JP2855022B2 - Liquid developer for electrostatography and method for producing printing plate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatographic liquid developer used for developing an electrostatic latent image. In addition, the present invention provides a printing plate having an organic photoconductive compound provided on a conductive substrate having a hydrophilic surface, forming a toner image using a liquid developer by electrophotography, and after fixing, aqueous alkaline etching. The present invention also relates to a method of manufacturing a printing plate in which a non-image portion other than a toner image portion is removed by etching with a liquid.
It is.

[0002]

2. Description of the Related Art Met is used as a liquid developer for electrostatography.
Many are already known, including the liquid developer described in US Patent No. 2,907,674 to Calfe et al. For example, pigments or dyes such as carbon black, phthalocyanine blue, and nigrosine, and resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers are mechanically dispersed in a highly insulating solvent using a ball mill, attritor, homogenizer, or the like. And a charge control agent such as metal soap, lecithin, linseed oil, higher fatty acid and the like. However, the liquid developer obtained by this method has the disadvantage that precipitates are generated due to the large size distribution of the developer particles, and the dispersion stability and charge stability are poor. Furthermore, when a toner image is formed and used as a resist layer using a liquid developer for a printing plate as described below, there are few liquid developers excellent in both resolution and resistability and printing durability. It was a fact. . The case where a toner image is formed using a liquid developer for electrostatography and used as a resist layer will be described in detail below.

Examples of printing plate materials (original printing plates) utilizing electrostatography include, for example, JP-B-47-47610, JP-B-48-40002, JP-B-48-18325, JP-B-51-15766 and JP-B-51-15766. Zinc oxide-resin dispersion type offset printing materials described in JP-B-51-25761 and the like are known, and these printing plate materials are made non-image-sensitive by a non-image portion after forming a toner image by electrophotography. It is used after being wetted with a desensitizing solution (for example, an acidic aqueous solution having a ferrocyan salt or a ferricyan). The offset printing plate subjected to such a treatment has a printing durability of about 5,000 sheets / 10,000 sheets, and is not suitable for printing more than that, and when a composition suitable for desensitization is used, the electrostatic characteristics deteriorate. And the image quality is degraded.

[0004] Many organic photoconductor-resin printing plate materials are also known, for example, Japanese Patent Publication No. 37-17162 and Japanese Patent Publication No.
8-7758, JP-B-46-39405, JP-A-5-79
Printing plate materials described in JP-A-2-24375 and JP-B-2-46944 can be used. In these printing plates, a styrene-maleic anhydride copolymer, a vinyl acetate-crotonic acid copolymer, a vinyl acetate-maleic anhydride copolymer or a phenol resin which is soluble in alkali and / or alcohol as a binder for an organic photoconductor Using an organic photoconductive compound, and the like, a photosensitive member coated on a conductive metal substrate such as an aluminum plate,
A toner image is formed by performing corona charging, exposure and toner development, and a non-image portion other than the toner image is removed by etching with an alkaline aqueous etching solution, thereby removing the non-image portion where the hydrophilic metal substrate is exposed. A printing plate is made as an image portion. As an organic photoconductor-resin printing plate according to this method, there is a printing plate practically used under the trade name of Elfasol from Kale. But Elf
The asol system is a system for forming a toner image using a dry developer, and has a low resolution of about 3 to 5 lines / mm even when a fine powder of toner particles is used as the dry developer. I can only get it.

On the other hand, when a toner image is formed using a liquid developer, an image having a resolution of about 15 to 50 lines / mm is obtained. A toner image with a liquid developer has excellent resolution and a sharp image can be obtained, but the thickness of the toner image is considerably thinner than that of a dry image, and the resist property against an etching solution is inferior. There was a disadvantage that it was inferior.

[0006]

Generally, the characteristics required for a liquid developer for electrophotography are to have a good particle size distribution and excellent dispersion stability and charge stability. Further, as a property required for the liquid developer used for the printing plate, in addition to the resist property to the etching solution, good chargeability, dispersion stability, redispersibility and fixability are required. You. Various types of liquid developers used in printing plates have been developed and proposed in the past, but the resolution, chargeability, dispersion stability, redispersibility, fixability,
In fact, there is no one that satisfies all characteristics such as resist properties.

A first object of the present invention is to provide a liquid developer for electrostatography which has a good particle size distribution and excellent dispersion stability and charge stability. A second object of the present invention is to provide a liquid developer for forming a toner image having a strong resist property against an alkaline aqueous etching solution in the method of making a printing plate. A third object of the present invention is to provide a printing plate liquid developer which has excellent dispersion stability and can withstand long-term use and storage in the printing plate making method. A fourth object of the present invention is to provide a liquid developer for a printing plate capable of producing an electrophotographic lithographic printing plate having excellent resolution and excellent image reproducibility and having a high printing durability.

[0008]

Means for Solving the Problems An object of the present invention is to disperse at least resin particles in a nonaqueous solvent having a volume resistivity of 10 ⁹ Ωcm or more, and the dispersed resin particles are represented by the following general formula: In the presence of a dispersion stabilizing resin mainly containing a graft copolymer composed of at least one macromonomer containing a polymer component represented by (Ia) or (Ib), it is soluble in the non-aqueous solvent. At least one or more of a) styrene or a styrene derivative; b) an acrylate having an alkyl group having 3 or less carbon atoms or a methacrylate having an alkyl group having 3 or less carbon atoms. The selected monomer (which is soluble in the non-aqueous solvent but is insolubilized by the polymerization reaction) is dispersed in the non-aqueous solvent obtained by insolubilization by the polymerization reaction with the non-aqueous solvent. It is achieved by a liquid developer for electrostatic photography which is a that resin particles. The dispersion stabilizing resin is represented by the following general formula (II) at the terminal of the main chain of a polymer containing at least one of the polymer components represented by the following general formula (Ia) or (Ib). A graft copolymer comprising at least one macromonomer (M) having a weight-average molecular weight of 1 × 10 ^{3 to} 1 × 10 ^{5 formed} by bonding a polymerizable double bond, and at least one monomer represented by the following general formula (III): Resin soluble or colloidally dispersed in the non-aqueous solvent, mainly containing coalesced particles.

[0009]

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In the general formula (Ia), X ₀ is -COO-,-
_{OCO -, - (CH 2)} k -OCO -, - (CH 2) k -C
OO-, -O-, -CONHCOO-, -CONHCO
_{-, - SO 2 -, -} CO -, - CONZ 1 -, and -S
Represents one or more linking groups selected from O ₂ NZ _1- . Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and k represents an integer of 1 to 3. a ₁ and a _{2, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₂ or -COO-Z ₂ (Z ₂ via a hydrocarbon hydrogen Atom or a hydrocarbon group which may be substituted.). Q ₀ represents an aliphatic group having 1 to 22 carbon atoms.

[0011]

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In the general formula (Ib), Q represents —CN or a phenyl group which may be unsubstituted or have a substituent.
As the substituent, a halogen atom, an alkoxy group or -C
OOZ ₃ (Z ₃ represents an alkyl group, an aralkyl group, or an aryl group). a ₁ and a ₂ are represented by the general formula (Ia)
Represents the same group as a ₁ and a _{2 in the above} .

[0013]

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In the general formula (II), V is -COO-, -O
_{CO -, - (CH 2)} k -OCO -, - (CH 2) k -CO
O-, -O-, -CONHCOO-, -CONHCO
_{-, - SO 2 -, -} CO -, - CONZ 1 -, - SO 2
It represents NZ ₁ -or a phenylene group (hereinafter, the phenylene group is represented by Ph, where Ph includes 1,2-; 1,3-; 1,4-phenylene groups). Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and k represents an integer of 1 to 3. b ₁ and b
₂ may be the same or different, and represent the same contents as a ₁ and a ₂ in the general formula (I).

[0015]

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In the general formula (III), X ₁ represents the general formula (I
It represents the same content as V in I), and Q ₁ represents a hydrogen atom, an aliphatic group having 1 to 22 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. c ₁ and c ₂ may be the same or different from each other, and represent the same contents as a ₁ and a _{2 in} formulas (Ia) and (Ib). However, in the macromonomer represented by the general formula (Ia) and the monomer component represented by the general formula (III), at least _one of Q ₀ and Q ₁ has 4 to 4 carbon atoms.
Represents 22 aliphatic groups. Further, the graft copolymer is a macromonomer represented by the general formula (Ib),
When it comprises the monomer component represented by II), Q ₁ represents an aliphatic group having 4 to 22 carbon atoms.

