate water retention: Each light-sensitive material itself (original plate which is not made into a plate: abbreviated as a raw plate) is a desensitizing treatment liquid ELP-EX manufactured by Fuji Photo Film Co., Ltd.
Using an aqueous solution diluted twice, set the etching machine to 1
Pass through, and further desensitize treatment solution of the following formulation: 3 in E-1
Soaked for a minute. Next, these editions are Hamada Star
Printing was performed using a Hamada Star 8005X type, and the presence or absence of background stains on the 50th printed material after printing was visually evaluated. Desensitizing treatment liquid: E-1 Ammonium sulfite 75 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 adjusted to pH 11.0 with potassium hydroxide. did.

Note 5) Background stain of printed matter: After plate-making each light-sensitive material by the same operation as the above-mentioned note 3), after passing through an etching machine once with ELP-EX, as fountain solution, These offset master original plates were printed using a solution obtained by diluting E-1 with water five times, and the number of printed sheets until the background stain of the printed matter could be visually discriminated was examined.

The electrostatic characteristics of the present invention and Comparative Example B were good, and the actual image pick-up and copied images were clear. However, in Comparative Example A, the electrostatic property was deteriorated, and the image pickup property was lacking in thin lines / characters / thin line parts of low density and was unclear.

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 Examples A and B were both found to cause background stains due to printing ink adhesion. However, the non-image area was not sufficiently hydrophilized.

Further, when the plate was actually made and then desensitized and printed, the planographic printing plate of the present invention was free from the occurrence of background stain, and 10,000 prints having a clear print quality were obtained. On the other hand, in Comparative Example A in which the resin [A] was not used together, scumming occurred on the printed surface after about 4,000 sheets. Although known resin particles are used, in Comparative Example B in which the amount of the resin particles used was reduced to the same amount as that of the photoconductor of the present invention, scumming occurred in about 3,000 sheets.

As described above, the electrophotographic lithographic printing plate precursor in which the hydrophilicity of the non-image area is sufficiently advanced and the background fog is not generated,
It was only the present invention. Example 2 In Example 1, 6 g of resin [A-3], resin [B-
1] 33 g, and resin particles [L-1] 1.0 g instead of resin [A-18] 4 g, resin [B-2] having the following structure
An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 35.0 g and 2.5 g of resin particles [L-26] were used.

[0353]

[Chemical 85]

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.

[0355] However, in the desensitizing treatment, E- used in Example 1 was used.
Instead of 1, the desensitizing treatment liquid E-2 having the following formulation was used.

Desensitizing treatment liquid: E-2 N-methyl-N- (3-sulfopropyl) amine 85 g Newcol B4SN (manufactured by Nippon Toray Agent Co., Ltd.) 8 g Methyl ethyl ketone 100 g was dissolved in distilled water to give a total amount of 1 The volume was adjusted to 0.0 liter and adjusted to pH 12.0 with potassium hydroxide.

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 16 Instead of the resin particles “L”, resin [A], and resin [B] used in Example 1, 2.0 g of resin particles [L] of the present invention shown in Table 11 below (solid content) Each) and each of the photosensitive materials were prepared in the same manner as in Example 1 except that 5 g of the resin [A] and 34 g of the resin [B-3] having the following structure were used.

The electrostatic characteristics and printing characteristics were evaluated by operating in the same manner as in Example 2.

[0359]

[Chemical formula 86]

[0360]

[Table 20]

With respect to each of the light-sensitive materials, the electrostatic property and the printing property were measured by operating in the same manner as in Example 2. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high at high temperature. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image was obtained with no background fog or fine line skipping.

