JP2003029470A - Liquid developer for electrostatic photography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer which has excellent charge stability of particles, dispersion stability, redispersibility and fixability and makes excellent printing ink sensitizability and printing resistance possible even in an electrophotographic plate making system which is speeded up in a developing- fixing process step and uses a master plat of a large size. SOLUTION: The liquid developer for electrostatic photography is prepared by dispersing at least resin particles into a non-aqueous solvent of >=10<9> Ωcm in electric resistance and <=3.5 in dielectric constant. The dispersed resin particles described above are the copolymer resin particles obtained by polymerizing and granulating a solution containing a monofunctional monomer (A) which is soluble in the non-aqueous solvent and is made insoluble therein by polymerization, a monofunctional monomer (B) which contains an amino group, a monofunctional monomer (C) which contains an acidic group selected from a -PO3 H2 group, -SO3 H group and -SO2 H group, a specific macromonomer (MM) which consists of a repeating unit having a substituent containing fluorine atoms and/or silicon atoms and a resin (P) for dispersion stability which contains specific components.

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 electrophotography, and particularly to dispersibility, storability, stability,
The present invention relates to a liquid developer for electrostatic photography, which has excellent redispersibility, image reproducibility, and fixability.

[0002]

2. Description of the Related Art A general liquid developer for electrostatic photography is 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. Dispersed in liquids with high insulation and low dielectric constant such as aliphatic hydrocarbons, metal soap, lecithin, linseed oil,
A charge control agent such as a polymer containing a higher fatty acid or vinylpyrrolidone is added. In such a developer, the resin has a diameter of several nm as insoluble latex particles.
Although dispersed in the form of particles of several hundreds of nm, in the conventional liquid developer, the soluble dispersion stabilizing resin and the charge adjusting agent and the insoluble latex particles are insufficiently bonded to each other, so that the soluble dispersion stabilizing resin and the charge adjusting agent are The agent was in a state of being easily diffused in the solution. Therefore, there is a drawback that the soluble dispersion stabilizing resin is desorbed from the insoluble latex particles due to long-term storage and repeated use, and the particles settle, aggregate, and accumulate, or the polarity becomes unclear. Further, since particles once aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to the failure of the developing machine such as dirt on the image area and clogging of the liquid feeding pump. In order to improve such problems, insoluble dispersed resin particles made of a copolymer of an insolubilizing monomer 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 them is disclosed in JP-A-60-179751 and JP-A-62-151.
No. 868, etc. In addition, an insoluble dispersion resin composed of a copolymer of a monomer that becomes insoluble and a monomer that contains a long-chain alkyl moiety in the presence of a polymer that uses a bifunctional monomer or a polymer that uses a macromolecular reaction A method for improving the dispersibility, storage stability and redispersibility of particles by using particles is disclosed in JP-A Nos. 62-166362 and 63-66567. Furthermore, as a dispersion stabilizing resin, storage stability and redispersion are achieved by using a block copolymer composed of a solvating polymer part and a non-solvating polymer part, instead of a conventional random copolymer. To improve the properties is disclosed in JP-A-3-12666 and 3-7.
No. 7965, No. 3-225353, No. 4-46354
No., etc.

[0003]

On the other hand, in recent years, a method of printing a large number of 5000 or more sheets by using a master plate for offset printing by an electrophotographic system has been attempted. It has become possible to print more than 10,000 sheets in plate size. or,
The operation time of the electrophotographic plate making system has been shortened, and the development-fixing process has been accelerated. 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.
No. 353 and No. 4-46354, the dispersed resin particles produced according to the means disclosed herein are those in the case where the developing speed is increased, the dispersibility and redispersibility of the particles are increased, and the fixing time is shortened. Alternatively, a large plate size (for example, A-
In the case of using a master plate of 3 sizes or more), the performance was not always satisfactory in terms of printing durability.

The present invention solves the above problems of the conventional liquid developer. The purpose of the present invention is to
To provide a liquid developer in which the development-fixing process is accelerated and the charge stability of particles, dispersion stability, redispersibility, and fixability are excellent even in an electrophotographic plate making system using a master plate of a large plate size. Is. Another object of the present invention is to provide a liquid developer which enables the production of 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 various ordinary electrophotography.