Next, means for obtaining a liquid developer comprising copolymer resin particles having excellent positive charge stability will be described. The first method for obtaining a positively charged liquid developer is
Macromonomer in which a terminal carboxyl group of the main chain of the polymer component represented by the above general formula (I) and an epoxy compound having a polymerizable double bond group are bonded using a tertiary amine or a quaternary ammonium salt as a reaction catalyst. It is a method using. That is, in the presence of a dispersion stabilizing resin having a graft copolymer composed of a macromonomer synthesized using a tertiary amine or quaternary ammonium salt as a reaction catalyst,
Polymerization reaction of a monomer that is soluble in the non-aqueous solvent (soluble in the non-aqueous solvent, but insolubilized by polymerization reaction) causes a positive charge comprising resin particles dispersed in the non-aqueous solvent. This is a method for obtaining an ionic liquid developer.
In the first method, it is considered that the quaternary ammonium salt used as the reaction catalyst is incorporated into the macromonomer, and thus the toner particles are given a positive charge by being contained in the dispersion stabilizing resin. Can be

The second method is a method in which a dispersion stabilizing resin containing the above graft copolymer as a main component is added to a dispersion solution of resin particles. That is, in the presence of a dispersion stabilizing resin mainly composed of a graft copolymer composed of a macromonomer having the above structure synthesized without using a tertiary amine or a quaternary ammonium salt as a catalyst, it is soluble in the non-aqueous solvent. The first method is used in a non-aqueous dispersion solution of resin particles obtained by insolubilizing a certain monomer (which is soluble in the non-aqueous solvent but is insolubilized by the polymerization reaction). This is a method for obtaining a positively charged liquid developer by adding a dispersion stabilizing resin.

In the second method, the amount added when a dispersion stabilizing resin mainly containing a graft copolymer composed of a macromonomer synthesized using a tertiary amine or a quaternary ammonium salt as a catalyst is added later. Is 0.1 to 20 parts by weight with respect to 10 parts by weight of the resin component in the resin particle dispersion. Preferably, 1 to 50 parts by weight of the resin component is 10 to 50 parts by weight.
Parts by weight.

The third method is a method in which a monomer component (C) for giving a positive charge to toner particles is introduced, and ions are transferred by adding a charge control substance to generate charges.
Examples of the monomer component (C) that imparts positive charge to the toner particles include a vinyl monomer having a basic nitrogen atom or an amide group. These monomers (C) are copolymerized with at least one or more monomers selected from a) styrene or a styrene derivative, b) an acrylate or methacrylate having an alkyl group having 3 or less carbon atoms. Monomer.

Examples of the vinyl monomer having a basic nitrogen atom or an amide group include aminoalkyl-substituted (meth) acrylates represented by the general formula (IV) and aminoalkyl-substituted (meth) acrylates represented by the general formula (V). Grade salts, N-vinylimidazole, N-vinyl-2-methylimidazole, 1-vinylpyrrole, N-β-acryloxyethylindole, 2-vinylquinoline, 4-vinylpyridine, 5-vinyl-4-methylthiazole, 3
-Methyl-5-isopropenylpyrazole, N-vinyl-2-pyrrolidone, N-vinylpiperidone, N-vinyloxazolidone, dimethylaminostyrene, dialkylaminomethylstyrene, quaternary salts of dialkylaminomethylstyrene and (meth) acrylamide. Can be

[0022]

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In the general formula (IV), d ₁ and d ₂ are
They may be the same or different and each represents a hydrogen atom or a methyl group. Z ₄ and Z ₅ may be the same or different from each other, and represent the same group as Z ₁ described above. p is 1
Represents an integer of 1 to 3.

[0024]

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In the general formula (V), d ₁ , d ₂ , p,
Z ₄ and Z ₅ represent the same contents as in the general formula (IV). Z
₆ is an alkyl group having 1 to 18 carbon atoms or 7 carbon atoms
-24 represents an aralkyl group. X is halogen (fluorine, chlorine, bromine or iodine), acetate,
BF _4, represents a sulfate, p- toluenesulfonate or alkylsulfonate.

Hereinafter, the liquid developer of the present invention will be described in detail. The carrier liquid used in the liquid developer of the present invention is a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more, preferably an electric resistance of 1 ⁹ Ωcm.
A non-aqueous solvent having a dielectric constant of 3 or more and a non-aqueous solvent of at least ^{9 9} Ωcm, such as linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like. At least one solvent from halogen substituents can be mentioned. Specifically, for example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (isoper; Solvents selected from Exxon Corp.), Cielsol 70, Cielsol 71 (Cielsol; Cieloil Corp.), AMSCO OMS and AMSCO 460 solvent (Amsco; Spirits Corp.) alone or in combination. Used.

The non-aqueous solvent-based dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are prepared by adding the above-mentioned dispersant, which is a graft copolymer, to a non-aqueous solvent. A monomer having at least one monomer selected from a) styrene or a styrene derivative, b) an acrylate or methacrylate having an alkyl group having 3 or less carbon atoms, and It is produced by polymerization and granulation by polymerization.

The non-aqueous solvent used in the production of the dispersed resin particles may be any one which is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. And a solvent selected from aromatic hydrocarbons and their halogen-substituted products. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, toluene, xylene, isoper E, isoper G, isoper H, isoper L, Cielsol 70, Cielsol 71, Amsco OMS, and Amsco 460 solvent, etc. The selected solvents are used alone or as a mixture.

Solvents which can be used by mixing with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohols) and ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.). ), Carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.) and halogenated carbonized Solvents such as hydrogens (eg, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methyl chloroform, etc.). It is desirable that the non-aqueous solvent used by mixing these be distilled off under heating or under reduced pressure after polymerization granulation. However, even if the non-aqueous solvent is brought into a liquid developer as a latex particle dispersion, the liquid There is no problem as long as the resistance is within the range of 10 ⁹ Ωcm or more.

In general, it is preferable to use the same solvent as the carrier liquid at the stage of preparing the resin dispersion. As described above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, A solvent selected from such halogenated hydrocarbons is used. Hereinafter, the content of the graft copolymer will be further described. The macromonomer (M) can be copolymerized with a monomer represented by the general formula (III) at one terminal of a main chain of a polymer comprising a repeating unit represented by the general formula (Ia) or (Ib). Having a weight average molecular weight of 1 by bonding a polymerizable double bond group represented by the general formula (II):
× 10 ³ to 1 × 10 ⁵ macromonomers.

In the general formulas (Ia), (Ib), (II) and (III), a ₁ , a ₂ , b ₁ , b ₂ , V, X
_The hydrocarbon groups contained in ₀ , X ₁ , Q ₀ and Q ₁ each have the indicated carbon number (not shown), but these hydrocarbon groups may be substituted. In the general formula (Ia), X ₀
Is, -COO -, - OCO -, - (CH 2) k -OCO
_{-, - (CH 2) k} -COO -, - O -, - CONHC
OO -, - CONHCO -, - SO 2 -, - CO -, -
CON (Z ₁₎ - and -SO ₂ N (Z ₁₎ - represents one or more linking groups selected from. Where Z ₁
Represents a hydrogen atom or a hydrocarbon group, and k represents an integer of 1 to 3.

As the hydrocarbon group, an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group,
Octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-
Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, etc.), having 4 to 1 carbon atoms
8 optionally substituted alkenyl groups (for example, 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, Aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methyl A benzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, -Cyclopentylethyl group, etc.), or
An optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, decyloxyphenyl, chlorophenyl, dichlorophenyl , Bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecylylamidophenyl, etc.) ~ 18 bridged hydrocarbon groups (e.g., bicyclo [1,1,0]
Butane, bicyclo [3,2,1] octane, bicyclo [5,2,0] nonane, bicyclo [4,3,2] undecane, adamantane and the like].

A ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, and a C 1 -C 1 atom.
3 alkyl group (e.g., methyl group, ethyl group or propyl group), - COOZ ₂ or -CH ₂ COOZ ₂
(Z ₂ preferably represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted. represents a represents) the same contents as those described above Z _1. Q ₀ represents an aliphatic group having 1 to 22 carbon atoms, and specifically has the same content as the alkyl group described for Z ₁ described above.

In the general formula (Ib), Q represents —CN or a phenyl group which may be unsubstituted or may have a substituent.
As the substituent, a chlorine atom, a bromine atom, a halogen atom such as a fluorine atom, a methoxy group, an ethoxy group, a propoxy group,
An alkoxy group such as a butyroxy group, or —COOZ ₃ (Z
₃ represents an alkyl group, an aralkyl group, an aryl group,
These may be substituted, and specifically, the above Z ₁
Represents the same content as described above). a ₁ and a ₂ represents a _1, a ₂ of the same group in the general formula (Ia).

[0035] In the general formula (II), Z ₁ in the substituent represented by V represent the same meaning as Z ₁ in the general formula (I). V is -C ₆ H ₄ - may represent a benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, a chlorine atom or a bromine atom) or an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group, and the like).
a ₁ and a ₂ may be the same or different from each other, and represent the same contents as a ₁ and a ₂ in the general formula (I). k is 1
Represents an integer of ~ 3. A of the general formula (Ia) or (Ib)
More preferred groups a hydrogen atom b ₁ and b ₂ of ₁ and a _2, or formula (II), and methyl group. Preferred among the macromonomers (M) of the present invention are those represented by the general formula (VIa) or (VIb).

[0036]

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[0037]

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In the general formula, a ₁ , a ₂ , b ₁ , b ₂ , X
₀ , Q ₀ , Q and V are represented by the general formula (Ia) or (Ib),
Represents the same contents as described in the general formula (II).

W ₁ is a mere bond or —C (Z ₇ ) (Z ₈ )
-[Z ₇ and Z ₈ represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), a cyano group hydroxyl group or the like. ],-(CH = CH)-, cyclohexylene group (hereinafter, cyclohexylene group is represented by Cy, where Cy includes 1,2-; 1,3-; 1,4-cyclohexylene group), -Ph- , -O-, -S-, -C (=
O) -, - N (Z 9) -, - COO -, - SO 2 -, -
_{CON (Z 9) -, -} SO 2 N (Z 9) -, - NHCO
O -, - NHCONH-, or _{-Si (Z 9) (Z 10} ) -
[Z ₉ and Z _{10 each} represent a hydrogen atom, a hydrocarbon group having the same content as Z ₁ , etc.] or a single linking group selected from atomic groups such as Represent.

The above-mentioned general formula (Ia) or (Ib), (I
Particularly preferred examples of each of X ₀ , V, a ₁ , a ₂ , b ₁ and b ₂ in I), (III), (VIa) or (VIb) are shown below. The X ₀ -COO
-, - OCO -, - O -, - CH 2 COO- and -CH ₂
One or more linking groups selected from OCO-, and one kind of linking group selected from all the above-mentioned V (wherein Z ₁ is a hydrogen atom) is a ₁ , a ₂ ,
Examples of b ₁ and b ₂ include a hydrogen atom and a methyl group. (A ₁ ) C in the general formulas (VIa) and (VIb)
Specific examples of the group represented by H = C (a ₂ ) -V-W ₁ -include the group described in Japanese Patent Application No. 1-253252. However, the content of the present invention is not limited to these.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example,
1. 1. A method by an ionic polymerization method in which various terminals are reacted with a terminal of a living polymer obtained by anionic or cationic polymerization to form a macromer; Oligomers having terminal reactive group bonds obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxy group, or an amino group in a molecule, and various reagents 2. a method by a radical polymerization method in which a isomer is reacted to form a macromer; A method by a polyaddition condensation method in which a polymerizable double bond group is introduced into the oligomer obtained by the polyaddition or polycondensation reaction in the same manner as in the above-mentioned radical polymerization method.

More specifically, P.S. Dreyfuss &
R. P. Quirk, Encyclopedia Polymer Science Engineering (Encycl. Po
lym. Sci. Eng. 7), p. 551 (198
7), p. F. Rempp & E. Franta, Advanced Polymer Science (Adv. Poly)
m. Sci. ), Vol. 58, p. 1 (1984); Pe
rsec, Applied Polymer Science (App
l. Polym. Sci. ), 285, 95 (19
84) R.C. Asami, M .; Takagi, Macromolecular Hemy Supplement (Makromol.
Chem. Suppl. ), Vol. 12, p. 163 (198
5), p. Rempp, et al, same (Makrom
ol. Chem. Suppl), vol. 8, p. 3 (198
7), Yusuke Kawakami, Chemical Industry, 38, 56 (198
7), Tatsuya Yamashita, Polymer, Vol. 31, p. 988 (198)
2), Shiro Kobayashi, Polymer, Vol. 30, p. 625 (198)
1), Toshinobu Higashimura, Journal of the Adhesion Society of Japan, 18 536 pages (1982), Koichi Ito, Polymer Processing, 35 262
Page (1986), Kishiro Higashi, Takashi Tsuda, Functional Materials, 198
7, no. Compounds can be synthesized according to the methods described in patents and literatures such as 10, 10, and JP-A-62-232408.

For example, an oligomer having a terminal carboxyl group bond obtained by radical polymerization using a polymerization initiator and / or a chain transfer agent containing a carboxyl group in the molecule and an epoxy compound having a polymerizable double bond group can be used. To a macromonomer using a tertiary amine or a quaternary ammonium salt as a reaction catalyst. Specifically, it can be synthesized according to the method described in JP-A-62-232408. Preferred examples of the epoxy compound having a polymerizable double bond group include, for example, glycidyl methacrylate and glycidyl acrylate.

As the reaction catalyst used in the above example, a tertiary amine and a quaternary ammonium salt can be used.
In order to prevent coloring of the macromonomer, it is preferable to use a quaternary ammonium salt. The use of a quaternary ammonium salt as a reaction catalyst not only prevents the coloration of the macromonomer, but also unexpectedly causes the quaternary ammonium salt to be contained in the macromonomer and thus in the dispersion stabilizing resin. Is preferable because it allows the toner particles to have positive chargeability.

The quaternary ammonium salt used as a reaction _{catalyst, R 1 R 2 R 3 R} 4 N + X - indicated by. R ₁ , R
₂ , R ₃ and R _{4 each} represent an optionally substituted alkyl group having 1 to 32 carbon atoms (eg, methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, docosanyl, 2-ethylhexyl, -Butoxybutyl group, N, N-dibutylaminopropyl group, etc., and an optionally substituted alkenyl group having 3 to 32 carbon atoms (for example, allyl group, 2-pentenyl group, 4-propyl-2-pentenyl group, decenyl) Group, oleyl group, linoleyl group, etc.), aralkyl group having 7 to 36 carbon atoms which may be substituted (eg, benzyl group, phenethyl group, etc.),
An alicyclic hydrocarbon group having 5 to 32 carbon atoms which may be substituted (for example, a cyclopentyl group, a cyclohexyl group, a bicyclo [2,2,1] -heptyl group, a cyclohexenyl group, etc.); An optionally substituted aryl group (for example, phenyl group, tolyl group, 4-butylphenyl group, 4-decylphenyl group, 4-butoxyphenyl group, etc.) or a heterocyclic group having 5 or more atoms (for example, furyl group , A thienyl group, etc.). Examples of the substituent include a fluorine, chlorine, bromine and iodine atom, a hydroxy group, a nitro group, a nitrile group, an amino group, an alkoxy group, a sulfo group and a carboxyl group. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. _{Two of} R ₁ , R ₂ , R ₃ , and R ₄ may be bonded to each other, interrupted by 1 to 4 hetero atoms, and contain 0 to 6 double bonds; And a mononuclear or polynuclear ring having 4 to 12 carbon atoms and substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a nitro group or an amino group. A system may be formed.

