JP2002169342A - Liquid developer for electrostatic printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer excellent in the stability of the charged state of particles, dispersion stability, redispersibility and fixability and capable of ensuring superior printing ink sensitivity and printing resistance even in an electrophotographic plate making system in which a developing-fixing step is speeded up and a large-sized master plate is used. SOLUTION: In the liquid developer for electrostatic printing obtained by dispersing at least resin particles in a nonaqueous solvent having >=109 Ωcm electric resistance and a dielectric constant of <=3.5, the dispersed resin particles are copolymer resin particles obtained by polymerizing and granulating a solution containing a monofunctional monomer (A) soluble in the nonaqueous solvent and made insoluble by polymerization, a monofunctional monomer (B) containing an amino group, a monofunctional monomer (C) containing an acidic group selected from -PO3H2, -SO3H and -SO2H and a resin (P) for dispersion stabilization containing a specified component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid developer for electrostatography, and more particularly, to a dispersibility, a storage stability and a stability.
The present invention relates to a liquid developer for electrophotography having excellent redispersibility, image reproducibility, and fixability.

[0002]

2. Description of the Related Art A general liquid developer for electrostatography uses an organic or inorganic pigment or dye such as carbon black, nigrosine or phthalocyanine blue and a natural or synthetic resin such as alkyd resin, acrylic resin, rosin or synthetic rubber as petroleum. Dispersed in high insulating and low dielectric constant liquids such as aliphatic hydrocarbons, and furthermore, metal soap, lecithin, linseed oil,
It contains a charge control agent such as a higher fatty acid and a polymer containing vinylpyrrolidone. In such a developer, the resin is insoluble latex particles with a diameter of several nm to
Although dispersed in the form of particles of several hundred nm, in the conventional liquid developer, the soluble dispersion stabilizing resin and the charge adjusting agent are not used due to insufficient binding between the soluble dispersion stabilizing resin and the charge controlling agent and the insoluble latex particles. The agent was in a state where it easily diffused into the solution. For this reason, there has been a drawback that the soluble dispersion stabilizing resin is detached from the insoluble latex particles due to long-term storage or repeated use, and the particles settle, aggregate, accumulate, and the polarity becomes unclear. Further, since the particles once aggregated and deposited are difficult to re-disperse, the particles remain adhered to various parts of the developing device, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding pump. In order to improve such problems, insoluble dispersion resin particles comprising a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components are used. A method for improving the dispersibility, storage stability and redispersibility of particles by using the same is disclosed in JP-A-60-179751, JP-A-62-151.
No. 868 and the like. In addition, in the presence of a polymer utilizing a bifunctional monomer or a polymer utilizing a polymer reaction, an insoluble dispersion resin comprising a copolymer of a monomer insolubilized and a monomer containing a long-chain alkyl moiety Methods for improving the dispersibility, storage stability, and redispersibility of particles by using the particles are disclosed in JP-A Nos. 62-166362 and 63-66567. Further, as a dispersion stabilizing resin, instead of the conventional random copolymer, storage stability and redispersion are achieved by using a block copolymer comprising a solvated polymer part and a non-solvable polymer part. JP-A-3-12666 and JP-A-3-7266 describe methods for improving the properties.
No. 7965, No. 3-225353, No. 4-46354
And the like.

[0003]

On the other hand, in recent years, a method of printing a large number of sheets of 5,000 or more using an electrophotographic offset printing master plate has been attempted. It has become possible to print 10,000 sheets or more in plate size. or,
The operation time of the electrophotographic plate making system has been shortened, and the development-fixing process has been improved to be faster. JP-A-60-179751, JP-A-62-151868, JP-A-62-166362, JP-A-63-66567, JP-A-3-12666, JP-A-3-77965, and JP-A-3-225
Nos. 353 and 4-46354 disperse resin particles when the developing speed is increased, the dispersibility and redispersibility of the particles are reduced, and the fixing time is shortened. Or large plate size (for example, A-
In the case of using a master plate of three sizes or more, the performance was not always satisfactory in terms of printing durability.

The present invention solves the above-mentioned problems of the conventional liquid developer. The purpose of the present invention is
Provided is a liquid developer that has a rapid development-fixing process and is excellent in charge stability, dispersion stability, redispersibility, and fixability of particles even in an electrophotographic plate making system using a large-size master plate. It is. Another object of the present invention is to provide a liquid developer capable of preparing an offset printing plate having excellent printing ink oil sensitivity and printing durability by electrophotography. Another object of the present invention is to provide a liquid developer suitable for ordinary various electrostatography.

[0005]

The above object is achieved by the following constitutions.
Has been found to be achieved by: (1) Electric resistance 10⁹Ωcm or more and dielectric constant of 3.5 or less
Consists of at least resin particles dispersed in the non-aqueous solvent below
In the electrostatographic liquid developer, the dispersed resin particles
Is soluble in a non-aqueous solvent and cannot be polymerized.
At least one of the monofunctional monomers (A) to be dissolved, generally
A monomer (A) containing an amino group represented by the formula (II)
At least one of the monofunctional monomers (B) copolymerizable with
Seed, -PO _ThreeH_TwoGroup, -SO_ThreeH group and -SO_TwoFrom group H
A monomer containing at least one selected acidic group
At least the monofunctional monomer (C) copolymerizable with (A)
Also include one kind, and a component represented by the following general formula (PI).
At least the polymer is a dispersion stabilizing resin having (P)
Obtained by polymerization granulation of a solution containing one kind
Electrostatic photographic, which is a copolymer resin particles that
Liquid developer.

[0006]

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In the general formula (II), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or R ¹ and R ² bond to form a nitrogen atom. A ring may be formed together with the atom.

[0008]

Embedded image In the general formula (PI), A ¹ is -COO-, -OCO-,-
_{(CH 2) a COO -,} - (CH 2) a OCO -, - O-,
Or

[0009]

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(Where E is a direct bond, -O-, -OCO
-Or -COO-). a represents an integer of 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. p ¹ and p ² may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO—
D ^1, or represents a -COO-D ¹ via a hydrocarbon group (wherein by D ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms).

(2) The dispersed resin particles are composed of a monofunctional monomer (A), a monofunctional monomer (B), a monofunctional monomer (C) and a dispersion stabilizing resin (P). In addition, the solution is obtained by polymerizing and granulating a solution containing at least one monofunctional monomer (D) represented by the following general formula (III) copolymerizable with the monomer (A). The liquid developer for electrophotography according to the above (1), which is a copolymer resin particle.

[0012]

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[0013] In the general formula (III), U¹Is -COO-, -C
ONH-, -CON (W¹¹)-[W¹¹Is aliphatic
Group or a substituent represented by the following general formula (IIIa)
Be], -OCO -, - CONHCOO -, - CH_TwoCO
O-,-(CH_Two) sOCO- (where s is an integer of 1-4
Represents-), -O- or -C₆H_FourRepresents -COO-. c
¹And c^TwoMay be the same or different from each other,
Element atom, alkyl group, halogen atom, cyano group, -CO
O-Q¹¹Or -CH_TwoCOO-Q¹¹(Where Q¹¹Is fat
Represents an aliphatic group). W¹Is an aliphatic group having 8 or more carbon atoms
Or a total of 8 or more atoms (excluding carbon atoms and nitrogen atoms
(Excluding indirectly bonded hydrogen atoms)
It is the representative of the group. General formula (IIIa)-(X¹-Y¹)_m − (X^Two-Y^Two)_n-Z¹ In the general formula (IIIa), Z¹Is a hydrogen atom or a carbon number of 1 to 1
8 represents an aliphatic group. Y¹And Y^TwoAre the same as each other
Or different, each -O -, - S -, - CO -, - C
O_Two-, -OCO-, -SO_Two-, -N (Z¹¹)-, -C
ON (Z¹¹) -, - N (Z¹¹) CO-, -N (Z¹¹) S
O_Two-, SO_TwoN (Z¹¹)-, -NHCO _Two-Or -N
HCONH- (where Z¹¹Is the Z¹Synonymous with
is there). X¹And X^TwoMay be the same or different from each other
And a group represented by the following general formula (IIIb)
At least one selected from the group consisting of
Represents two groups. m and n are the same or different
And each represents an integer of 0 to 4. Where the sum of m and n is
It cannot be zero.

[0014]

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In the general formula (IIIb), Y ³ and Y ⁴ may be the same or different from each other, and have the same meanings as Y ¹ and Y ² , respectively, and X ⁴ is a hydrocarbon group having 1 to 18 carbon atoms. And Z ² has the same meaning as Z ¹ described above, and p represents an integer of 0 to 4.

(3) The dispersion stabilizing resin (P) has a polymerizable double bond group represented by the following general formula (PII) at one end of the polymer main chain or in a substituent of the polymer repeating component. The liquid developer for electrophotography according to the above (1) or (2), which is combined.

[0017]

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In the general formula (PII), A ² represents —COO—,
_{OCO -, - (CH 2)} b COO -, - (CH 2) b OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - CON (E 1} ) -, - SO 2 N
(E ¹ )-(E ¹ is a hydrogen atom or a carbon number of 1 to 22;
And b represents an integer of 1 to 4) or

[0019]

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(Where E ² is a direct bond, —O—, —OCO
-Or -COO-). q ¹ and q ² may be the same or different from each other, and each of p ¹ ,
It is synonymous with p ^2.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid developer for electrostatography of the present invention will be described below. As the non-aqueous solvent having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less used for the liquid developer for electrostatography of the present invention, preferably a linear or branched aliphatic hydrocarbon, alicyclic ring Examples include formula hydrocarbons, aromatic hydrocarbons, halogen-substituted products of these hydrocarbons, and silicone solvents such as silicone liquids and silicone oils.

For example, hydrocarbon solvents include pentane, isoheptane, octane, isooctane, decane,
Isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane,
Benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L (Isoper; trade name of Exxon), Shellsol 70,
Shellsol 71 (Shellsol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits) and the like.