[0005]

[Means for Solving the Problems] The above-mentioned objects are constituted as follows.
It has been found that (1) Electric resistance 10⁹Ωcm or more and dielectric constant 3.5 or less
At least resin particles are dispersed in the non-aqueous solvent below.
In the liquid developer for electrostatic photography, the above-mentioned dispersed resin particles
If the child is soluble in a non-aqueous solvent,
At least one type of soluble monofunctional monomer (A), generally
Monomer (A) containing an amino group represented by formula (I)
At least one monofunctional monomer (B) copolymerizable with
Seed, -PO ₃H₂Group, -SO₃H group and -SO₂From H group
Monomer containing at least one selected acidic group
At least a monofunctional monomer (C) copolymerizable with (A)
And a substituent containing a fluorine atom and / or a silicon atom
One end of the main chain of the polymer composed of repeating units having
Polymerizable double bond represented by the following general formula (MI) only at one end
The mass average molecular weight formed by combining groups is 2 × 10.^FourBelow
Monofunctional macromonomer copolymerizable with monomer (A)
At least one of (MM) and the following general formula (P
For stabilizing dispersion, which is a polymer containing the component I)
Polymerization and granulation of a solution containing at least one resin (P)
Copolymer resin particles obtained by
A liquid developer for electrostatic photography.

[0006]

[Chemical 7]

In the general formula (I), 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 combined to form a nitrogen atom. You may form a ring with an atom.

[0008]

[Chemical 8]

In the formula (MI), J ¹ is --COO-- or --OC.
_{O -, - (CH 2)} d COO -, - (CH 2) d OCO -, -
_{O -, - SO 2 -,} - CONHCOO -, - CONHC
^{ONH -, - CON (K 1} ) -, - SO 2 N (K 1) -, or a phenylene group (where K ¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, d is 1 Indicates an integer of 4). m ¹ and m ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO—K ² , or —COO via a hydrocarbon group. It represents the -K ² (where K ² is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms).

[0010]

[Chemical 9]

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

[0012]

[Chemical 10]

(Here, E is a direct bond, -O-, -OCO.
-Or-COO-) is represented. a represents the integer of 1-12. 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 is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, or —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 dispersion stabilizing resin (P) has a polymerizable double bond group represented by the following general formula (PII) in one end of the polymer main chain or in the substituent of the polymer repeating component. The liquid developer for electrostatic photography according to (1) above, wherein the liquid developer is bonded.

[0015]

[Chemical 11]

In the general formula (PII), A ² is -COO-,-
_{OCO -, - (CH 2)} b COO -, - (CH 2) b OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - CON (E 1} ) -, - SO 2 N
(E ¹ ) − (where E ¹ is a hydrogen atom or 1 to 22 carbon atoms)
Represents a hydrocarbon group, and b represents an integer of 1 to 4) or

[0017]

[Chemical 12]

(Here, E ² is a direct bond, —O—, —OCO
-Or -COO-) is represented. q ¹ and q ² may be the same as or different from each other, and each is p ¹ in the formula (PI),
Synonymous with p ² .

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid developer for electrostatic photography of the present invention will be described below. 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 in the liquid developer for electrostatic photography of the present invention is preferably a linear or branched aliphatic hydrocarbon or alicyclic ring. Formula hydrocarbons, aromatic hydrocarbons, halogen-substituted products of these hydrocarbons, silicone liquids, silicone solvents such as silicone oil, and the like can be mentioned.

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 (Isopar; trade name of Exxon Corporation), Shersol 70,
Shelsol 71 (Shellsol; trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Co., Ltd.) and the like.