[0046] X ^- represents an organic or inorganic anion. R
₁ to R ₄ may be substituted by —COO ⁻ and —SO ₃ ^— groups, in which case X ⁻ is unnecessary. X ^- include the halogen atoms anion (Cl ^-, Br ^-, I
^-), PF ₆ ^-, sulfate, phosphate, cyanate, thiocyanate, BF ₄ ^-, B (aryl) ₄ ^-
(Eg, tetraphenylborate, p-chlorotetraphenylborate, p-methyltetraphenylborate, etc.), phenolates, nitrophenolates, saturated or unsaturated fatty acids or aromatic carboxylates (eg,
Acetate, lactate, benzoate, salicylate, etc.), and sulfonates (eg, ethyl sulfonate, phenyl sulfonate, p-toluene sulfonate, etc.).

Next, specific examples of the quaternary ammonium salt will be shown, but it should not be construed that the invention is limited thereto. Tetramethylammonium chloride, tetramethylammonium p-toluenesulfonate, tetramethylammonium tetraphenylborate, tetraethylammonium bromide, tetraethylammonium salicylate, tetran
-Propylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium phenylsulfonate, tetraoctylammonium iodide, cetyltrimethylammonium chloride, cetyldimethylethylammonium bromide, benzyltrimethylammonium chloride, butylpyridinium bromide,
Laurylpyridinium bromide, cetylpyridinium chloride, 1-hexadecylpyridinium chloride, 2-dodecylisoquinolium bromide. The reaction solvent used in the production of the macromonomer may be any solvent that dissolves the macromonomer, and includes toluene, xylene, benzene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, N-dimethylformamide, and the like. Is particularly preferred. In addition to these, it is preferable to add a radical polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether in the macromonomerization reaction step in order to prevent polymerization during the production of the macromonomer.

The amount of the polymerization inhibitor to be charged is preferably 10 to 1000 PPM based on the total amount of the reaction solution. The amount of the epoxy compound having a polymerizable double bond such as glycidyl methacrylate is 0.9 to 0.9% based on the carboxyl group in the reaction solution.
A 3.0 equivalent is preferred. The amount of the quaternary ammonium salt such as tetrabutylammonium bromide used as the reaction catalyst is preferably 0.1 to 10.0% by weight based on the total amount of the reaction solution.

Next, the monomer represented by the general formula (III) which is a copolymer component of the graft copolymer together with the macromonomer (M) will be described. In the general formula (III), X ₁ has the same content as the linking group represented by V ₁ in the general formula (II), and preferably represents-
COO -, - OCO -, - CH 2 OCO -, - CH 2 C
OO-, -O- and a phenylene group. Q ₁ represents an aliphatic group having 1 to 22 carbon atoms. Specifically, it has the same content as the aliphatic group represented by Z ₁ in the general formula (I).

C ₁ and c ₂ may be the same or different from each other, and specifically represent the same contents as a ₁ and a _{2 in} formula (Ia) or (Ib). Preferably, one of c ₁ and c ₂ represents a hydrogen atom.

The graft copolymer may contain, in addition to the monomer represented by the general formula (III) as a copolymerization component, another monomer copolymerizable with this monomer.
For example, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, hydroxyethyl methacrylate, dialkylaminoethyl methacrylate (for example, dimethylaminoethyl methacrylate), styrene, chlorostyrene, bromostyrene, vinylnaphthalene, a complex containing a polymerizable double bond group Ring compounds (eg, vinylpyridine, vinylimidazoline, vinylthiophene, vinyldioxane, vinylpyrrolidone, etc.), unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc.), itaconic anhydride and And maleic anhydride.

The monomer other than the general formula (III) may be any monomer as long as it is a copolymerizable monomer. The content ratio is preferably 30% by weight or less.

Further, the graft copolymer of the present invention may have the following specific polar group bonded only to one end of the polymer main chain. Sokuchi, -PO ₃ H ₂ group, -SO ₂ H group, -
COOH group, -OH group, -SH _{group, - (Z 0) P (} O)
It is at least one polar group selected from an OH group (here, Z ₀ represents a —Z ₁₁ group or —OZ ₁₁ group, and Z ₁₁ represents a hydrocarbon group), a formyl group or an amino group.

In the polar group, in the — (Z ₀ ) P (O) OH group, Z ₀ represents a —Z ₁₁ group or —OZ ₁₁ group, and Z ₁₁ preferably represents a hydrocarbon group having 1 to 18 carbon atoms. Express. Is more preferably a hydrocarbon group of Z _11, an optionally substituted aliphatic group (e.g., methyl group having 1 to 8 carbon atoms, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a butenyl group, Bae Nteniru Group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group or bromobenzyl group), or an aromatic group which may be substituted (for example, phenyl group) , A tolyl group, a xylyl group, a mesityl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group or a cyanophenyl group).

In the polar group of the present invention, the amino group is -NH
_2, -NHZ ₁₂ or -NZ ₁₂ represents a (Z _13). Z ₁₂ and Z ₁₃ each independently represent a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, the hydrocarbon group of Z ₁ described above. Represents the same content as.

Still more preferably, Z ₁₁ , Z ₁₂ and Z ₁₃
Examples of the hydrocarbon group include an alkyl group having 1 to 4 carbon atoms which may be substituted, a benzyl group which may be substituted, and a phenyl group which may be substituted.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or is bonded via an arbitrary linking group. Examples of the bond connecting the graft copolymer component and the polar group include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Atoms), and any combination of heteroatom-heteroatom bond atomic groups.

Graft copolymers having a specific polar group bonded only to one end of the polymer main chain are described in Yoshiki Nakajo and Yuya Yamashita, "Dyes and Chemicals", Vol. 30, p. 232 (198).
5) Akira Ueda, Susumu Nagai, "Chemistry and Industry", 60, 57
It can be easily produced by the method described in the reviews on page (1986) and the literature cited therein.

The dispersed resin particles of the present invention comprise a monomer containing at least one of each of (a) styrene or a styrene derivative and (b) a (meth) acrylate having an alkyl group having 3 or less carbon atoms. It is formed by polymerization in a solution in the presence of a dispersion stabilizing resin. If the resin particles synthesized using these monomers are insoluble in the non-aqueous solvent, they can be used as desired dispersed resin particles.

In the dispersion resin particles, other monomers (c) copolymerizable with these monomers may be contained together with the above-mentioned monomers. Examples of the monomer (c) include a vinyl monomer having a basic nitrogen atom or an amide group.

Specific examples thereof include aminoalkyl-substituted (methacrylate) represented by the general formula (IV), quaternary salt of aminoalkyl-substituted (meth) acrylate represented by the general formula (V), N-vinylimidazole, -Vinyl-2-methylimidazole, 1-vinylpyrrole, N-
β-acryloxyethylindole, 2-vinylquinoline, 4-vinylpyridine, 5-vinyl-4-methylthiazole, 3-methyl-5-isopropenylpyrazole,
N-vinyl-2-pyrrolidone, N-vinylpiperidone,
N-vinyloxazolidone, dimethylaminostyrene,
And vinyl monomers selected from the group consisting of dialkylaminomethylstyrene, quaternary salts of dialkylaminostyrene, and (meth) acrylamide.

[0062]

Embedded image

In the general formula (IV), d ₁ and d ₂ are
They may be the same or different and each represents a hydrogen atom or a methyl group. Z ₄ and Z ₅ may be the same or different from each other, and represent the same group as Z ₁ described above. p is 1-3
Represents an integer.

[0064]

Embedded image

In the general formula (V), d ₁ , d ₂ , p,
Z ₄ and Z ₅ represent the same contents as in the general formula (IV). Z
₆ is an alkyl group having 1 to 18 carbon atoms or 7 carbon atoms
-24 represents an aralkyl group.

X represents halogen (fluorine, chlorine, bromine or iodine), acetate, BF ₄ , sulfate, p-toluenesulfonate or alkylsulfonate.

The content of the other monomer (c) copolymerizable with the above monomers (a) and (b) is 3% of the total monomer.
0 mol% or less. The weight average molecular weight of the dispersed resin particles of the present invention is 10 ³ to 10 ⁶ .