Perfluoroalkanes represented by C _n F _{2n + 2} such as C ₇ F ₁₆ and C ₈ F ₁₈ (for example, “Fluorinert” manufactured by Sumitomo 3M) include fluorocarbon solvents as halogen-substituted hydrocarbon solvents. PF5080 "," Florinert PF5070 "(trade name), fluorinated inert liquid (" Fluorinert FC series "(trade name) manufactured by Sumitomo 3M), fluorocarbons (" Crytox GPL series manufactured by DuPont Japan Limited ") "(Trade name) etc.), CFCs (" HCF "manufactured by Daikin Industries, Ltd.)
C-141b "(trade name), _{etc.), F (CF 2) 4} CH 2 CH
_{2 I, F (CF 2)} 6 iodinated fluorocarbons such as I (Daikin Fine Chemical Laboratory, Ltd., "I-142
0 "," I-1600 "(product name) and the like.

Examples of the silicone solvent for the silicone liquid and silicone oil include dialkylpolysiloxanes (for example, hexamethyldisiloxane, tetramethyldisiloxane, octamethyltrisiloxane, hexamethyltrisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, Trifluoropropyl heptamethyltrisiloxane, diethyltetramethyldisiloxane, etc.), cyclic dialkylpolysiloxane (for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane,
Examples thereof include tetra (trifluoropropyl) tetramethylcyclotetrasiloxane and the like, methylphenyl silicone oil (for example, KF56, KF58 (trade name, manufactured by Shin-Etsu Silicon Co., Ltd.)) and the like.

In the present invention, these solvents are used alone or as a mixture. The upper limit of the electric resistance of such a non-aqueous solvent is preferably about 10 ¹⁶ Ωcm, and the lower limit of the dielectric constant is preferably about 1.80.

[0026] The most important structure in the liquid developer of the present invention
Non-aqueous dispersed resin particles (hereinafter referred to as “resin particles”)
), And sometimes referred to as “latex particles”)
The water solvent contains a specific component (formula (PI))
Monofunctional monomer in the presence of dispersion stabilizing resin (P)
At least one of (A), an amine represented by the general formula (II)
At least one of the monofunctional monomers (B)
Seed, and -PO_ThreeH_TwoGroup, -SO _ThreeH group and -SO_TwoH
One officer containing at least one acidic group selected from the group
Obtained by polymerizing and granulating at least one of the functional monomers (C)
It is.

Here, as the non-aqueous solvent, basically,
As long as it is miscible with the non-aqueous solvent of the liquid developer, it can be used.

That is, the solvent used for producing the dispersed resin particles preferably includes linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogen-substituted products thereof. Can be For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shellsol 70, Shellsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

Organic solvents which can be used in combination with these non-aqueous solvents include alcohols (for example, ethyl alcohol, propyl alcohol, butyl alcohol,
Ethylene glycol monomethyl ether, fluorinated alcohols, etc., ketones (eg, methyl ethyl ketone, acetophenone, cyclohexanone, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate) , Ethylene glycol monomethyl ether acetate, etc.), ethers (eg, dipropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg,
Chloroform, dichloroethane, methyl chloroform and the like).

It is desirable that the organic solvent used by mixing these is distilled off under heating or reduced pressure after polymerization granulation. However, even if the organic solvent is brought into the liquid developer as a latex particle dispersion, There is no problem as long as the resistance is in the range of 10 ⁹ Ωcm or more and the dielectric constant is 3.5 or less.

Usually, it is preferable to use the same solvent as the non-aqueous solvent of the liquid developer at the stage of producing the resin particle dispersion.
As described above, straight-chain or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like can be mentioned.

The monofunctional monomer (A) in the present invention comprises
Any monofunctional monomer that is soluble in a nonaqueous solvent but insolubilized by polymerization may be used. Specifically, for example, monomers can be cited represented by the following general formula (I).

[0033]

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In the general formula (I), V ¹ is -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO -, - O-,
-CONHCOO -, - CONHOCO -, - SO
^{_{2 -, - CON (Q 1}} ) -, - SO 2 N (Q 1) -., Or a phenylene group (hereinafter sometimes to be referred to as a phenylene group and "-Ph-" Incidentally, phenylene group 1,2 -, 1,
Including the 3- and 1,4-phenylene group. ). Here, Q ¹ represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
-Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxy Ethyl group, 3-methoxypropyl group, etc.).

T is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2,2-dichloroethyl, 2-bromoethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2
-Nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2- Carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-carboxyamidoethyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

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, a bromine atom), a cyano group, an alkyl group (e.g. methyl group having 1 to 3 carbon atoms, an ethyl group, a propyl group, etc.), - COO-Q ² or -CH ₂ -COO-Q ² [wherein Q ² is a hydrogen atom or 1 carbon atom which may be substituted
And 0 or less hydrocarbon groups (for example, representing an alkyl group, an alkenyl group, an aralkyl group, an aryl group, etc.).

Specific monofunctional monomers (A) include:
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid Alkyl esters or amides of a carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-hydroxy group) Ethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-
Benzenesulfonylethyl group, 2-carboxyethyl group, 4-carboxybutyl group, 3-chloropropyl group,
2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-carboxyamidoethyl group, etc.);

Styrene derivatives (for example, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Vinylbenzenecarboxylic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); acrylic acid, methacrylic acid, crotonic acid,
Unsaturated carboxylic acids such as maleic acid and itaconic acid; cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile;
Methacrylonitrile: a heterocyclic compound containing a polymerizable double bond group (specifically, for example, described in “Polymer Data Handbook -Basic Edition-” edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986)) (E.g., N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.). Two or more monomers (A) may be used in combination.

Next, the monofunctional monomer (B) which can be copolymerized with the monomer (A) used in the present invention and has an amino group represented by the general formula (II) will be described. In the monofunctional monomer (B), the polymerizable double bond and the amino group are not directly bonded.

In the formula (II), R ¹ and R ² may be the same or different, and are preferably a hydrogen atom or a carbon atom having 1 to 22 carbon atoms.
Alkyl group which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, Octadecyl, eicosyl, docosyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc., an optionally substituted alkenyl group having 4 to 18 carbon atoms (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, decenyl group, dodecenyl group, tridecenyl group,
Hexadecenyl group, octadecenyl group, linolenyl group, etc.),

An aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl, phenethyl, 3-phenylpropyl, naphthylmethyl, 2-naphthylethyl, chlorobenzyl, bromobenzyl, methyl) A benzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc., an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, A cyclopentylethyl group or the like, or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl) , Methoxyphenyl, ethoxyphenyl, butoxyphenyl, decylio Shifeniru group, chlorophenyl group,
Dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propionamidophenyl, dodecyloylamidophenyl, etc.)
Is mentioned.

R ¹ and R ² may represent an organic residue which forms a ring together with a nitrogen atom. The organic residue may further contain a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). Examples of the cyclic group formed include a morpholino group, a piperidino group, a pyridinyl group, an imidazolyl group, and a quinolinyl group. Amino group may be contained plural in the molecule of the monomer (B). Since the resin particles of the present invention contain an amino group-containing monomer (B) as a copolymerization component, the particles become detectable, the amount of charge of the particles increases, and environmental conditions (low temperature / low humidity to (High temperature / high humidity) or long-term storage can significantly reduce the change in charging characteristics, and as a result, a formed image can be obtained with stable image quality. The monomer (B)
Is preferably from 1 to 45 with respect to the total amount of the monomer (A).
% By mass, more preferably 5 to 30% by mass.

The specific examples of the monomer (B) are shown below.
The present invention is not limited to these.

[0044]

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Next, the monofunctional monomer (C) used in the present invention will be described. The monofunctional monomer (C) is-
It is a monomer copolymerizable with the monomer (A), which contains at least one acidic group selected from a PO ₃ H ₂ group, a —SO ₃ H group and a —SO ₂ H group. The monomer (C) may contain a plurality of the above acidic groups in the molecule. The monomer (C) replenishes the effect of the monomer (B), further improves the charge characteristics of the resin particles, and acts to always provide a stable and excellent image. Monomer (C) is monomer (B) / monomer (C)
At a molar ratio of 0.2 to 2.5, more preferably 0.5 to 2.0.

[0046] Hereinafter, specific examples of the monomer (C),
The present invention is not limited thereto.

[0047]

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[0048]

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Next, in the present invention, a monomer having a specific substituent represented by the above general formula (III), which is preferably used as a copolymer component of the resin particles and is copolymerizable with the monomer (A). The functional monomer (D) will be described.

First, the case where W ¹ in formula (III) represents an aliphatic group having 8 or more carbon atoms will be described in detail.
W ¹ preferably represents an optionally substituted alkyl group having 10 or more carbon atoms or an optionally substituted alkenyl group having 10 or more carbon atoms.

U ¹ is preferably -COO-, -CONH
-, -CON (W ¹¹ )-wherein W ¹¹ is preferably an aliphatic group having 1 to 32 carbon atoms (as the aliphatic group, for example, an alkyl group, an alkenyl group, an aralkyl group, or the like) or the general formula ( IIIa)), —O
CO -, - represents a CH ₂ OCO- or -O-.

C ¹ and c ² may be the same or different and are preferably a hydrogen atom, a fluorine atom, a chlorine atom,
A bromine atom, a cyano group, a methyl group, -COO-Q ¹¹ or an -CH ₂ COO-Q ¹¹ (where Q ¹¹ is preferably an alkyl group having 32 or less carbon atoms, an alkenyl group, an aralkyl group or cycloalkyl group ).

More preferably, in the formula (III), U ¹ is -C
OO -, - CONH- or -CON (W ¹¹⁾ - represents, c ¹ and c ^2, which may be the same or different,
It represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or a methyl group, W ¹¹ are as defined above.

In the above monomer (D) represented by the general formula (III), when W ¹ represents an aliphatic group having 8 or more carbon atoms, specific examples thereof include: 32 aliphatic groups (the aliphatic group may contain a substituent such as a halogen atom, a hydroxyl group, an amino group, or an alkoxy group;
Or an oxygen atom, a sulfur atom, a hetero atom such as a nitrogen atom, and the like, and a carbon atom-carbon atom bond in its main chain may be interposed).
Esters of unsaturated carboxylic acids such as chloroacrylic acid, α-cyanoacrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid (for example, aliphatic groups such as decyl, dodecyl, tridecyl, tetradecyl,
Hexadecyl group, octadecyl group, docosyl group, dodecenyl group, hexadecenyl group, oleyl group, linoleyl group, docosenyl group, etc.); amides of the above-mentioned unsaturated carboxylic acids (the aliphatic groups are the same as those shown for the esters) Vinyl esters or allyl esters of higher fatty acids (higher fatty acids include, for example, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc.); or total carbon Vinyl ethers in which several 10 to 32 aliphatic groups are bonded to an oxygen atom (the aliphatic groups include the same aliphatic groups as those exemplified for the unsaturated carboxylic esters described above) and the like can be mentioned.