There are fluorocarbon solvents as halogen-substituted hydrocarbon solvents, for example, perfluoroalkanes represented by C _n F _{2n + 2} such as C ₇ F ₁₆ and C ₈ F ₁₈ (“Fluorinert manufactured by Sumitomo 3M Ltd.”). PF5080 "," Florinert PF5070 "(trade name), etc., fluorine-based inert liquid (" Fluorinert FC series "(trade name) manufactured by Sumitomo 3M, etc.), fluorocarbons (" Krightox GPL series "manufactured by DuPont Japan Limited) (Brand name), 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 I, etc. iodinated fluorocarbons (“I-142 manufactured by Daikin Fine Chemical Laboratories”
0 "," I-1600 "(trade name), etc.

Examples of silicone solvents for silicone liquids and silicone oils include dialkyl polysiloxanes (eg hexamethyldisiloxane, tetramethyldisiloxane, octamethyltrisiloxane, hexamethyltrisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, Trifluoropropylheptamethyltrisiloxane, diethyltetramethyldisiloxane, etc.), cyclic dialkylpolysiloxane (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane,
Tetra (trifluoropropyl) tetramethylcyclotetrasiloxane, etc.), methylphenyl silicone oil (eg, KF56, KF58 (trade name of Shin-Etsu Silicon Co., Ltd.), etc.) 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.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as "resin particles" or "latex particles"), which is the most important constituent part of the liquid developer of the present invention, are a specific component in the non-aqueous solvent. In the presence of the dispersion-stabilizing resin (P) containing (formula (PI)), at least one kind of monofunctional monomer (A), a monofunctional group containing an amino group represented by the general formula (II) A monofunctional monomer (C) containing at least one acidic group selected from at least one of the monomer (B), a —PO ₃ H ₂ group, a —SO ₃ H group and a —SO ₂ H group. At least one, and fluorine atom and /
Alternatively, a specific monofunctional macromonomer (MM) comprising a repeating unit having a silicon atom-containing substituent is polymerized and granulated.

Here, as the non-aqueous solvent, basically,
Any material that is miscible with the non-aqueous solvent of the liquid developer can be used.

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

Organic solvents that can be mixed with these non-aqueous solvents include alcohols (eg, ethyl alcohol, propyl alcohol, butyl alcohol,
Ethylene glycol monomethyl ether, fluoroalcohol, etc.), ketones (eg, methyl ethyl ketone, acetophenone, cyclohexanone, etc.), carboxylic acid 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, etc.) and the like.

It is desirable that the organic solvent to be mixed and used is distilled off under heating or under reduced pressure after the polymerization and granulation. However, even if it is brought into the liquid developer as a latex particle dispersion, There is no problem as long as the condition that the resistance is 10 ⁹ Ωcm or more and the dielectric constant is 3.5 or less is satisfied.

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

The monofunctional monomer (A) in the present invention is
Any monofunctional monomer that is soluble in the non-aqueous solvent but is insolubilized by polymerization may be used. Specific examples include monomers represented by the following general formula (II).

[0031]

[Chemical 13]

In the general formula (II), V ¹ is --COO-- or --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,
Includes 3- and 1,4-phenylene groups. ) Represents. Here, Q ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2
-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 and the like).

T is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group, 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.).

B ¹ and b ² may be the same or different from each other, and preferably a hydrogen atom or a halogen atom (for example,
Chlorine atom, bromine atom, etc.), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), —COO-Q ² or —CH ₂ —COO-Q ² [wherein Q ² is a hydrogen atom or optionally substituted carbon atom 1
It represents a hydrocarbon group of 0 or less (for example, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or the like).

As a specific monofunctional monomer (A),
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.); Unsaturation of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Alkyl esters or amides of carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxy group as alkyl 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-carboxamidoethyl group, etc.);

Styrene derivatives (for example, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Vinylbenzenecarboxylic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); acrylic acid, methacrylic acid, crotonic acid,
Unsaturated carboxylic acids such as maleic acid and itaconic acid; cyclic acid 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 Polymer Society of Japan, p175-184, Baifukan (1986). Compounds such as N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, and vinylthiazole). The monomer (A) may be used in combination of two or more kinds.

Next, the monofunctional monomer (B) containing an amino group represented by the above general formula (I), which is copolymerizable with the monomer (A) used in the present invention, will be explained. In the monofunctional monomer (B), the polymerizable double bond group and the amino group are not directly bonded.