In order to produce the dispersion resin particles (latex particles) used in the present invention, the dispersion stabilizing resin, a styrene monomer and a (meth) acrylate monomer as described above are generally used. Benzoyl peroxide in a non-aqueous solvent,
The polymerization may be carried out in the presence of a polymerization initiator such as azobis (2,4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile), azobisisobutyronitrile or butyllithium.

Specifically, 1. 1. a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (a), a monomer (b) and, if necessary, a monomer (c); Monomer (a) and monomer (b) in a solution in which a dispersion stabilizing resin is dissolved
2. a method in which the monomer (c) is added dropwise together with the polymerization initiator, if necessary, or In a mixed solution containing the whole amount of the dispersion stabilizing resin and a mixture of the monomer (a), the monomer (b) and, if necessary, a part of the monomer (c), the remaining monomer and the polymerization initiator are mixed together. 3. a method of arbitrarily adding a body mixture; There is a method of arbitrarily adding a mixed solution of the dispersion stabilizing resin and the monomer together with the polymerization initiator to the non-aqueous solvent, and any method can be used.

Monomer (a) forming latex particles,
The total amount of monomer (b) and optionally monomer (c) is
The amount is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent. The amount of the soluble or colloidally dispersed resin serving as the dispersion stabilizer is 1 to 100 parts by weight, preferably 3 to 50 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of the polymerization initiator is 0.1 to 5 of the total monomers.
Molar% is appropriate. The polymerization temperature is about 20 to 180 ° C, preferably 30 to 120 ° C. The reaction time is preferably 1 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination with the non-aqueous solvent used in the reaction, or when the monomer (a) to be polymerized and granulated, When the unreacted product of the compound (b) and, if necessary, the monomer (c) remains, the solvent or the monomer is removed by heating to a boiling point or higher, or by distillation under reduced pressure. Is preferred.

The non-aqueous latex particles produced as described above exist as fine particles having a uniform particle size distribution, and at the same time, exhibit extremely stable dispersibility. In particular, they can be used repeatedly for a long time in a developing device. However, even if the dispersibility is good and the developing speed is improved, re-dispersion is easy, and it is not recognized at all that there is no adhesion stain on each part of the apparatus.

When fixing was performed by heating or the like, a strong film was formed, and excellent fixing properties were exhibited. Further, the liquid developer of the present invention has excellent dispersion stability, re-dispersibility and fixability even when the development-fixing step is speeded up and the maintenance interval is long.

In the liquid developer of the present invention, a coloring agent may be used if desired. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used.

In the case of coloring the dispersion resin itself, for example, as one of the coloring methods, there is a method of physically dispersing in the dispersion resin using a pigment or a dye. Are known. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red,
And phthalocyanine blue.

Another method of coloring is disclosed in
As described in JP-A-7-48738, there is a method of dyeing a dispersion resin with a preferable dye. Or,
As another method, there is a method of chemically bonding a dispersing resin and a dye as disclosed in JP-A-53-54029, or as described in JP-B-44-22955. As described above, there is a method in which a pigment-containing monomer is used in advance to produce a pigment-containing copolymer when producing by a polymerization granulation method.

Various charge control agents may be added to the liquid developer of the present invention, if desired, in order to enhance charge characteristics or improve image characteristics. As the charge control agent for the liquid developer used in the present invention, conventionally known charge control agents can be used. For example, naphthenic acid, octenoic acid,
Aliphatic metal salts such as oleic acid and stearic acid, and metal salts of sulfosuccinates are disclosed in JP-B-45-556, JP-A-52-37435 and JP-A-52-37049. A metal salt of an oil-soluble sulfonic acid, a metal salt of a phosphate ester disclosed in JP-B-45-9594, a metal salt of abietic acid or hydrogenated abitinic acid described in JP-B-48-25666, Alkaline benzene sulfonic acid Ca salts disclosed in JP-B-55-2620, JP-A-52-107837.
JP-A-52-38937, JP-A-57-9064
No. 3, metal salts of aromatic carboxylic acids or sulfonic acids described in JP-A-57-139753,
Nonionic surfactants such as polyoxyethylated alkylamines, lecithin, fats and oils such as linseed oil, polyvinylpyrrolidone, organic acid esters of polyhydric alcohols, phosphorus compounds described in JP-A-57-210345. Acid ester-based surfactants such as sulfonic acid resins disclosed in JP-B-56-24944 can be used.
JP-A-60-21056 and JP-A-61-5095
Amino acid derivatives described in each publication of No. 1 can also be used. Copolymers containing a maleic acid half-amide component described in JP-A-60-173558 and JP-A-60-179750 can also be used.
JP-A-54-31739 and JP-B-56-249.
44 quaternary amine polymers.

Of these, preferred are a metal salt of naphthenic acid, a metal salt of dioctylsulfosuccinic acid,
Copolymers containing the maleic acid half-amide component, lecithin, and the amino acid derivatives can be mentioned.

As these charge regulators, two or more compounds can be used in combination. The charge control agent as described above is preferably used in an amount of 0.001 to 10.0 parts by weight based on 1,000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, the electric resistance of the liquid developer from which the toner particles have been removed is 10 ⁹
If it is lower than Ωcm, it becomes difficult to obtain a high quality continuous tone image, so it is necessary to control the amount of each additive within this limit.

Various supports can be used as the conductive substrate of the electrophotographic printing original plate of the present invention. For example, plastic sheets with conductive surfaces or papers made especially solvent-impermeable and conductive, aluminum plates,
Bimetallic plate such as zinc plate, copper-aluminum plate, copper-stainless plate, chrome-copper plate, or hydrophilic such as tri-metal plate such as chrome-copper-aluminum plate, chrome-lead-iron plate, chrome-copper-stainless plate A conductive substrate having a conductive surface is used, and its thickness is preferably from 0.1 to 3 mm, particularly preferably from 0.1 to 0.5 mm. Among these substrates, an aluminum plate is preferably used. The aluminum plate used in the electrophotographic printing plate precursor of the present invention is a plate-like body such as pure aluminum containing aluminum as a main component or an aluminum alloy containing a trace amount of a different atom. , And public materials can be appropriately used. This aluminum plate can be used after graining and anodizing by a conventionally known method. Prior to the graining treatment, a degreasing treatment with a surfactant or an alkaline aqueous solution is performed, if desired, to remove the rolling grease on the surface of the aluminum plate, and the graining treatment is performed. The graining method includes a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of chemically selectively dissolving the surface. As a method for mechanically roughening the surface, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution. Further, a method combining both of them can be used as disclosed in JP-A-54-63,902.

The roughened aluminum plate is subjected to an alkali etching treatment and a neutralization treatment as required. The aluminum plate thus treated is anodized. As the electrolyte used for the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and the electrolyte and the concentration thereof are appropriately determined depending on the type of the electrolyte. Since the anodizing treatment conditions vary depending on the electrolyte used, they cannot be specified unconditionally. Generally, however, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 50 minutes. Anodized film weight is preferably 0.1 to 10 g / m ^2, but more preferably from 1 to 6 g / m ^2. The thickness of these aluminum plates is preferably 0.1 to 3 mm, and particularly preferably 0.1 to 3 mm.
1 to 0.5 mm is preferred. Furthermore, Japanese Patent Publication No. 47-512
An aluminum plate as described in No. 5 which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. Also, U.S. Pat.
Electrodeposition of silicate as described in No. 8662 is also effective. The treatment with polyvinyl sulfonic acid described in German Patent No. 162,478 is also suitable.

As the organic photoconductive compound used in the present invention, many conventionally known compounds can be used. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, N, N-bicarbazyl derivatives,
Oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, benzidine derivatives, stilbene derivatives and the like. Further, in addition to the low molecular weight photoconductive compound as described above, the following high molecular weight compounds can also be used. For example, polyvinyl carbazole and derivatives thereof, polyvinyl pyrene, polyvinyl anthracene, poly-2-vinyl-4- (4′-dimethylaminophenyl) -5-phenyloxazole, poly-3
Vinyl polymers such as -vinyl-N-ethylcarbazole,
Examples include polyacenaphthylene, polyindene, polymers such as copolymers of acenaphthylene and styrene, and condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, and ethylcarbazole-formaldehyde resin.