In the monomer (D) represented by the general formula (III), W ¹ has a total of 8 or more atoms (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom).
The case of representing the substituent represented by Ia) will be described in detail.

X ¹ and X ² represent at least one group selected from the group represented by the general formula (IIIb) and the hydrocarbon group having 1 to 18 carbon atoms (provided that two or more groups Represents a combination of two or more groups selected from the group of the formula (IIIb) and a hydrocarbon group). More specifically, these include -C (R ¹¹ ) (R ¹² )-[R ¹¹ , R
¹² each represents a hydrogen atom, an alkyl group, a halogen atom, etc.], - (CH = CH) -, cyclohexylene group [hereinafter, a cyclohexylene group - expressed in, "-C ₆ H _10"
“—C ₆ H ₁₀ —” is a 1,2-cyclohexylene group,
3-cyclohexylene group and 1,4-cyclohexylene group], and any combination of atomic groups such as the group represented by the general formula (IIIb).

When W ¹ represents a substituent represented by the general formula (IIIa) having a total number of atoms of 8 or more, the bonding group [-U
^{1 - (X 1 -Y 1)} m - in _{^{(X 2 -Y 2) n -Z}} 1 ], U ¹
To Z ¹ (that is, U ¹ , X ¹ , Y ¹ , X ² , Y ^2, and Z ¹ ) is a “linking main chain” in which the total number of atoms constituting the linking main chain is 8 or more. Preferably, there is.

Here, the number of atoms constituting the “linking main chain” means, for example, when U ¹ represents —COO— or —CONH—, an oxo group (＝ O group) or a hydrogen atom The carbon atoms, ether-type oxygen atoms, and nitrogen atoms that constitute the connecting main chain are included in the number of atoms. Therefore, -COO- and -CONH- have 2 atoms.
Counted as At the same time, if Z ¹ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included. Therefore, in this case, it is counted as 9 atoms.

Note that U ¹ represents -CON (W ¹¹ )-,
And substituents W ¹¹ are represented by the general formula (IIIa), i.e., when it represents a ^{[- - (X 1 -Y 1)} m (X 2 -Y 2) n -Z 1 ], in W ^{1 1} The composed connecting main chain is also included in the above “connecting main chain”. Further X ^1, X ² in the case of having a group represented by the general formula (IIIb) ^{[-Y 3 - (X 4 -Y 4} ) p -Z 2 ]
Groups are also included in the aforementioned “linking backbone”.

In the above monomer (D) represented by the general formula (III), when W ¹ represents a substituent represented by the general formula (IIIa), specific examples include the following compounds. Examples include, but are not limited to:

The following formulas (D-1) to (D-19)
Here, each symbol represents the following contents. r ₁ : —H, —CH ₃ , —Cl or —CN, r ₂ : —H or —CH ₃ l: an integer of 2 to 10, p: an integer of 2 to 6, q: an integer of 2 to 4, m : An integer of 1 to 12, n: an integer of 4 to 18,

[0062]

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[0063]

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[0064]

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By using the monomer (D), the dispersibility, stability and redispersibility of the dispersed resin particles are further improved. This is because the copolymerization component corresponding to the monomer (D) has a high affinity for the dispersion medium and is oriented on the particle surface portion, whereby the affinity for the dispersion medium of the particle itself with the dispersion medium is obtained. This is presumed to increase the properties and suppress the aggregation and precipitation of the particles. When the monomer (D) is used, the amount used is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass of all the monomers.
It is. Next, the dispersion stabilizing resin (P) used in the present invention will be described.

In the present invention, the dispersion stabilizing resin (P) used to make a non-aqueous solvent-insoluble polymer produced by polymerizing a monomer in a non-aqueous solvent into a stable resin dispersion is:
It is a polymer soluble in a non-aqueous solvent containing at least one kind of the repeating unit represented by the general formula (PI). The component represented by the general formula (PI) is a component that becomes soluble in a dispersion medium used in a liquid developer.

In the formula (PI), A ¹ is preferably -CO
O -, - OCO -, - CH 2 COO -, - CH 2 OCO-
Or -O-, more preferably -COO-, -OC
O -, - represents a CH ₂ COO-.

L is preferably an optionally substituted alkyl or alkenyl group having 8 to 32 carbon atoms. Examples of the substituent include a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom, ^{etc.), - O-D 2,} -COO-D 2,
—OCO—D ² (where D ² represents an alkyl group having 6 to 22 carbon atoms, and examples thereof include a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group). . More preferably, L represents an alkyl or alkenyl group having 10 to 22 carbon atoms. For example, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosyl, eicosyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,
And a docosenyl group.

P¹And p^TwoAre the same but different
And preferably a hydrogen atom, a halogen atom (eg,
If, fluorine atom, chlorine atom, bromine atom), a cyano group,
Alkyl group having 1 to 3 carbon atoms, -COO-D^ThreeOr -C
H_TwoCOO-D^Three(Where D^ThreeIs an aliphatic having 1 to 22 carbon atoms
It represents a group, for example, a methyl group, an ethyl group, a propyl group,
Butyl, hexyl, octyl, decyl, dodecyl
Group, tridecyl group, tetradecyl group, hexadecyl
Group, octadecyl group, docosyl group, pentenyl group, hexyl
Cenyl, heptenyl, octenyl, decenyl,
Dodecenyl, tetradecenyl, hexadecenyl group,
Octadecenyl group and the like, these aliphatic groups wherein
L may have the same substituents as those represented by L)
You. More preferably, p¹And p^TwoAre the hydrogen sources
And an alkyl group having 1 to 3 carbon atoms (for example, a methyl group,
Tyl group, propyl group, etc.), -COO-D^FourOr -CH_Two
COO-D ^Four(Where D^FourIs alkyl having 1 to 12 carbons
Group or alkenyl group, for example, methyl group, ethyl group
Group, propyl group, butyl group, hexyl group, octyl
Group, decyl group, dodecyl group, pentenyl group, hexenyl
Group, heptenyl group, octenyl group, decenyl group, etc.
These alkyl groups and alkenyl tombs are represented by L above.
Which may have the same substituents as described above).

The dispersion stabilizing resin (P) of the present invention is preferably a monomer corresponding to the repeating unit represented by the above general formula (PI) and another monomer copolymerizable with the monomer. It is a copolymer containing a copolymer component obtained by copolymerizing a copolymer.

Other monomers that can be copolymerized may be any as long as they contain a polymerizable double bond group. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; Ester derivatives or amide derivatives of unsaturated carboxylic acids having a number of 6 or less; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. . More specifically, the same compounds as those of the monomer (A) to be insolubilized as described above can be used.

In the polymer component of the dispersion stabilizing resin (P), the content of the repeating unit represented by the general formula (PI) is at least 50% by mass, preferably at least 60% by mass, based on all the components of the polymer. , More preferably 70% by mass or more. In addition, in the dispersion stabilizing resin (P), another monomer that is copolymerizable with the copolymerization component represented by the general formula (PI) that is soluble in the dispersion medium used for the liquid developer (for example, insoluble in the dispersion medium). The polymerization component corresponding to the monomer (A)) may be any of random copolymerization and block copolymerization. Preferably, it is a block copolymer. The dispersion stabilizing resin (P) of the present invention does not have a crosslinked structure between polymer main chains.

Further, in a preferred embodiment of the dispersion stabilizing resin (P) of the present invention, the above-mentioned general formula (PI) is contained in one terminal of the polymer main chain or in a substituent of a repeating component constituting the polymer.
The polymerizable double bond group represented by I) is bonded (hereinafter sometimes referred to as a dispersion stabilizing resin (PG)), and this polymerizable double bond group constitutes the dispersed resin particles. Any functional group copolymerized with the monomer (A) may be used.

In the formula (PII), A ² represents —COO—, —OC
_{O -, - (CH 2)} b COO -, - (CH 2) b OCO -, -
_{O -, - SO 2 -,} - CONHCOO -, - CONHC
ONH-, -CONE ^1- , -SO ₂ NE ^1- (where E ¹
Represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms,
b represents an integer of 1 to 4) or

[0075]

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(Where E ² is a direct bond, —O—, —OCO
-Or -COO-).

Q ¹ and q ² may be the same or different from each other, and have the same meanings as p ¹ and p ² in the formula (PI), respectively. q
It is preferable that ^{one of 1} and q ² is a hydrogen atom.

In A ² , -CONE ^1- , -S
E ¹ in the O ₂ NE ¹ — linking group is preferably a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group. Represents

Examples of the resin (PG) having a polymerizable double bond group bonded to one terminal of the polymer main chain include those represented by the following general formula (Pa).

[0080]

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In the general formula (Pa), except for G, the formula (PI)
And the same as each symbol in (PII). G represents a bond directly linked to one end of the polymer main chain, or a bonding group via an arbitrary linking group.

As the bonding group, a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and the like), a hetero atom It is composed of any combination of atomic groups of atom-heteroatom bonds. For example,

[0083]

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Z ¹ and z ² each represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ). z ³ and z ⁴ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a benzyl group, a phenethyl group, a phenyl group, tolyl) or -Oz ⁵ (z ⁵ represents the same meaning as the hydrocarbon group) in the z ^3), and the like.

With respect to the polymerizable double bond group represented by the general formula (PII) bonded to one end of the polymer main chain as described above,
The details are shown below. However, in the following specific examples,
A represents -H, a -CH ₃ or -CH ₂ COOCH _3,
B represents -H or -CH _3. Further, n represents an integer of 2 to 10, m represents 2 or 3, t represents 1, 2 or 3, p represents an integer of 1 to 4, and q represents 1 or 2.