In the formula (I), R ¹ and R ² may be the same or different and are preferably a hydrogen atom or a carbon number of 1 to 22.
Optionally substituted alkyl group (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 group, eicosyl group, docosyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxycarbonylethyl group, 2-methoxyethyl group,
3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms and which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group). 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.),

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

Further, R ¹ and R ² may represent an organic residue which is bonded to form a ring with a nitrogen atom. The organic residue may further contain a hetero atom (eg, oxygen atom, nitrogen atom, sulfur atom, etc.). Examples of the formed cyclic group include a morpholino group, a piperidino group, a pyridinyl group, an imidazolyl group, and a quinolinyl group. A plurality of amino groups may be contained in the molecule of the monomer (B). The monomer (B) is preferably 1 to 45% by mass, and more preferably 5 to 3 with respect to the total amount of the monomer (A).
0 mass% is used.

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

[0042]

[Chemical 14]

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), containing at least one acidic group selected from PO ₃ H ₂ group, —SO ₃ H group and —SO ₂ H group. The monomer (C) may contain a plurality of the above acidic groups in the molecule. The resin particles of the present invention contain an amino group-containing monomer (B) and a specific acidic group-containing monomer (C) as a copolymerization component in a specific ratio,
The particles express an extremely high amount of positive charge, and the changes in the charging characteristics are significantly reduced even when the environmental conditions (low temperature / low humidity to high temperature / high humidity) are changed or stored for a long time. As for the image, the image quality is always stable and excellent. The monomer (C) is used in a molar ratio of monomer (B) / monomer (C), preferably 0.2 to 2.5, more preferably 0.5 to 2.0. To be

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

[0045]

[Chemical 15]

[0046]

[Chemical 16]

Next, the monofunctional macromonomer (MM) used in the present invention will be described. The monofunctional macromonomer (MM) has the above formula (M) only at one end of the polymer main chain containing at least the repeating unit (m) having a substituent containing a fluorine atom and / or a silicon atom.
It is a monofunctional macromonomer copolymerizable with the monomer (A) having a mass average molecular weight of 2 × 10 ⁴ or less, which is formed by binding a polymerized double bond group represented by I).

The substituent containing a fluorine atom and / or a silicon atom in the repeating unit constituting the macromonomer will be described below. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues. _{-C n (F) 2n + 1} (n is 1 to 22 integer), - CF
_{H 2, -CFHCl, -CFCl 2,} -CF 2 Cl, -
(CF ₂ ) _m CF ₂ H (m is 0 or an integer of 1 to 17),-
_{CF 2 -, - CFH -,} - CFCl-

These fluorine atom-containing organic residues may be constituted in combination, and in this case, they may be directly bonded or may be combined via another linking group. The linking radicals, specifically include divalent organic residues, -O -, - S -, - N (g 1) -, - CO
-, - SO -, - SO 2 -, - COO -, - OCO-,
-CONHCO -, - NHCONH -, - CON (g 1)
A divalent aliphatic group or a divalent aromatic group which may have a bonding group selected from —, —SO ₂ N (g ¹ ) — and the like,
Alternatively, an organic residue composed of a combination of these divalent residues can be mentioned. Here, g ¹ represents an alkyl group having 1 to 3 carbon atoms.

As the substituent containing a silicon atom, those containing the following siloxane structure (or silyloxy structure) or silyl group are preferable.