Various pigments can be used as the organic photoconductive compound. Examples of these include monoazo, bisazo, trisazo pigments, phthalocyanine pigments such as metal phthalocyanine or metal-free phthalocyanine, perylene pigments, indigo, thioindigo derivatives,
Examples thereof include quinacridone pigments, polycyclic quinone pigments, bisbenzimidazole pigments, squarium salt pigments, and azurenium salt pigments. These organic photoconductive compounds can be used alone or in combination of two or more.

Further, a sensitizer such as a sensitizing dye can be used in the photoconductive layer of the present invention for the purpose of improving sensitivity. As sensitizing charges, "Sensitizer", page 125, Kodansha 8198
7), "Electrophotography", Vol. 12, page 9 (1973)
“Synthetic Organic Chemistry,” Vol. Known compounds described on pages 111010 (1966) and the like can be used. For example, there are pyrylium dyes, triarylmethane dyes, cyanine dyes, styryl dyes, and the like.
As a sensitizer other than the sensitizing dye, for example, electron withdrawing compounds such as trinitrofluorenone, chloranil, and tetracyanoethylene can be used.

The binder resin used in the electrophotographic printing plate precursor of the present invention is not particularly limited as long as the non-image portion can be removed with the above-mentioned etching solution after toner development, and examples thereof include the following. Styrene / maleic anhydride copolymer, styrene / maleic anhydride monoalkyl ester copolymer, (meth) acrylic acid / (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid / (meth) Acrylic ester copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid copolymer /
(Meth) acrylate copolymer, vinyl acetate / C
2-18 vinyl ester of carboxylic acid / (meth) acrylic ester such as crotonic acid, styrene, vinyl acetate, etc. and (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, maleic anhydride monoester Copolymers with carboxylic acid-containing monomers such as alkyl esters and fumaric acid or monomers containing acid anhydride groups, (meth) acrylamide, vinylpyrrolidone, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonimide groups, etc. A copolymer containing a monomer having, phenol, o-cresol, m-cresol or p-cresol and a novolak resin obtained by condensing formaldehyde or acetaldehyde, a partially saponified vinyl acetate resin, polyvinyl acetal such as polyvinyl butyral Cal such as resin It can be exemplified a urethane resin having a phosphate.

Among these, (meth) acrylic acid esters, styrene, vinyl acetate and the like and carboxylic acid-containing monomers or copolymers such as (meth) acrylic acid are particularly excellent in electrophotographic properties, etching properties, printability and the like. And can be preferably used. More preferably, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, benzyl alcohol, phenethyl alcohol Copolymers of (meth) acrylic acid esters of aliphatic or aromatic alcohols and (meth) acrylic acid can be used.

The printing plate for electrophotographic plate making of the present invention can be obtained by applying a photoconductive layer on an aluminum substrate according to a conventional method. In producing the photoconductive layer, a method of including the components constituting the photoconductive layer in the same layer or a method of using the charge carrier generating material and the charge carrier transport material separately in different layers is known. It can also be created by the method of. The coating liquid is prepared by dissolving each component constituting the photoconductive layer in an appropriate solvent. When a component insoluble in a solvent such as a pigment is used, it is used after being dispersed to a particle size of 5 μm or less by a dispersing machine such as a ball mill, paint shaker, dyno mill, and attritor. The binder resin and other additives used in the photoconductive layer can be added during or after the dispersion of the pigment or the like. The coating solution prepared in this manner is applied onto a substrate by a known method such as spin coating, blade coating, knife coating, reverse roll coating, dip coating, rod bar coating, spray coating, and dried to form an electrophotographic printing plate precursor. Can be obtained.

Solvents for preparing the coating solution include halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform; alcohols such as methanol and ethanol; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethylene glycol monomethyl ether; Examples include glycol ethers such as methoxyethyl acetate, ethers such as tetrahydrofuran and dioxane, and esters such as ethyl acetate and butyl acetate. The photoconductive layer of the present invention is a photoconductive compound, in addition to the binding resin, for the flexibility of the photoconductive layer, for improving the coating surface state, etc.
If necessary, a plasticizer, a surfactant, a matting agent and other various additives can be added. These additives can be contained within a range that does not deteriorate the electrostatic properties and etching properties of the photoconductive layer. Further, the film thickness of the photoconductive layer of the present invention, if too thin, it is not possible to charge the surface potential required for development, and conversely, if too thick, side etching tends to occur,
A good printing plate cannot be obtained. As the thickness of the photoconductive layer,
It is 0.1 to 30 µ, preferably 0.5 to 10 µ.

The content of the binding resin and the photoconductive compound in the photoconductive layer of the present invention is such that if the content of the photoconductive compound is small, the sensitivity is reduced. It is preferably used in the range of 0.05 to 1.2 parts by weight, more preferably 0.1 to 1.0 part by weight. As the etchant for removing the photoconductive insulating layer in the non-image portion of the toner after the formation of the toner image, any solvent can be used as long as it can remove the photoconductive insulating layer, but is not particularly limited. Preferably, an alkaline solvent is used. The alkaline solvent mentioned here is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, lithium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate, ammonia and monohydrate. Examples thereof include any organic and inorganic alkaline compounds such as ethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, triisopropanolamine, diethylaminoethanol, and 2-amino-2-methylpropanol. Among them, particularly, the general formula mSiO ₂ / nM ₂ O (M: alkali metal atom, m / n
= 0.5 to 8.5) in the etching solution, it is possible to obtain better etching properties and printing characteristics. MSiO used in the present invention
₂ / nM ₂ O mole ratio m / n is 0.5 to 8.5 is preferred.

Various organic solvents can be added to the etching solution mainly composed of water, if necessary. Preferred organic solvents include methanol, ethanol, propanol, butanol, benzyl alcohol, lower alcohols and aromatic alcohols such as phenethyl alcohol and ethylene glycol, diethylene glycol, triethylene glycol, polyhydric alcohols such as polyethylene glycol, ether alcohols, Organic solvents such as ether esters, ethers, ketones, and esters, or surfactants, defoamers, and other various additives can be contained.

[0093]

EXAMPLES Examples of the production of the dispersion stabilizing resin of the present invention, examples of the production of latex particles, and examples are shown below, but the present invention is not limited thereto. In the following examples, the term “copolymer resin particles” used in the text is not used to clarify the distinction from the dispersion stabilizing resin, but the term “latex particles” is used.

The specific examples will be described below. Production example 1 of macromonomer (M-1) 100 g of methyl methacrylate, thioglycolic acid 4.
A mixed solution of 5 g and 100 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 2.0 g of azobisisobutyronitrile (abbreviation AIBN) was added, and 4
Reacted for hours. The reaction solution was cooled to room temperature, and 9.0 g of glycidyl methacrylate and 0.1 g of hydroquinone were added.
g and 3.6 g of tetrabutylammonium bromide, and reacted at 90 ° C. for 5 hours.

After cooling the reaction solution, it was reprecipitated in 2 liters of methanol. The precipitated white solid was collected by decantation, dissolved in 300 ml of tetrahydrofuran, and reprecipitated in 3 liters of methanol. The precipitated white powder was collected and dried under reduced pressure to obtain a polymer having a weight average molecular weight of 15,500 in a yield of 94.0 g. The molecular weight is G
It is a polystyrene equivalent value by the PC method.

[0096]

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Production Example 2 of Macromonomer (M-2) A mixed solution of 100 g of octadecyl methacrylate, 1.4 g of thioglycolic acid and 100 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. A. I.
B. N. Was added and reacted for 4 hours. The reaction solution was cooled to room temperature, 2.8 g of 2-hydroxyethyl methacrylate was added, and a mixed solution of 4.5 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 10 g of methylene chloride was added dropwise over 1 hour. did. 0.1 g of 4-dimethylaminopyridine and 0.1 g of t-butylhydroquinone were added, and the mixture was stirred for 4 hours.

The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated white solid was collected by decantation, and this was added to tetrahydrofuran 3
It was dissolved in 00 ml and reprecipitated again in 3 liters of methanol. The precipitated white powder was collected and dried under reduced pressure to obtain a polymer having a weight average molecular weight of 13,200 in a yield of 94.0 g. The molecular weight is a value in terms of polystyrene by the GPC method.