[0086]

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[0087]

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[0088]

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[0089]

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The dispersion stabilizing resin (PG) of the present invention having a polymerizable double bond group bonded to one end of the polymer main chain can be prepared by known radical polymerization (for example, iniferter method), anionic polymerization or cationic polymerization. The terminal of the living polymer obtained by polymerization is reacted with a reagent containing various double bond groups, or a specific reactive group (for example, -OH, -COOH, -SO
_{3 H, -NH 2, -SH,} -PO 3 H 2, -NCO, -NC
S,

[0091]

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[0092] -COCl, after reacting the reagent containing -SO ₂ Cl, etc.), the method according to the method (ion polymerization method for introducing a polymerizable double bond group by a polymer reaction), or the specific in the molecule After radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group of
The polymer can be easily produced by a synthesis method such as a method of introducing a polymerizable double bond group by conducting a polymer reaction using a specific reactive group bonded only to one end of the polymer main chain.

[0093] More specifically, Takayuki Otsu, polymer, 33 (No.
3), 222 (1984), P.Dreyfuss & RPQuirk, Encycl. P
olym. Sci. Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Chemistry and Industry", 60 , 57 (1986), PFRempp & E.Frant
a, Advances in Polymer Science, 58 , 1 (1984), Koichi Ito "Polymer Processing", 35 , 262 (1986), V. Percec, Ap
A polymerizable double bond group can be introduced according to a method described in a review such as plied Polymer Science, 285 , 97 (1984) and the references cited therein.

[0094] Further, specifically, i) at least one of the general formula (monomers corresponding to the repeating unit represented by PI)
A method in which a mixture of a species and a chain transfer agent containing the above specific reactive group in a molecule is polymerized with a polymerization initiator (for example, an azobis compound, a peroxide or the like); ii) without using the above chain transfer agent the method for polymerization using a polymerization initiator containing the specific reactive group in the molecule or iii) any compound containing the above specific reactive group in a molecule is also a chain transfer agent and a polymerization initiator, To synthesize a polymer in which a specific reactive group is bonded only to one end of the polymer main chain, and then use the specific reactive group to polymerize the polymerizable double There is a method for introducing a bond.

As the chain transfer agent to be used, for example, a mercapto compound containing a specific reactive group or a substituent capable of being induced to a specific reactive group {eg, thioglycolic acid,
Thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine,
2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N-
(2-Mercaptoethyl) amino] propionic acid, N-
(3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 1-mercapto-2-propanol, 3
-Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol or the like, or containing a specific reactive group or a substituent capable of being induced to a specific reactive group (E.g., iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Examples of the polymerization initiator containing a specific reactive group or a substituent which can be derived to the specific reactive group include:
For example, azobis compounds {eg, 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric chloride), 2,2′-azobis (2-cyanopropanol), , 2'-Azobis (2-cyanopentanol), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2-
Yl) propane], 2,2'-azobis {2-methyl -
N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide {, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2 , 2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis (2-amidinopropane)}, a thiocarbamate compound {eg, benzyl N
- methyl -N- hydroxyethyl dithiocarbamate,
2-carboxyethyl N, N-diethyldithiocarbamate, 3-hydroxypropyl N, N-dimethyldithiocarbamate} and the like.

The amount of the chain transfer agent or the polymerization initiator to be used is 0.05 to 100 parts by mass of all monomers.
It is 10 parts by mass, preferably 0.1 to 5 parts by mass.

Specific examples of the resin (PG) having a polymerizable double bond group in the substituent of the polymerization component in the polymer include those represented by the following general formula (Pb). .

[0099]

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In the formula (Pb), p¹, P^Two, A¹, L, q¹,
q^TwoIt has the same meaning as defined above. x component and y component are resin
Two or more kinds may be contained in (P). t¹, T^TwoIs each
People, the p ¹, P^TwoIs synonymous with A^ThreeAnd A^Four, Each
A in formula (PII)^TwoIs synonymous with G⁰Is a bonding group A
^ThreeAnd bonding group A^FourAnd at least one carbon
Atom, oxygen atom, sulfur atom, silicon atom or nitrogen atom
Represents the following.

Examples of the bonding group include a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom, It is composed of any combination of atom groups, heteroatom bonds, and heterocyclic groups. For example, as the above atomic group,

[0102]

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[R ^{1 to} r ⁴ each represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group) shows etc.) and the like. r ^{5 to} r ⁷ each represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.). r ⁸ ~r ⁹ each represents a hydrogen atom, a hydrocarbon 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 benzyl group, a phenethyl group, a phenyl group, tolyl) or -Or ¹⁰ (r ¹⁰ represents a hydrocarbon representative of the group and is synonymous)] and the like in the r ^8.

The heterocyclic group includes heteroatoms containing a heteroatom such as an oxygen atom, a sulfur atom and a nitrogen atom (for example, a thiophene ring, a pyridine ring, a pyran ring, an imidazole ring, a benzimidazole ring, a furan ring and a piperidine ring). ,
Pyrazine ring, pyrrole ring, piperazine ring, etc.).

In the y component in the general formula (Pb), the connecting main chain composed of the bonding group: [-A ⁴ -G ⁰ -A ^3- ] is
Those having a total number of atoms of 8 or more are preferred.
Here, the number of atoms in the connecting main chain means that, for example, A4 is -CO
When O— and —CONH— are represented, the oxo group (＝ O group) and the hydrogen atom are not included in the number of atoms, and the carbon atom, the ether-type oxygen atom, and the nitrogen atom constituting the connecting main chain are included in the number of atoms. It is. Therefore, -COO- and -CONH
-Is counted as 2 atoms.

Hereinafter, specific examples of the repeating unit (y component) containing a polymerizable double bond group will be shown.
It is not limited to these. In the following formula, each symbol represents the following contents.

[0107]

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[0108]

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[0109]

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The dispersion stabilizing resin (PG) containing a polymerizable double bond group in the substituent of the polymerization component can be easily synthesized by a conventionally known synthesis method. Namely, in the resin, as a method for introducing a polymerizable component (y component) containing a polymerizable double bond group, pre-specific reactive group (e.g. _{-OH, -COOH, -SO 3 H,} -NH 2 , -S
_{H, -PO 3 H 2, -NCO} , -NCS, -COCl, -
A monomer containing a polymerizable double bond group is reacted with a monomer containing a polymerizable double bond group after polymerization of a monomer containing the compound (SO ₂ Cl, epoxy group, etc.) with a monomer corresponding to the component x in the general formula (Pb). Then, a method of introducing a polymerizable double bond group by a polymer reaction is exemplified.

Specifically, the polymerizable double-bonding group may be prepared according to the method described in the review described in the resin (PG) containing a polymerizable double-bonding group at one end of the polymer main chain and the method described in the literature cited therein. Can be introduced.

As another method, bifunctional monomers having different polymerization reactivity in a radical polymerization reaction are used.
A method described in JP-A-60-185962, in which a polymerization reaction is carried out with a monomer corresponding to the x component to synthesize a copolymer represented by the general formula (Pb) without causing a gelling reaction, is mentioned.

In the resin represented by the general formula (Pb),
The proportions of the x component and the y component are from 90/10 to 99/1 by mass, preferably from 92/8 to 98/2 by mass. Within this range, there is no danger of gelling the reaction mixture or increasing the particle size of the resulting resin particles during the polymerization granulation reaction.

Further, the dispersion stabilizing resin (PG) used in the present invention may contain other repeating units as copolymer components together with each repeating unit of the general formulas (Pa) and (Pb). As other copolymerizable components, the general formula (P
Any compound may be used as long as it is composed of a monomer copolymerizable with a monomer corresponding to each of the repeating units a) and (Pb). However, in order to obtain good dispersion stability of the dispersed resin particles, it is preferable to use the dispersed resin particles in an amount not exceeding 20 parts by mass in 100 parts by mass of all polymer components.

[0115] The weight average molecular weight of the dispersion stabilizing resin (P) of the present invention (Mw) ^{of, 2 × 10 4 ~1 × 10} 6 is preferred,
More preferably, it is 3 × 10 ⁴ to 2 × 10 ⁵ .

As described above, it is preferable to use a dispersion stabilizing resin (P) comprising a block copolymer of a soluble component and an insoluble component represented by the general formula (PI). In this case, the block portion of the insoluble component of the dispersion stabilizing resin (P) is sufficiently adsorbed on the insoluble resin particles. Further, it is preferable to use a dispersion stabilizing resin (PG) containing a polymerizable double bond group. In this case, the resin (PG) chemically bonds to the insoluble resin particles. It is considered that this enhances the affinity of the soluble component of the dispersion stabilizing resin (P), which is sufficiently adsorbed or chemically bonded to the dispersed resin particles, to the dispersion medium, thereby producing a so-called steric repulsion effect, and further improving the dispersibility.

To produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin (P) as described above,
Monomer (A), monomer (B) and monomer (C), and if necessary, monomer (D) in a non-aqueous solvent with benzoyl peroxide;
Heat polymerization may be performed in the presence of a polymerization initiator such as azobisisobutyronitrile and butyllithium. In particular,
Dispersion stabilizing resin (P), monomer (A), monomer (B)
A method of adding a polymerization initiator to a mixed solution of a monomer (C) and a monomer (D), if necessary, a method of dispersing a monomer (A) in a solution in which a dispersion stabilizing resin (P) is dissolved. , Monomer (B)
And a method of dropping the monomer (C) and, if necessary, the monomer (D) together with the polymerization initiator, or a method of dissolving the dispersion-stabilizing resin (P) in the solution of the monomer (A). ), A mixture of the monomer (B) and a half of the monomer (A), a monomer (C) and a polymerization initiator, and if necessary, a mixture of the monomer (D), respectively. It can be manufactured by any of these methods. The monomer (A), monomer (B), monomer (C) and, if necessary, monomer (D) used in the present invention are copolymerized by a polymerization reaction and are insoluble in a non-aqueous solvent. Of resin.

The total amount of the monomer (A), the monomer (B) and the monomer (C) and, if necessary, the monomer (D) is preferably based on 100 parts by mass of the non-aqueous solvent. It is about 10 to 100 parts by mass, more preferably 10 to 80 parts by mass.
The dispersion stabilizing resin (P) is composed of all the monomers 1 used in the above.
The amount is preferably about 3 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 00 parts by mass. The amount of the polymerization initiator is suitably about 0.1 to 10% by mass of all the monomers. Further, the polymerization temperature is preferably about 40 to 180 ° C.,
More preferably, it is 50 to 120 ° C. Reaction time is 3 ~
About 15 hours are preferable.