[0051]

[Chemical 17]

In the above structure, R ¹¹ and R ¹² and R
¹³ , R ¹⁴ and R ^{15, which} may be the same or different, each represents an aliphatic group, an aromatic group or a heterocyclic group. R ¹¹ ~ R ¹⁵
Are each preferably a linear or branched alkyl group having 1 to 18 carbon atoms 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 group, 2-fluoroethyl group, trifluoromethyl group, 2-
Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, 2-methylcarbonylethyl group, 2,3-dimethoxypropyl group, fluorinated alkyl group [for example _{- (CH 2) h C i} F 2i + 1 group (wherein h is 1
~ Integer of 6, i represents an integer of 1 to 12) group,-(CH
_{2) h - (CF 2)} j -R 16 group (wherein j is 0 or an integer of 1 to 12, R ¹⁶ groups are alkyl groups having 1 to 12 carbon atoms, -CF
₂ H, -CFH _2, represents a -CF _3), - CH (C
_{F 3) 2, -CF 2 Cl} , -CFCl 2, -CFClH,
_{-CF (CF 3) OC i F} 2i + 1, -OC i F 2i + 1, -C (C
F ₃ ) ₂ OC _i F _{2i + 1} etc.],

An alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-methyl-1-propenyl group, 2-
Butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-
Hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolenyl group, etc.), carbon number 7 to
12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, Polyfluorohexyl group, methylcyclohexyl group, methoxycyclohexyl group, etc.), 6 to 6 carbon atoms
12 optionally substituted aromatic groups (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxy group Phenyl group, fluorophenyl group, chlorophenyl group, difluorophenyl group, bromophenyl group,
Cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, trifluoromethylphenyl group, etc.), or nitrogen atom, oxygen atom, sulfur atom A heterocyclic group which may be condensed with at least one atom selected from (for example, the heterocycle includes pyran ring, furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring) , Piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring and the like).

Particularly preferably, each of the substituents of R ¹¹ and R ¹² and the two or more substituents of R ¹³ , R ¹⁴ and R ¹⁵ are each an alkyl group or an alkenyl group. is there.

A plurality of fluorine atom-containing substituents and silicon atom-containing substituents may be contained in the molecule of the repeating unit (m). Specific examples of the repeating unit (m) are shown below, but the invention is not limited thereto.

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

The content of the repeating unit (m) is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more based on the total polymer components of the macromonomer (MM).

The macromonomer (MM) of the present invention comprises a polymer main chain having a polymerizable double bond group represented by the general formula (MI) bonded to one end thereof. In formula (MI), J ¹ is —COO—, —OCO—, — (CH ₂ ) _d COO—, —.
_{(CH 2) d OCO -,} - O -, - SO 2 -, - CONHC
OO -, - CONHCONH -, - CON (K 1) -, -
SO ₂ N (K ¹ ) — or a phenylene group (wherein K ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and d represents an integer of 1 to 4). m ¹ and m ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, or —CO.
O-K ^2, or an -COO-K ² via a hydrocarbon group (wherein K ² is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

The hydrocarbon groups contained in m ¹ , m ² and J ¹ in the general formula (MI) each have the indicated carbon number (as an unsubstituted hydrocarbon group), but these hydrocarbon groups are substituted. It may have been done. The hydrocarbon group is preferably an alkyl group having 1 to 22 carbon atoms 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 group, eicosyl group,
Docosyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), which may be substituted with 4 to 18 carbon atoms. Alkenyl group (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4- Methyl-2-hexenyl group, decenyl group,
Dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolenyl group, etc.), and optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group,
Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or carbon An optionally substituted aromatic group of the formulas 6 to 12 (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group,
Dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxy Carbonylphenyl group, acetamidophenyl group, propionamidophenyl group, dodecyloylamidophenyl group and the like).

J ¹ represented by the general formula (MI) is -Ph-
When representing (phenylene group), the benzene ring may have a substituent. Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.) and the like.

The macromonomer (MM) of the present invention has a polymerizable double bond group represented by the above general formula (MI) bonded to the above-mentioned repeating unit (m) component. ) Is attached to the end of the polymer main chain.

[0065]

[Chemical formula 22]

In general formula (MIa), other than G ¹ , formula (MI)
It is synonymous with each symbol inside. G ¹ represents a bond directly linked to one end of the polymer main chain or a linking group via an arbitrary linking group. The linking group to be linked is a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom -Composed of any combination of atomic groups of heteroatom bonds. For example,

[0067]

[Chemical formula 23]

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

With respect to the polymerizable double bond group represented by the general formula (MI), which is bonded to one end of the polymer main chain as described above,
The details are shown below. In the following specific examples, A is −
It represents H, -CH ₃ or -CH ₂ COOCH _3, the 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.