[0099]

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Preparation Examples of Macromonomer 3 to 17 (M-3
~ M-17) In the production examples of the macromonomers M-1 and M-2,
A methacrylate monomer (corresponding to methyl methacrylate or octadecyl methacrylate), a chain transfer agent (corresponding to thioglycolic acid), an initiator (corresponding to AIBN), and a compound having a polymerizable double bond group (2- (Equivalent to hydroxyethyl methacrylate and glycidyl methacrylate), respectively, and in the same manner as in the production example of the macromonomer M-1 or M-2, the macromonomer shown in Table-A below was produced. The weight average molecular weight of each obtained macromonomer was 1,000 to 60,000.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

[Table 7]

[0108]

[Table 8]

Production Example 1 of Dispersion Stabilizing Resin: P-1 Graft copolymerization using a styrene macromonomer (terminal group: methacryloyl group, number average molecular weight: 6000) marketed as AS-6 by Toa Gosei Chemical Co., Ltd. The coalescence was synthesized. AS-6, 50 g, a mixed solution of 50 g of 2-ethylhexyl methacrylate and 200 g of toluene were mixed in 4 parts.
The temperature is 80 ° C in a one-necked flask while stirring under a nitrogen stream.
Was heated.

As a polymerization initiator, 1 g of 1,1'-azobis (1-cyclohexanecarbonitrile) was added, and 8
Polymerization was performed at 0 ° C. for 24 hours. After the polymerization, the mixture was cooled to room temperature, 200 g of toluene was further added, and the mixture was reprecipitated in 4 liters of methanol. After filtration, the resulting white powder is dried,
Graft copolymer having a weight average molecular weight of 8.9 × 10 ⁴ [P
(2-ethylhexyl methacrylate) -g-P (styrene)] was obtained in an amount of 92 g.

Production Examples 2-8 of Dispersion Stabilizing Resins: (P-2
ＰP-8) The same reaction as in Production Example 1 except that AS-6 and 2-ethylhexyl methacrylate were replaced with the monomers and macromonomers shown in Table B below in Production Example 1 of P-1. Thus, each dispersion stabilizing resin was manufactured. The weight average molecular weight of each resin was 1.1 × 10 ^{4 to} 1.4 × 10 ⁵ .

Here, AA-6 and AA-2 are methyl methacrylate-based macromonomers having a methacryloyl terminal group and sold by Toa Gosei Chemical Co., Ltd., and have a number average molecular weight of 6,000 and 2,000, respectively.

[0113]

[Table 9]

Production Example 9 of dispersion stabilizing resin: A mixed solution of 10 g of P-9 methyl methacrylate, 90 g of macromonomer M-9 and 200 g of toluene was placed in a four-necked flask and heated to a temperature of 80 ° C. while stirring under a nitrogen stream. did.

1 g of 1,1'-azobis (1-cyclohexanecarbonitrile) was added as a polymerization initiator,
Polymerization was performed at 0 ° C. for 24 hours. After the polymerization, the mixture was cooled to room temperature, 200 g of toluene was further added, and the mixture was reprecipitated in 4 liters of methanol. After filtration, the resulting white powder is dried,
95 g of a powder having a weight average molecular weight of 6.4 × 10 ⁴ was obtained.

[0116]

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Production Examples of Dispersion Stabilizing Resins 10 to 18: (P
-10 to P-18) In Production Example 9 of P-9, the same reaction as in Production Example 9 was carried out except that methyl methacrylate and the macromonomer M-9 were replaced with the compounds shown in Table-C below, Each dispersion stabilizing resin was manufactured. Weight average molecular weight of each resin 3.0 × 10
^{4 to} 9.0 × 10 ⁴ .

[0118]

[Table 10]

Production Example of Comparative Dispersion Stabilizing Resin 1: 50 g of R-1 styrene, 2-ethylhexyl methacrylate 5
0 g and 200 g of toluene were placed in a four-necked flask in the same manner as in Production Example 1 of dispersion stabilizing resin, and nitrogen gas was passed through the flask.
For 1 hour, and then the polymerization initiator, 1,1'-azobis (1
-Cyclohexanecarbonitrile) at 80 ° C.
For 24 hours. The polymer was reprecipitated in methanol in the same manner as in Production Example 1 to obtain a polymer. The polymer obtained here is a random copolymer. The weight average molecular weight is 8.
It was 3 × 10 ⁴ .

Comparative Production Example 2: R-2 A random copolymer was prepared in the same manner as in Comparative Production Example 1, except that 10 g of methyl methacrylate was used instead of styrene, and 90 g of stearyl methacrylate was used instead of 2-ethimehexyl methacrylate. Comparative synthesis example 2 of merging
Was synthesized. The weight average molecular weight was 6.4 × 10 ⁴ .

Production Example 1 of Latex Particles: D-1 20 g of dispersion stabilizing resin P-9, 44.9 g of styrene,
45.2 g of methyl acrylate and 400 g of Isopar H
Was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. 6.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added and reacted for 24 hours. 90 minutes after the addition of the initiator, cloudiness occurred, and the temperature of the reaction solution increased by about 2 ° C. The temperature was raised to 90 ° C. and the mixture was stirred for 2 hours to distill off unreacted monomers. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having a conversion of 91% and an average particle size of 0.23 μm. In addition, the size distribution was good and uniform particles were obtained. The white dispersion also had a good dispersion state after being stored for one month.

Preparation Examples of Latex Particles 2 to 18: D-2
~ D-18 In Production Example 1 of latex particles, the dispersion stabilizing resin P
Each latex particle was produced in the same manner as in Production Example 1 except that the dispersion stabilizing resin shown in Table D below was used instead of -9. The results are shown in Table D. The conversion of each particle was 88 to 95%. In addition, the size distribution was good and uniform particles were obtained.

[0123]

[Table 11]

Production Examples 1-2 of Comparative Latex Particles: S
-1 to S-2 The dispersion stabilizing resin P in Production Example 1 of latex particles
In place of -9, comparative dispersion stabilizing resins R-1, R-2,
The same operation as in Production 1 was carried out except for using, to produce each latex particle. The results are shown in Table-E. The polymerization rate of each particle was 85 to 95%.

[0125]

[Table 12]

The latex particles produced using the comparative dispersion stabilizing resins R-1 and R-2 are the latex particles (D-1 to D-1) produced using the dispersion stabilizing resin of the present invention.
Compared with 8), the particles were too large to be used as a liquid developer because the particles were large and the dispersed state was such that a large amount of precipitates were observed.

Preparation Examples of Latex Particles 19 to 27: D-
19 to D-27 In Production Example 1 of latex particles, the same operation as in Production Example 19 was performed, except that the monomers described in Table-F below were used instead of styrene and methyl acrylate as the monomer components, Each latex particle was produced. The results are shown in Table-F. The conversion of each particle was 92 to 95%. In addition, the size distribution was good and uniform particles were obtained.

[0128]

[Table 13]

Production Example 28 of Latex Particles: D-28 The same procedure as in Production Example 1 of latex particles except that 1.7 g of dimethylaminoethyl methacrylate was used as a monomer component in addition to styrene and methyl acrylate. As in Example 1, the polymerization rate was 93% and the average particle size was 0.3.
A 26 μm white dispersion was obtained. In addition, the size distribution was good and uniform particles were obtained. The obtained dispersion had a good dispersion state after being left standing for one month.

Production Examples of Comparative Latex Particles 3 to 6: S
-3 to S-6 The same operation as in Production Example 1 was carried out except that the monomer components described in Table-G below were used instead of styrene and methyl acrylate in Production Example 1 of latex particles, and a comparative latex was used. Particles were produced. The results are shown in Table-G. Except for Comparative Example 3, the polymerization rate of each particle was 88% to 95%. The polymerization rate of the particles of Comparative Example 3 was 46%.

[0131]

[Table 14]

As can be seen from Tables F and G, the comparative latex particles (S-3 to S-6) produced by using styrene and an alkyl methacrylate having 4 or more carbon atoms as the monomer component have particle sizes. , And its particle size distribution was wide, and its dispersion state was poor such that a large amount of precipitates were observed a few weeks later, so that it could not be used as a liquid developer. On the other hand, the latex particles (D-1 to D-27) of the present invention have a small particle size, a narrow particle size distribution, uniform fine particles, and a good dispersion state. It turns out that it can be used enough for the use of.