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 unreacted products of monomers to be polymerized and granulated may be used. If it remains, it is preferable to remove it by heating it to a temperature higher than the boiling point of the polar solvent or monomer or distilling it off under reduced pressure.

The non-aqueous dispersed resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution. Its average particle size is preferably 0.15
To 1.5 μm, more preferably 0.2 to 1.0 μm. This particle size is CAPA-500 (HORIBA, Ltd.)
Manufactured). Further, the dispersed resin particles of the present invention exhibit positive charge due to the action of the polymerization components corresponding to the monomers (B) and (C).

The weight average molecular weight (M
w) (value in terms of polystyrene by GPC method) is preferably 5 × 10 ³ to 1 × 10 ⁶ , more preferably 8 × 1
0 ^{3 to} 5 × 10 ⁵ . In addition, the thermophysical properties are such that the glass transition point is 0 ° C to 80 ° C or the softening point is 35 ° C to 12 ° C.
0 ° C. is preferred, and more preferably the glass transition point is 10 ° C.
770 ° C. or a softening point of 38 ° C. to 90 ° C.

The liquid developer of the present invention is excellent in dispersibility, storage stability, stability and re-dispersibility of dispersed resin particles, has good fixability after image formation, and maintains sufficient image strength during printing. Shows high printing durability. That is, it shows very stable dispersibility,
In particular, in a developing device, even if used repeatedly for a long time, the dispersibility is good and the re-dispersion is easy, and it is not recognized at all that the toner adheres to each part of the device and generates stains.

Furthermore, because of good fixability, a solid film is easily formed on the surface of the lithographic printing original plate when fixing by rapid processing such as heating after image formation. Thereby, even in offset printing, printing of a large number of sheets (high printing durability) becomes possible. The liquid developer of the present invention resulting in an effect as described above is made possible by the non-aqueous latex provided by this invention.

In the liquid developer of the present invention, a charge adjusting agent (C
D) is used. Charge control agents are well known in the technical field of liquid developers for electrostatography. Specifically, "Recent developments and developments of electrophotographic development systems and toner materials" 139-1
48 pages, Electrographic Society of Japan, "Basics and Application of Electrophotographic Technology" 49
Compounds described on pages 7 to 505 (Corona Co., 1988), Yuji Harasaki “Electrophotography” 16 (N0.2), page 44 (1977), and the like can be used. Preferred charge regulators include:
Examples include metal soaps, organic phosphoric acids or salts thereof, organic sulfonic acids or salts thereof, and amphoteric surface active compounds.

For example, metal soaps include fatty acids having 6 to 24 carbon atoms (for example, 2-ethylhexynic acid,
Ethyl caproic acid, lauric acid, palmitic acid, elaidic acid, linoleic acid, ricinoleic acid, oleic acid, stearic acid, enanthic acid, naphthenic acid, ethylenediaminetetraacetic acid, etc.), resin acid, dialkyl succinic acid, alkyl phthalic acid, alkyl salicylic acid Metal salts such as Na, K, Li, B, Al, Ti, Ca,
Pb, Mn, Co, Zn, Mg, Ce, Ag, Cd, Z
r, Cu, Fe, Ba, etc.) (eg, US Pat.
No. 11,936, No. 3,900, 412, Shoko 49
-27707, JP-A-51-37651, and 52-
No. 38937, No. 52-107837, No. 53-12
3138).

Examples of the organic phosphoric acid or salts thereof include mono-, di- or trialkyl phosphoric acid or dialkyl dithiophosphoric acid comprising an alkyl group having 3 to 18 carbon atoms (for example, British Patent Nos. 1,411,739 and 1,1). 276,3
63, etc.). Examples of the organic sulfonic acids and salts thereof include long-chain aliphatic sulfonic acids, long-chain alkylbenzenesulfonic acids, dialkylsulfosuccinic acids, and metal salts thereof (for example, Japanese Patent Publication No. 47-3712).
No. 8, JP-A-53-123138 and JP-A-51-4743.
7, No. 50-79640, No. 53-30340, etc.).

As the amphoteric surfactant, lecithin,
Phospholipids such as cephalin (for example, JP-B-51-470
No. 46 etc.), β containing an alkyl group having 8 or more carbon atoms
-Alanines (for example, described in JP-A Nos. 50-17642 and 49-17741), metal complexes of β-diketones (for example, described in JP-B-49-27707),
A copolymer containing a maleic acid half-amide component (for example,
Kokoku 6-19596 No., same 6-19595 JP, the 6-
According to 23865 No., etc.).

The charge control agents can be used alone or in combination of two or more. Charge control agent is 0.001 relative to 1000 parts by weight non-aqueous solvent in the carrier liquid
It is preferable to use about 1.0 part by mass.

As described above, the dispersed resin particles of the present invention themselves have a positive charge property, but a sufficient charge amount can be maintained by further using a charge control agent. Further, it is possible to maintain a state in which the ratio of the amount of charge of the dispersed particles in the liquid developer (charge fraction of the particles) is extremely high. The charge fraction of the particles will be described in detail in Examples.

As a result, in the liquid developer of the present invention, the amount of charge of the dispersed particles is selectively increased, and the particles are quickly charged with electricity corresponding to the electrostatic latent image on the electrostatic recording medium. It migrates and adheres to form a high-definition image. Incidentally, even if the overall charge amount of the liquid developer is high, if the charge amount of the carrier liquid is large, those soluble ionic components adhere to the electrostatic latent image, and the adhesion of charged particles that should originally adhere is inhibited. In addition, the adhesion of particles is reduced due to the decrease in the charge of the latent image, and as a result, image defects such as insufficient reproduction of minute dots, bleeding of an edge portion of an image portion, and flowing are caused. In addition, the liquid developer of the present invention is almost free from the influence of moisture due to a change in humidity due to the fact that the charge is held firmly and selectively to the particles, and the plate making environment changes from low humidity to high humidity. However, it is possible to stably form images with good reproducibility.
Further, after the liquid developer of the present invention is stored for a long time, or after storage under high temperature / high humidity (for example, 35 ° C./80% RH),
Even when plate making is performed, the performance is completely the same as when a fresh product immediately after the production of the liquid developer is used. This is because the charge characteristics of the liquid developer of the present invention, in particular, the chargeability of positively charged particles is stably maintained, and sufficient dispersibility is maintained without causing aggregation or precipitation between dispersed particles. It is thought that.

Various additives may be further added to the liquid developer of the present invention, if desired. The upper limit of the total amount of these additives is regulated by the electric resistance of the liquid developer. That is, the electric resistance of the ink from which the dispersed particles have been removed is 10%.
^If it is lower than ⁹ Ωcm, it becomes difficult to obtain a high quality continuous tone image. Therefore, it is desirable to control the amount of each additive within this limit.

The liquid developer of the present invention preferably contains a coloring material as a coloring component together with the above-described dispersed resin particles, for example, for plate inspection of a plate after plate making. As the coloring material, any pigments and dyes conventionally used in oil-based ink compositions or liquid developers for electrostatography can be used.

As the pigment, any of inorganic pigments and organic pigments which are generally used in the technical field of printing can be used. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, pyridian, cobalt green, ultramarine blue, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment , Quinacridone-based pigments, isoindolinone-based pigments, dioxazine-based pigments, threne-based pigments, perylene-based pigments, perinone-based pigments, thioindigo-based pigments, quinophthalone-based pigments, metal complex pigments, and other known pigments. It can be used without.

As the dyes, azo dyes, metal complex dyes,
Naphthol dye, anthraquinone dye, indigo dye,
Oil-soluble dyes such as carbonium dyes, quinone imine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes and metal phthalocyanine dyes are preferred.

These pigments and dyes may be used alone or in an appropriate combination, but may be contained in the range of 0.05 to 5% by mass based on the whole liquid developer. Is desirable.

These coloring materials may be dispersed in a non-aqueous solvent as dispersed particles themselves in addition to the dispersed resin particles, or may be contained in the dispersed resin particles. One of the methods for adding the dye is to dye the dispersed resin material with an appropriate dye as described in JP-A-57-48738. Another method is disclosed in JP-A-53-54.
As disclosed in Japanese Patent No. 029 or the like, there is a method of chemically bonding a dispersing resin and a dye. In addition, Tokiko Sho 44-2
As described in No. 2955 and the like, there is a method of producing a dye-containing copolymer by using a dye-containing monomer in advance when producing by a polymerization granulation method. The preparation of a printing plate by electrophotography using the liquid developer for electrostatography of the present invention can be performed by a conventional method. Further, the liquid developer of the present invention,
It can also be used for ordinary electrostatographic copying.

[0137]

EXAMPLES The present invention will be described in more detail with reference to Production Examples and Examples of resin particles used in the present invention, but the present invention is not limited to these.

Production Example 1 of Resin Particles (L)
-1) A mixture of 20 g of a dispersion stabilizing resin (P-1) having the following structure and 385 g of Isopar G was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. Methyl methacrylate 15
g, 29.4 g of methyl acrylate, 6 g of 2- (N, N-dimethylamino) ethyl methacrylate and 2,2-
Azobisisovaleronitrile (abbreviation: AIV
N. ) 1.5 g of the mixture and methyl methacrylate 15
g, 31.6 g of methyl acrylate, 3 g of 2-phosphonoethyl methacrylate, and 10 g of ethanol were simultaneously added dropwise for 1 hour, and the mixture was stirred for 2 hours.