When the performance of the offset lithographic original plate was evaluated after desensitization, the water retention of the original plate was good and the actual printing result after plate-making was 10,000 sheets. Example 17 and Comparative Examples C to D Resin [A-7] 6.0 g, Resin [B-4] 3 having the following structure
4 g, zinc oxide 200 g, uranine 0.02 g, rose bengal 0.04 g, bromphenol blue 0.03
g, 0.25 g phthalic anhydride and 300 g toluene, in a homogenizer at 1 × 10 ⁴ r.p. p. m. Was dispersed for 5 minutes at the rotation speed of. Resin particles [L-24]
1.0g (as solid content) was added and the rotation speed was 1 × 1.
0 ³ r. p. m. Dispersed for 1 minute. This is applied to a conductive-treated paper with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dried at 100 ° C. for 3 minutes, and then at 20 ° C. and 65% RH in the dark. An electrophotographic light-sensitive material was prepared by leaving it for a period of time.

[0363]

[Chemical 87]

Comparative Example C An electrophotographic photosensitive material was produced in the same manner as in Example 1, except that 1.0 g of the resin particles [L-24] in Example 17 was not added. Comparative Example D In Example 17, 6 g of resin [A-1] and resin [B-
4] Instead of 34 g, resin [R-2] 39 having the following structure
An electrophotographic photosensitive material was produced in the same manner as in Example 15 except that g was used.

[0365]

[Chemical 88]

The film properties (surface smoothness), film strength, electrostatic properties, imaging properties and environmental conditions of these light-sensitive materials were set to 30.
The electrostatic characteristic image pickup device at the temperature of 80% RH was examined. Further, the photoconductive desensitizing property (water retention) and printability (background stain, printing durability, etc.) when these photosensitive materials were used as a master plate for offset master were examined.

The above results are summarized in Table-12.

[0368]

[Table 21]

Among the embodiments of the evaluation items shown in Table-12, the following items were operated according to the following contents. Note 6) Electrostatic characteristics: Corona discharge for 20 seconds at -6 kV using a paper analyzer (Paper Analyzer-SP-428 type manufactured by Kawaguchi Electric Co., Ltd.) for each photosensitive material in a dark room at a temperature of 20 ° C. and 65% RH. After being allowed to stand for 10 seconds, the surface potential at this time was measured as V ₁₀ . Then, the potential V ₇₀ after standing still for 60 seconds in the dark is measured,
Retention of potential after dark decay for 60 seconds, that is, dark decay retention [D. R. R (%)] is [(V ₇₀ / V ₁₀ ) × 10
0 (%)]. Also, after the surface of the photoconductive layer is charged to -400 V by corona discharge, the surface of the photoconductive layer is then irradiated with visible light having an illuminance of 2.0 lux, and the time until the surface potential V ₁₀ is attenuated to 1/10 Then, the exposure amount E _1/10 (lux · second) is calculated from this. Similarly, V ₁₀ is 1 /
The time until it attenuates to 100 is calculated, and the exposure amount E
Calculate _1/100 (lux · sec). Note 7) Imaging: Each photosensitive material and fully automatic plate-making machine ELP4
04V (manufactured by Fuji Photo Film Co., Ltd.) is left at room temperature and normal humidity (20 ° C, 65%) for one day and then plate-formed 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%).

The photoconductors of Example 15 of the present invention and Comparative Example C were good in both electrostatic characteristics and imaging properties. On the other hand, in Comparative Example D, the electrostatic property was deteriorated, and the influence was remarkably affected especially when the environmental conditions were changed, and the ground fog and the breakage of characters and fine lines were generated even in the actual copy image.

On the other hand, in the desensitized original plate, only in the present invention, the non-image area was made sufficiently hydrophilic and printing ink or the like was not seen, and up to 10,000 sheets could be printed. In Comparative Example C, the hydrophilization was insufficient, and in Comparative Example D, since the copied image was actually deteriorated in the original plate after plate making, even the printed matter was affected by imprinting so that only insufficient printed matter was obtained. There wasn't. Examples 18 to 31 In Example 17, 5 g (as solid content) of each resin [A] in Table 13 below and 2.0 g (solid) in place of the resin [A] and the resin particles [L]. As a quantity)
And a resin [B-5] having the following structure as the resin [B]
An electrophotographic light-sensitive material was produced in the same manner as in Example 17 except that 33.5 g was used.