Example 1 Preparation of Latex Particles The resin dispersion D-1 of Production Example 1 was diluted with Isopar H so that the resin content was 4 g / liter. Zirconium naphthenate as a charge modifier 1 × 10 ^- thereof charged amount was measured to prepare a ⁵ was added so as to be M positively charged liquid developer. The amount of charge was measured using a development characteristic measuring device described in JP-B 64-696 (applied voltage: 500 V, initial value of time change of voltage induced on the back surface of the applied electrode was measured). It was found that the prepared liquid developer showed a clear positive charge of 96 mv, and that the charge amount could be easily controlled by the amount of the charge control agent. Using this developer, a printing plate precursor described below was positively charged with a corona charger, image-exposed, and then subjected to reversal development according to a conventional method. 12 for printing
The image was fixed by heating at 0 ° C. for 10 minutes.

This original plate for printing was prepared by adding 40 parts of potassium silicate,
10 parts of potassium hydroxide, 20 parts of benzyl alcohol, and 20 parts of ethanol were immersed in an etching solution diluted with 900 parts of water to remove non-image portions, and sufficiently washed with water. By measuring the resolving power of the obtained printing plate, the resist property of the toner image portion was evaluated. As a result, the resolving power was 45 lines / mm, indicating a good resist property.

Preparation of Printing Master Plate The following coating solution for a photoconductive layer was coated on a grained and positively oxidized aluminum plate using a bar coater.
After drying at 0 ° C. for 10 minutes, a printing master having a coating film thickness of 3.0 μm was prepared.

(Coating Solution for Photoconductive Layer) 1. X-type metal-free phthalocyanine 20 parts 2. Copolymer of butyl methacrylate and methacrylic acid ... 140 parts (methacrylic acid 35 mol%) The following thiobarbituric acid derivatives: 1.5 parts

[0137]

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4. 1-Methoxy-2 propanol: 555 parts Methyl ethyl ketone: 555 parts The mixture having the above composition was uniformly dispersed by Dynamill (KDL) (dispersion residence time: 2 hours) to obtain a coating solution for a photoconductive layer.

Example 2 In Example 1, the latex particles shown in Table H were used instead of the white resin dispersion of Production Example 1 of latex particles, and octadecene-octadecyl hemimaleate was used as a charge control agent. A liquid developer was prepared in the same manner as in Example 1 except that the amide copolymer was added so as to be 0.01 g / 1 liter of Isopar H, and the charge amount was measured.

The charge amount of each liquid developer of the present invention is from +40 to +40.
At 160 mv, a clear positive charge was exhibited, and it was found that the charge amount could be easily adjusted by the addition amount of the charge control agent. Using the liquid developer, a printing original plate was exposed, developed, and etched in the same manner as in Example 1 to evaluate the resist properties of the printing plate. Furthermore, this printing original plate is
After the above-described processing was performed on 00 sheets, the toner adhesion stain on the developing device was evaluated. The results are shown in Table-H.

[0141]

[Table 15]

[0142]

[Table 16]

As can be seen from Table-H, the liquid developer of the present invention exhibited excellent resist properties and dispersion stability, and did not cause toner adhesion to the developing device. The image quality of the obtained printing plate was clear, and the image quality of the printed matter after printing 10,000 sheets was very clear.

[0144]

According to the present invention, it is possible to form a toner image having a strong resist property against an etching solution, to provide a clear chargeability, to easily control the charge amount, and to improve the dispersion stability. A liquid developer which was excellent and could withstand long-term use and storage was obtained. Furthermore, since there is no toner adhesion to the developing device, a liquid developer which is easy to maintain, has excellent resolving power, and has good image reproducibility was obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shu Watari 210 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji-Shin Shin Film Co., Ltd. (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 9/13

Claims (3)

(57) [Claims] 1. A resin composition comprising at least resin particles dispersed in a non-aqueous solvent having a volume resistivity of 10 ⁹ Ωcm or more, wherein the dispersed resin particles are represented by the following general formula (Ia) or (Ib). It is soluble in the non-aqueous solvent in the presence of a dispersion stabilizing resin mainly composed of a graft copolymer comprising at least one macromonomer containing a polymer component, a) styrene or a styrene derivative b) monomers acrylic acid <br/> ester le or selected from the main <br/> methacrylic acid ester having an alkyl group having 3 or less carbon atoms, each of at least one or more kinds having an alkyl group having not more than 3 carbon atoms ( Resin particles which are soluble in the non-aqueous solvent, but are insolubilized by the polymerization reaction) and are insolubilized by the polymerization reaction in the non-aqueous solvent. When Liquid developers for electrostatic photography that. Embedded image In the general formula (I), X ₀ is -COO-, -OCO-,-
(CH ₂ ) _K —OCO—, — (CH ₂ ) _K —COO—, —O
-, - CONHCOO -, - CONHCO -, - SO 2
Represents _one or more linking groups selected from-, -CO-, -CONZ _1- , and -SO ₂ NZ _1- . Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and K is 1 to 3.
Represents an integer. a ₁ and a _{2, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₂ or -COO-Z ₂ (Z ₂ via a hydrocarbon hydrogen Atom or a hydrocarbon group which may be substituted.). Q ₀ represents an aliphatic group having 1 to 22 carbon atoms. Embedded image In the general formula (Ib), Q represents —CN or a phenyl group which may be unsubstituted or have a substituent. As the substituent, a halogen atom, an alkoxy group or -COOZ ₃ (Z ₃
Represents an alkyl group, an aralkyl group, or an aryl group)
Is mentioned. a ₁ and a ₂ are a ₁ in the general formula (Ia), a ₂
Represents the same group as 2. The dispersion stabilizing resin according to the above general formula (Ia)
Or a weight average obtained by bonding a polymerizable double bond group represented by the following general formula (II) to a terminal of a main chain of a polymer containing at least one of the polymer components represented by (Ib): The non-aqueous solution containing, as a main component, a graft copolymer comprising at least one macromonomer (M) having a molecular weight of 1 × 10 ³ to 1 × 10 ⁵ and at least one monomer represented by the following general formula (III): The liquid developer for electrostatography according to claim 1, which is a resin soluble or colloidally dispersed in a solvent. Embedded image In the general formula (II), V represents -COO-, -OCO-,-
_{(CH 2) k -OCO -,} - (CH 2) k -COO -, - O
-, - CONHCOO -, - CONHCO -, - SO 2
-, -CO-, -CONZ _1- , -SO ₂ NZ ₁ -or a phenylene group (hereinafter, a phenylene group is represented by Ph, provided that Ph includes a 1,2-; 1,3-; 1,4-phenylene group ). Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and k represents an integer of 1 to 3. b ₁ and b ₂ may be the same or different from each other, and a ₁ and a ₁ in the general formula (I)
Represents the same content as ₂ . Embedded image In the general formula (III), X ₁ represents the same content as V in the general formula (II), and Q ₁ represents a hydrogen atom, an aliphatic group having 1 to 22 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. Represents a group. c ₁
And c ₂ may be the same or different from each other, and have the general formula (I
The same contents as a ₁ and a _{2 in} a) and (Ib) are shown. However, in the macromonomer represented by the general formula (Ia) and the monomer component represented by the general formula (III), at least _one of Q ₀ and Q ₁ represents an aliphatic group having 4 to 22 carbon atoms. Further, the above graft copolymer has the general formula (Ib)
In the case of comprising a macromonomer represented by the formula (III) and a monomer component represented by the general formula (III), Q ₁ has 4 to 22 carbon atoms.
Represents an aliphatic group. 3. A toner image is formed by electrophotography using a liquid developer on a printing original plate having an organic photoconductive compound provided on a conductive substrate having a hydrophilic surface, and after fixing, an alkaline aqueous etching solution. A non-image portion other than a toner image portion by etching in a printing plate manufacturing method.
Claims 1 is used as an agent.
Printing plate manufacturing method.