Next, A.I. I. V. N. Was added, and the mixture was heated to a temperature of 75 ° C. and stirred for 3 hours. Further, 2,2′-azobisisobutyronitrile (abbreviation: AIBN) was added.
Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Then, the temperature was raised to 100 ° C., and the degree of decompression was 200 mmH
Then, the mixture was stirred for 2 hours under g and ethanol and unreacted monomers were distilled off. After cooling, pass through a 200 mesh nylon cloth,
The resulting white dispersion had a conversion of 99% and an average particle size of 0.25.
μm latex. Particle size is CAPA-500
(Manufactured by Horiba, Ltd.). A part of the white dispersion is centrifuged (rotation speed: 1 × 10 ⁴ rpm, rotation time: 1 hour), sedimented resin particles are collected, dried, and mass average molecular weight (Mw). (Polystyrene equivalent value by GPC; the same applies hereinafter) and glass transition point (Tg).
Mw was 2 × 10 ⁵ , Tg was 41 ° C.
Met.

[0140]

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[0141] Production examples of the resin particles (L) 2: resin particles (L
-2) for dispersion stabilization resin of the following structure (P-2) was a mixture of 15g of Isopar G 385 g was warmed to a temperature 70 ° C. under nitrogen gas stream with stirring. Methyl methacrylate 20
g, 22 g of ethyl acrylate, 4 g of octadecyl acrylate, 8 g of 2- (N, N-diethylamino) ethyl methacrylate and A.I. I. V. N. 1.5 g of the mixture and 15 g of methyl methacrylate, 27.8 g of methyl acrylate and 3.2 of 2-phosphonoethyl acrylate
g and 10 g of ethanol were simultaneously added dropwise in 1 hour, and the mixture was stirred for 2 hours. Next, A. I.
V. N. Was added, and the mixture was heated to a temperature of 75 ° C. and stirred for 3 hours. I. B. N. It was stirred for 3 hours warming to a temperature 80 ° C. In addition 0.8 g. Then raise the temperature to 100
C. and stirred for 2 hours under a reduced pressure of 200 mmHg to distill off ethanol and unreacted monomers. 200 after cooling
The resulting white dispersion was passed through a mesh nylon cloth and was a latex having a conversion of 99% and an average particle size of 0.24 μm. The Mw of the resin particles was 3 × 10 ⁵ , and the Tg was 41 ° C.

[0142]

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Production Examples 3-5 of Resin Particles (L): Resin Particles (L-3)-(L-5) In Production Example 1 of resin particles (L), 20 g of dispersion stabilizing resin (P-1) and 2- (N, N-dimethylamino)
Each particle was prepared in the same manner as in Production Example 1 except that instead of 6 g of ethyl methacrylate, 18 g of a dispersion stabilizing resin (P-3) having the following structure and 6 g of each monomer (B) in Table-A below were used. Manufactured. Each of the obtained dispersions was a latex having an average particle size of 0.20 to 0.26 μm.
Mw for the resin particles is 1 × 10 ^{6 to} 3 × 10 ⁵ , and Tg is 4
It was in the range of 0-50 ° C.

[0144]

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[0145]

[Table 1]

Production Example 6 of Resin Particle (L): Resin Particle (L)
-6) A mixture of 16 g of a dispersion stabilizing resin (P-4) having the following structure and 380 g of Isopar G was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. In addition, methyl methacrylate 1
5 g, methyl acrylate 22 g, dodecyl acrylate 4 g, 4- (N, N-dimethylamino) methylstyrene 8 g and A. I. B. N. 1.5 g of the mixture and 10 g of methyl methacrylate, 34.4 methyl acrylate
g and a mixture of 6.6 g of 4-sulfomethylstyrene and 15 g of ethanol were simultaneously added dropwise over 1 hour, followed by stirring for 2 hours. Next, A. I. B. N. 1.0 g
In addition, the mixture was stirred for 3 hours. I. B. N. To 0.8
g and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. next,
The temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off ethanol and unreacted monomers.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a degree of polymerization of 98% and an average particle size of 0.22 μm. Mw of resin particles is 9 × 10 ⁴ , Tg
Was 42 ° C.

[0147]

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Production Examples 7 to 14 of Resin Particles (L): Resin Particles (L-7) to (L-14) In Production Example 6 of resin particles (L), 4 g of dodecyl acrylate was used in place of 4 g of dodecyl acrylate. 4g of each monomer (D)
Except for using were prepared each particle in the same manner as in Production Example 6. Each of the obtained dispersions has an average particle diameter of 0.22 to 0.22.
The latex was in the range of 0.28 μm. Mw of resin particles is 8 × 10 ⁴ to 2 × 10 ⁵ , Tg is 38 to 42 ° C.
Was in the range.

[0149]

[Table 2]

Production Examples 15 to 22 of Resin Particles (L): Resin Particles (L-15) to (L-22) In Production Example 6 of resin particles (L), instead of 6.6 g of 4-sulfomethylstyrene, 0.028 mol of each monomer (C) in Table-C below (monomer (B) / monomer (C))
= 1.8 mol ratio), except that particles were produced in the same manner as in Production Example 6 above. Each of the obtained dispersions was a latex having an average particle diameter of 0.22 to 0.28 μm. The Mw of the resin particles is 9 × 10 ⁴ to 2 × 10 ⁵ , T
g ranged from 40 to 48 ° C.

[0151]

[Table 3]

Production Example 23 of Resin Particles (L): Resin Particles (L-23) A mixture of 15 g of a dispersion stabilizing resin (P-5) having the following structure and 385 g of Isopar G was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. Heated. To this, 42 g of vinyl acetate, 2-
7 g of (N, N-dimethylamino) ethylcrotonate and A.I. I. B. N. , 1.5 g of a mixture and 45 g of vinyl acetate, 6 g of 3-phosphonopropylcrotonate and 10 g of ethanol were simultaneously added dropwise over 30 minutes, and the mixture was stirred for 2.5 hours. Next, A. I. B.
N. Was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. I. B. N. And add 85g at a temperature of 85
C. and stirred for 3 hours. Next, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours under a reduced pressure of 200 mmHg to distill off ethanol and unreacted monomers. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 90% and an average particle size of 0.23 μm.
Mw of the obtained resin particles is 8 × 10 ⁴ , and Tg is 45 ° C.
Met.

[0153]

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Production Examples 24 to 28 of Resin Particles (L): Resin Particles (L-24) to (L-28) In Production Example 6 of resin particles (L), 16 g of dispersion stabilizing resin (P-4) was prepared. Instead, instead of 20 g of the dispersion stabilizing resin (P-6) having the following structure and 8 g of 2- (N, N-dimethylamino) methylstyrene, 0.04 mol of each monomer (B) shown in Table D below was used. Except for using, each particle was produced in the same manner as in Production Example 6 above. Each of the obtained dispersions was a latex having an average particle diameter of 0.20 to 0.25 μm. Mw of resin particles is 1 × 10 ^{5 to} 3 × 10
^5, Tg ranged from 40 to 50 ° C..

[0155]

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[0156]

[Table 4]

Production Example 29 of Resin Particles (L): Resin Particles (L-29) 14 g of a dispersion stabilizing resin (P-7) having the following structure, 85 g of vinyl acetate, 2- (N, N-dimethylamino) ethylcroto 6g, 3-phosphonomethylstyrene 7g, hexadecyl methacrylate 2g and Isopar H286g
Was heated to a temperature of 75 ° C. while stirring under a stream of nitrogen. In addition, A. I. V. N. 1.8 g was added and stirred for 4 hours. Next, A. I. B. N. Add 1.0g,
The temperature was raised to 80 ° C. to react for 3 hours. I.
B. N. 0.8 g was added and stirred for 3 hours. Subsequently, the temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off unreacted monomers. After cooling, the mixture was passed through a nylon cloth of 200 mesh, and the resulting white dispersion was converted to a conversion of 94%.
Was a latex having an average particle size of 0.24 μm.

[0158]

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Production Example of Comparative Resin Particle 1: Resin Particle (L
L-1) 15 g of methyl methacrylate and 3 g of 2-phosphonoethyl methacrylate in Production Example 1 of resin particles (L)
Was changed to 18 g of methyl methacrylate, and particles were produced in the same manner as in Production Example 1 of resin particles (L). The average particle diameter of 0.24μ The resulting white dispersion in polymerization rate of 99%
m latex. Mw of resin particles is 2 × 10
⁵ , Tg was 41 ° C.

Production Example 2 of Comparative Resin Particles: Resin Particles (L
L-2) Production example of resin particles (L) except that in Preparation Example 1 of resin particles (L), 15 g of methyl methacrylate and 6 g of 2- (N, N-dimethylamino) ethyl methacrylate were changed to 21 g of methyl methacrylate. Particles were produced in the same manner as in Example 1. The obtained white dispersion was a latex having a conversion of 99% and an average particle size of 0.23 μm. The Mw of the resin particles was 2 × 10 ⁵ , and the Tg was 43 ° C.

[0161] Production Example of Comparative resin particle 3: the resin particles (L
L-3) In Production Example 2 of the resin particles (L), 15 g of methyl methacrylate and 3.2 g of 2-phosphonoethyl acrylate were used.
Particles were produced in the same manner as in Production Example 2 of resin particles (L), except that g was changed to 18.2 g of methyl methacrylate. The obtained white dispersion was a latex having a conversion of 99% and an average particle size of 0.23 μm. Mw for resin particles
Was 3 × 10 ⁵ and Tg was 38 ° C.

Production Example 4 of Comparative Resin Particles: Resin Particles (L
L-4) Production Example 2 of resin particles (L) except that in Preparation Example 2 of resin particles (L), 20 g of methyl methacrylate and 8 g of 2- (N, N-diethylamino) ethyl acrylate were changed to 28 g of methyl methacrylate. Particles were produced in the same manner as described above. The obtained white dispersion was a latex having a conversion of 99% and an average particle size of 0.23 μm. The Mw of the resin particles was 3 × 10 ⁵ , and the Tg was 42 ° C.

Example 1 and Comparative Examples A and B <Preparation of an original plate for printing> 200 g of photoconductive zinc oxide, 2 g of a resin (B-1) having the following structure, and a resin (B-2) having the following structure
18 g, 0.018 g of a cyanine dye (1) having the following structure,
A mixture of 0.15 g of phthalic anhydride and 300 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a rotation speed of 6 ×.
The composition was dispersed at 10 ³ rpm for 10 minutes to prepare a photosensitive layer-forming composition, which was applied to a support for ELP Master 2X type (manufactured by Fuji Photo Film Co., Ltd.) at a dry adhesion amount of 20 g /
m ² and apply at 110 ° C with 1 wire bar.
After drying for 0 second, the plate was allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours to prepare a printing original plate.