[0372]

[Chemical 89]

[0373]

[Table 22]

Each of the light-sensitive materials has high temperature and high humidity (30 ° C.,
Even under 80% RH), excellent electrostatic properties were obtained in the present invention. In addition, both the image pick-up property and the water retention property were good, and when used as an offset master original plate and printed, 10,000 or more prints with clear image quality without scumming were obtained. Examples 32 to 43 Instead of 60 g of thiomalic acid and 100 g of benzyl alcohol in the desensitizing treatment liquid E-1 used in Example 1, 0.5 mol of each compound shown in Table 14 below and 100 solvents.
Each photographic material shown in Table 14 below was prepared in the same manner as in Example 1 except that each processing solution prepared in the same manner as the processing solution E-1 was used except that g was used.
The same process as above was carried out to obtain a printing original plate.

[0375]

[Table 23]

When each printing original plate was printed in the same manner as in Example 1, the same good results as in Example 1 were obtained.

[0377]

INDUSTRIAL APPLICABILITY According to the present invention, an electrophotographic photoreceptor having excellent electrostatic properties and mechanical properties can be obtained even under severe conditions. It is possible to print a large number of prints with clear image quality.

Furthermore, the original plate of the present invention is effective for a scanning exposure system using a semiconductor laser beam.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03G 13/28 7818-2H

Claims (4)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive support and at least one photoconductive layer containing at least photoconductive zinc oxide particles, a spectral sensitizing dye, and a binder resin. The photoconductive layer contains at least one resin [A] having the following content as the binder resin, and the photoconductive layer has a particle size equal to or smaller than the maximum particle size of the photoconductive zinc oxide particles. An electrophotographic photosensitive member containing at least one kind of non-aqueous dispersion resin particles [L] having the following content having an average particle diameter is subjected to image exposure to form a toner image, and then a non-image other than the toner image portion is formed. Part of the photoconductive layer is desensitized with a treatment liquid containing a hydrophilic compound having a nucleophilic constant n of at least a value of 5.5 or more to obtain a lithographic printing plate. Original plate manufacturing method. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , and having 30% by weight or more of a repeating unit represented by the following general formula (I) as a polymer component, -PO ₃ H ₂ , -S
_{O 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 0.5 as a polymer component having at least one polar group selected from a cyclic acid anhydride-containing group.
Resin containing about 15% by weight. [Chemical 1] [However, in the above formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ₀₃ represents a hydrocarbon group. Non-aqueous dispersion resin particles [L]: at least a formyl group and / or a functional group represented by the following general formula (II) which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the non-aqueous solvent. A monofunctional monomer (C) having one kind and a monofunctional monomer (C) containing a substituent containing a silicon atom and / or a fluorine atom and copolymerizable with the monofunctional monomer (C) ( Copolymer resin particles obtained by subjecting D) to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. [Chemical 2] [However, in the above formula (II), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or
₁ , A ₂ represents an organic residue which is linked to each other to form a ring] 2. The above-mentioned resin [A] is an aryl group-containing methacrylate component represented by the following general formula (Ia) and general formula (Ib) as a copolymer component represented by the general formula (I). The method for producing a lithographic printing plate precursor according to claim 1, comprising at least one. [Chemical 3] [In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ₀₄ or —COOR.
₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent a single bond or a connecting atom number of 1 to 4 which connects —COO— and the benzene ring. Represents a linking group of. ] 3. In the non-aqueous solvent-based dispersed resin particles,
The method for producing a lithographic printing plate precursor according to claim 1 or 2, wherein the polymer component having a formyl group and / or the functional group represented by the general formula (II) forms a crosslinked structure. 4. The dispersion stabilizing resin, in the polymer chain,
The method for producing a lithographic printing plate precursor according to any one of claims 1 to 3, further comprising at least one polymerizable double bond group moiety represented by the following general formula (III). [Chemical 4] [In the general formula (III), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CONR 1 -, - S
O ₂ NR ₁ —, —C ₆ H ₄ —, —CONHCOO— or —CONHCONH— (where p represents an integer of 1 to 4, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). , B ₁ and b ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or —CO via a hydrocarbon group.
Represents O—R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)