[0164]

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<Preparation of Liquid Developer (LD-1)> A paint shaker (Toyokyo Seiki Co., Ltd.) was prepared by adding 10 g of a dodecyl methacrylate / acrylic acid (95/5 mass ratio) copolymer, 10 g of alkali blue and 30 g of Isopar H together with glass beads. (Manufactured by Co., Ltd.) and dispersed for 4 hours to obtain a fine blue dispersion of alkali blue.

Preparation of Resin Particles (L)
-1) 6 g (as solid content) of the above blue dispersion 2.5
g (as solid content), tetradecyl alcohol (FO
A liquid developer for electrostatic photography (LD-1) was prepared by diluting 15 g of C-1400 (manufactured by Nissan Chemical Industries, Ltd.) and 0.1 g of cobalt naphthenate into 1 liter of Isopar G.

<Production of Comparative Developers A and B> In the production of the liquid developer (LD-1), the resin particles (L-
Liquid developers A and B for comparison were prepared in the same manner except that 1) was replaced with the following resin particles. Comparative liquid developer A: resin particles (LL-1) obtained in Production Example 1 of comparative resin particles. Comparative liquid developer B: resin particles (LL-2) obtained in Production Example 2 of comparative resin particles. The charging characteristics, image reproducibility, printability, and the like of these liquid developers were examined, and the results are shown in Table-E.

[0168]

[Table 5]

The evaluation described in Table-E was performed as follows. Note 1) Charging characteristics ・ AC electric conductivity AC electric conductivity (pS / c)
m) with an LCR meter (AG-431 manufactured by Ando Electric Co., Ltd.)
It measured using 1). At the time of measurement, an LCR meter was placed in a self-made aluminum shield box containing 2.3 ml of the liquid developer to be measured via a test lead (AG-4912, manufactured by Ando Electric Co., Ltd.). Electrode (Kawaguchi Electric Co., Ltd. LP-05, electrode constant 198), conductance is measured at an applied voltage of 5 V and a measurement frequency of 1 kHz, and the value is converted into an electric conductivity by dividing the value by the electrode constant. did. In the measurement, the measurement parameters of the LCR meter were set to capacitance, and the circuit mode was set to parallel mode.

Particle Charge Ratio As shown by the following formula, the charge ratio of the dispersed particles in the liquid developer is represented.

[0171]

(Equation 1)

Here, the charge amount of the supernatant was determined by centrifuging the liquid developer (conditions: 1 × 10 ⁴ rpm 2 hours).
Represents the AC electric conductivity of the transparent liquid, which is the supernatant obtained by sedimenting the particles.

The conditions I and II are obtained by changing the state of aging after the production of the liquid developer. The condition I is that the liquid developer obtained by mixing all the components is subjected to room temperature and normal humidity ( 25 ° C,
Those obtained by one week aged at RH 65%) (fresh product)
On the other hand, the condition II is that the fresh product is stored under the condition of high temperature and high humidity (35 ° C., 85% RH) for one month,
This is a product that has been forcibly aged (aged product).

Note 2) Image reproducibility The printing original plate was charged at -6 kV, and 2.8 was used as a light source.
A gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) having a mW output is exposed on a printing original plate surface at a pitch of 25 μm and a scanning speed of 300 m / sec under irradiation of 6.4 μjoul / cm ^2. as a developed using the liquid developer described above, a isoparaffinic solvent Isopar G (produced by Esso chemical Co.,
Was washed with a rinsing solution prepared in (1), and fixed at a plate surface temperature of 70 ° C. for 10 seconds to form an image. The obtained plate-making image was visually evaluated for fog, image quality and the like. Note 3) Printability The original plate on which an image was formed according to the above-described image reproducibility method was treated with a desensitizing solution ELP-E2 (Fuji Photo Film Co., Ltd.)
The printing plate was prepared by passing through an etching machine once. The printing plate thus obtained was printed using a solution obtained by diluting ELP-E2 (manufactured by Fuji Photo Film Co., Ltd.) 20 times with water as a dampening solution, and using neutral paper as a printing base paper. Printing was performed using a Hamadastar 800SX model (manufactured by Hamadastar Co., Ltd.) as a press, and the quality of the tenth printed material and the number of printed sheets in which the image portion of the printed material did not have any missing portions were examined. As shown in Table-E, the charge characteristics of the liquid developer of the present invention were extremely stable, even when stored under severe conditions, with almost no change in the overall charge amount and the charge fraction of the particles. . On the other hand, in Comparative Example A, the change in the overall charge amount with time was relatively small, but the change in the charge fraction of the particles was large. In Comparative Example B, the total charge amount and the charge fraction of the particles were low, and further decreased over time. When an image was actually formed, the liquid development of the present invention was good in both conditions I and II. Comparative Example A, occurrence of background fog was observed in the condition II, Comparative Example B image flow occurs over the entire surface. When printing was performed as a printing plate, when the liquid developer of the present invention was used, 10,000 or more clear prints were obtained even under the condition II.
On the other hand, in Comparative Examples A and B, printing was not practical for printing.

Example 2 and Comparative Examples C to D <Preparation of Liquid Developer (LD-2)> Tetradecyl methacrylate / methacrylic acid (95/5 mass ratio) copolymer 1
0g, Nigrosine 10g and Isopar G 30g together with glass beads in a paint shaker (Toyo Seiki Co., Ltd.)
And dispersed for 6 hours to obtain a fine dispersion of nigrosine. 6 g of resin particles (L-2) (as solid content),
3 g (as solid content) of the above nigrosine dispersion, 0.12 g of zirconium naphthenate, and branched hexadecyl alcohol (FOC-1600, manufactured by Nissan Chemical Co., Ltd.) 10
g was diluted to 1 liter of Isopar G to prepare a liquid developer for electrostatic photography (LD-2). <Preparation of Comparative Developers C and D> The above liquid developer (LD
Liquid developer C for comparison, except that the resin particles (L-2) are replaced with the following resin particles in the production of
And D were produced. Comparative liquid developer C: resin particles (LL-3) obtained in Production Example 3 of comparative resin particles. Comparative liquid developer D: resin particles (LL-4) obtained in Production Example 4 of comparative resin particles.

The above-mentioned liquid developer was applied to a fully automatic plate making machine ELP58.
ELX-PEX (manufactured by Fuji Photo Film Co., Ltd.), and ELP-PEX (manufactured by Fuji Photo Film Co., Ltd.) used as a developer for ORX (manufactured by Fuji Photo Film Co., Ltd.)
The master 2X type (manufactured by Fuji Photo Film Co., Ltd.) was exposed, developed and desensitized. Blackening rate (image area)
35% of the originals were used. The plate making speed was 6 plates / min. After processing 10,000 sheets of the ELP Master 2X type, it was observed whether or not the toner adhered to the developing device. The results are shown in Table-F.

[0177]

[Table 6]

When plate making is performed using the liquid developer of the present invention,
Even after 10,000 plates, the developing device was not stained. Comparative Example C
In D and D, contamination of the developing device due to adhesion of toner residue was observed. In addition, using the 10,000th printing plate for offset obtained by plate making, printing was performed by a conventional method, and the number of printed sheets until the occurrence of missing characters, blurred solid portions, etc. in the printed image was examined. The printing plate obtained by using the developer of the present invention was good even at 10,000 sheets or more. On the other hand, in Comparative Examples C and D, image defects and the like of printed matter occurred from the start of printing. Further, when the developer (LD-2) aged under the condition II of the example (stored at 35 ° C./85% RH for one month) was subjected to the same test as above, the performance was almost the same as that of the fresh product. showed that. From the above results, it can be seen that the liquid developer of the present invention does not cause any staining of the developing device, and the obtained printing plate has excellent printing durability.

Example 3 <Preparation of an original plate for printing> The following coating solution for a photoconductive layer was applied on an aluminum plate subjected to graining and positive oxidation treatment by a bar coater, and dried at 120 ° C. for 10 minutes. Thickness 3.
A printing master having a thickness of 0 μm was prepared.

X-type metal-free phthalocyanine 20 parts Copolymer of butyl methacrylate and methacrylic acid (methacrylic acid 35 mol%) 140 parts 1-methoxy-2-propanol 555 parts Methyl ethyl ketone 555 parts A mixture having a composition of at least It was dispersed for 2 hours with a dispersion mixer Dynamill (KDL-5, manufactured by WABACHOFEN) to obtain a coating solution for a photoconductive layer.

<Preparation of Liquid Developer (LD-3)> 9 g (as a solid content) of the resin particles (L-1) of Production Example 1 of the resin particles (L) were added to tetradecyl alcohol (FOC140).
0) A liquid developer (LD-3) was prepared by mixing 10 g and 0.15 g of octene-half-maleic acid dodecylamide copolymer with Isopar H so as to be 1 liter. When the charging characteristics were measured by the same method as described in Example 1,
With the results shown in Table -G.

[0182]

[Table 7]

Even after the elapse of time under severe conditions, the charge characteristics were almost the same as that of a fresh product and extremely stable.

The printing master having the photoconductive layer was subjected to corona discharge so that the surface of the photoconductive layer was uniformly charged to +400 V, and then 3 μjoul / cm ² was applied on the surface using a semiconductor laser (light source wavelength: 780 nm). Under irradiation, pitch 25μ
m and a scanning speed of 300 m / sec.
Subsequently, after performing reversal development under the condition of a bias voltage of +180 V using the liquid developer (LD-3) of the present invention, the image was fixed by heating at 120 ° C. for 1 minute. 40 parts of potassium silicate, 10 parts of potassium hydroxide, 20 parts of benzyl alcohol and 20 parts of ethanol
The non-image area was removed by immersion in an etching solution diluted to 10 parts for 10 seconds, sufficiently washed with water and dried to prepare a printing plate. The printing plate was visually evaluated with a 60-fold loupe (manufactured by PEAK Co., Ltd.). As a result, no loss of fine lines and fine characters was observed in the image portion, and the image was extremely clear. Next, this printing plate
After gumming, the offset printing machine (Oliver 52)
Mold, manufactured by Sakurai Seisakusho Co., Ltd.). Even after printing 100,000 sheets or more, the image quality of the printed matter was clear, and no background fog was seen at all. Further, plate making, etching treatment and printing were performed in the same manner as described above using the liquid developer of Condition II, and the result was completely equivalent to that of a fresh product.

Further, when the printing original plate was made into a 5,000 plate plate and stains of the developing portion were examined, no stains such as adhesion of toner residue were found, and the liquid developer was excellent in redispersibility. showed that. In addition, when the image on the printing plate after the 5000th plate etching treatment was visually evaluated, fine lines and fine characters were clear and no difference was seen from the printing plate of the first plate. As described above, the liquid developer of the present invention shows a stable charge characteristic even under aging under severe conditions in an electrophotographic plate making system in which a non-image portion is eluted to form a printing plate, and has excellent dispersibility. And redispersibility. In addition, the printing durability was satisfactory.

[0186] In Example 4-19 Example 1, in place of the resin particles (L-1), except for using the resin particles described below in Table -H, each liquid in the same manner as in Example 1 a developer was prepared. The AC conductivity of the obtained developer was 95 to 100 (ps / cm), and the charged fraction of particles was 90 to 95%. Also, under the condition II, almost no change occurred.

[0187]

[Table 8]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1 to examine the performance. Each liquid developer shows the same performance as in Example 1,
Image reproducibility, dispersibility, and printability were all good. Also,
Each developer showed the same performance under the condition II and was good.

Examples 20 to 30 The same procedures as in Example 2 were repeated except that the resin particles (L-2) were replaced by the resin particles shown in Table I below, and the respective liquids were used. A developer was prepared.

[0190]

[Table 9]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 to examine the performance. In each liquid developer showed similar performance as in Example 2,
Image reproducibility, dispersibility was good also as printability. Also, contamination of the developing apparatus did not occur in the same manner as in Example 2. Further, each developer showed the same performance under the condition II and was good.

Example 31 A photosensitive drum made of amorphous silicon was rotated at a peripheral speed of 10 mm / sec, and while supplying the following dispersion liquid to the surface of the photosensitive member using a slit electrodeposition device, the photosensitive member side was grounded, applying a voltage of the electrode side to + 200V of the wearing device resin particles was electrodeposited. Next, the dispersion was removed by an air squeeze, and the film was melted and formed into a film with an infrared line heater to form a 1.5 μm-thick thermoplastic resin transfer layer on the photoreceptor. <Transfer layer forming dispersion liquid> dispersion stabilizing resin [octadecyl methacrylate / acrylamide (97/3 weight ratio) copolymer, weight average molecular weight: ⁴ × 10 4] 12g, vinyl acetate 98 g, stearyl methacrylate 2g of Isopar H384g The mixed solution was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviated AIVN) was added as a polymerization initiator, and the mixture was reacted for 3 hours. Add initiator and add 2
After 0 minutes, cloudiness occurred and the reaction temperature rose to 88 ° C.
Further, 0.5 g of the above initiator was added and reacted for 2 hours. Then, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth and passed through a white dispersion (90% polymerization rate, average particle size 0.23 μm).
m) was obtained. 10 g (as solid content) of the above thermoplastic resin dispersion and 0.001 g of zirconium naphthenate were added to 1 liter of Isopar H to obtain a positively charged resin particle dispersion. An electrophotographic process was immediately performed while maintaining the surface temperature of the photoreceptor at 40 ° C. First, the photoreceptor is corona-charged to +700 V in a dark place, read in advance from a document, and is exposed to light of 780 nm using a semiconductor laser based on information stored in a hard disk in the system as digital image data. did. The potential of the exposed portion was +220 V, and the potential of the unexposed portion was +660 V. Subsequently, after pre-bathing by Isopar H by a pre-bath device incorporated in the developing unit, the following positively charged liquid developer of the present invention was supplied from the developing unit to the surface of the photoreceptor. This time by applying a developing bias voltage to the developing unit side + 500V, the toner is to be electrodeposited to the unexposed portion by performing reversal development. Next, rinsing was carried out in a single bath of Isopar H to remove stains in the non-image area, and the liquid was cut off with an air squeeze and dried under an infrared line heater. <Preparation of the liquid developer (LD-4)> blue pigment (Linol Blu
e 4 g of Isopar G dispersion consisting of 1/1 mass ratio of FG-7350, manufactured by Toyo Ink Co., Ltd.) / octadecyl methacrylate-methacrylate (7/3 mass ratio) block copolymer
A liquid developer (LD) was prepared by diluting 8 g (as a solid content), 8 g (as a solid content) of resin particles (L-20) and 0.08 g of octadecyl vinyl ether-hemo maleic acid dodecylamide copolymer into 1 liter of Isopar G.
-4) was produced. Then it passed under an infrared line heater, generally by measuring the surface temperature by a radiation thermometer 80
After preheating to 0 ° C, the coated paper is overlaid on a photoreceptor having a transfer layer, and is in contact with a pressure of 10 kgf / cm ² (980 kPa). At a speed of 15 mm / sec. Thereafter, when the coated paper was peeled off after passing under the cooling roller and cooled, all the toner on the photoconductor was thermally transferred to the coated paper side together with the transfer layer, and a color image was obtained. The obtained color image was extremely clear, and no fog was observed in the non-image area. or,
When the liquid developer (CD-4) was forcibly aged in the same manner as in Example 1 (condition II), no difference from the fresh product was observed.
It was clear.

[0193]

According to the liquid developer of the present invention, the development-fixing process is speeded up by using specific resin particles, and the charge stability of the particles is improved even in an electrophotographic plate making system using a large-size master plate. An offset printing plate having excellent properties, dispersion stability, redispersibility, and fixability, and having excellent printing ink oil sensitivity and printing durability can be provided.

Claims (3)

[Claims] An electrophotographic liquid developer comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less. A monomer (A) containing at least one monofunctional monomer (A) which is soluble in a non-aqueous solvent and becomes insoluble by polymerization, and which contains an amino group represented by the general formula (II) ) and at least one copolymerizable monofunctional monomer (B), -PO ₃ H ₂ group, -SO ₃ H group and -SO ₂ H
Containing at least one monofunctional monomer (C) copolymerizable with the monomer (A), which contains at least one acidic group selected from the following groups, and a component represented by the following general formula (PI) A liquid developer for electrophotography, comprising copolymer resin particles obtained by polymerizing and granulating a solution containing at least one dispersion stabilizing resin (P), which is a polymer to be formed. Embedded image In the general formula (II), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or R ¹ and R ² are bonded to form a ring together with a nitrogen atom. May be formed. Embedded image In the general formula (PI), A ¹ is -COO-, -OCO-,-
_{(CH 2) a COO -,} - (CH 2) a OCO -, - O-,
Or (Where E is a direct bond, -O-, -OCO- or -CO
O-). a represents an integer of 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. p ¹ and p ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO—D ¹ , or —COO via a hydrocarbon group. −D ¹ (where D ¹
Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). 2. The dispersed resin particles form a monofunctional monomer.
(A), monofunctional monomer (B), monofunctional monomer (C)
And dispersed with stabilizing resin (P), further, the monomer
One of the following general formula (III) copolymerizable with (A)
Solution containing at least one functional monomer (D)
Is a copolymer resin particles obtained by Gozotsubu
Electrostatographic liquid developer according to claim 1, wherein the
Agent. Embedded imageIn general formula (III), U¹Is -COO-, -CONH-,-
CON (W¹¹)-[W¹¹Is an aliphatic group or
Represents a substituent represented by the general formula (IIIa)], -OCO
-, -CONHCOO-, -CH_TwoCOO-,-(C
H_Two) sOCO- (where s represents an integer of 1 to 4),-
O- or -C₆H_FourRepresents -COO-. c¹And c
^TwoMay be the same or different from each other, and each represents a hydrogen atom,
Alkyl group, halogen atom, cyano group, -COO-Q¹¹
Or -CH_TwoCOO-Q¹¹(Where Q¹¹Represents an aliphatic group
Represents). W¹Carbon atoms 8 or more aliphatic groups or total
8 or more atoms (but directly bonded to carbon and nitrogen atoms)
Represented by the following general formula (IIIa)
Represents General formula (IIIa)-(X¹-Y¹)_m − (X^Two-Y^Two)_n-Z¹ In the general formula (IIIa), Z¹Is a hydrogen atom or a carbon number of 1 to 1
8 represents an aliphatic group. Y¹And Y^TwoAre the same as each other
Or different, each -O -, - S -, - CO -, - C
O_Two-, -OCO-, -SO_Two-, -N (Z¹¹)-, -C
ON (Z¹¹) -, - N (Z¹¹) CO-, -N (Z¹¹) S
O_Two-, SO_TwoN (Z¹¹)-, -NHCO _Two-Or -N
HCONH- (where Z¹¹Is the Z¹Synonymous with
is there). X¹And X^TwoMay be the same or different from each other
And a group represented by the following general formula (IIIb)
At least one selected from the group consisting of
Represents two groups. m and n are the same or different
And each represents an integer of 0 to 4. Where the sum of m and n is
It cannot be zero. Embedded imageIn the general formula (IIIb), Y^ThreeAnd Y^FourAre the same but different
And each of the above Y¹, Y^TwoIs synonymous with X^FourIs
A hydrocarbon group having 1 to 18 carbon atoms, Z^TwoIs Z¹Same as
It is the righteousness, p is an integer of 0 to 4. 3. The dispersion stabilizing resin (P) has a polymerizable double bond represented by the following general formula (PII) bonded to one end of the polymer main chain or a substituent of a polymer repeating component. 3. The liquid developer for electrostatography according to claim 1, wherein: Embedded image In the general formula (PII), A ² represents —COO—, —OCO—,
(CH ₂ ) _b COO-,-(CH ₂ ) _b OCO-, -O-,
-SO _2- , -CONHCOO-, -CONHCONH
—, —CON (E ¹ ) —, —SO ₂ N (E ¹ ) — (E ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and b represents an integer of 1 to 4) Or [0001] (Where E ² is a direct bond, —O—, —OCO
-Or -COO-). q ¹ and q ² may be the same or different from each other, and each of p ¹ ,
It is synonymous with p ^2.