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

The macromonomer (MM) of the present invention having a polymerizable double bond group bonded to only one end of the polymer main chain is
A living polymer obtained by conventionally known radical polymerization (for example, iniferter method), anionic polymerization or cationic polymerization is reacted with a reagent having various double bond groups, or a specific reaction is caused at the end of this living polymer. Group (for example, -OH, -COO
_{H, -SO 3 H, -NH 2} , -SH, -PO 3 H 2, -NC
O, -NCS,

[0075]

[Chemical 28]

After reacting a reagent containing -COCl, -SO ₂ Cl, etc.), a polymeric double bond group is introduced by a polymer reaction (method by ionic polymerization method), or the above-mentioned specific in the molecule. After radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group of
It can be easily produced by a synthetic method such as a method of introducing a polymerizable double bond group by performing a polymer reaction using a specific reactive group bonded to only one end of the polymer main chain.

Specifically, Takayuki Otsu, Polymer, 33 (No.
3), 222 (1984), P. Dreyfuss & RP Quirk, Encycl.
Polym. Sci. Eng., 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai "Chemistry and Industry", 60 , 57 (1986), PF Rempp & E. Fr
anta, Advances in Polymer Science, 58 , 1 (1984),
Koichi Ito "Polymer Processing", 35 , 262 (1986), V. Percec,
Applied Polymer Science, 2 85, 97 can be introduced into the polymerizable double bond group according to the method described in the review and literature cited to that of (1984) or the like.

More specifically, a mixture of i) at least one monomer corresponding to the repeating unit (m) and a chain transfer agent containing the above-mentioned specific reactive group in the molecule is used as a polymerization initiator. (For example, azobis compounds, peroxides, etc.)
Ii) without using the above chain transfer agent,
Method of polymerizing using a polymerization initiator containing the specific reactive group in the molecule, or iii) a compound containing the specific reactive group in the molecule in both the chain transfer agent and the polymerization initiator Depending on the method used, etc., a polymer in which a specific reactive group is bonded to only one end of the main chain of the polymer is synthesized, and then the specific reactive group is utilized to carry out a polymeric double bond by a polymer reaction. The method of introducing is mentioned.

As the chain transfer agent to be used, for example, a mercapto compound containing the specific reactive group or a substituent capable of being induced to the 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, etc.} or the "specific reactive group" or the "specific reactive group" Examples thereof include iodinated alkyl compounds having an inducible substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferred are mercapto compounds.

Further, as the polymerization initiator containing a specific reactive group or a substituent capable of being introduced into the specific reactive group,
For example, azobis compounds (for example, 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis (2-cyanopropanol), 2 , 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] propionamide}, 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), dithiocarbamate compound {eg, benzyl
N-methyl-N-hydroxyethyldithiocarbamate, 2-carboxyethyl N, N-diethyldithiocarbamate, 3-hydroxypropyl N, N-dimethyldithiocarbamate} and the like can be mentioned.

The amount of each of these chain transfer agents or polymerization initiators used is 0.1 to 1 with respect to 100 parts by weight of all monomers.
It is 5 parts by mass, and preferably 0.5 to 8 parts by mass.
The mass average molecular weight of the macromonomer (MM) is preferably 1 × 10 ³ to 2 × 10 ⁴ , and more preferably 3 × 10 ^3.
Is about 1.5 × 10 ⁴ . By using the macromonomer (MM), the oil-based ink of the present invention prevents the occurrence of deposits on the recording apparatus, particularly the ejection head even during continuous use, and is excellent in redispersibility after storage. There is. The amount of macromonomer (MM) used is based on the total amount of all monomers.
Preferably 0.5 to 15% by mass, more preferably 2 to 1
It is 0 mass%.

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 form a non-aqueous solvent-insoluble polymer produced by polymerizing a monomer in a non-aqueous solvent into a stable resin dispersion is represented by the general formula It is a polymer soluble in a non-aqueous solvent and containing at least one repeating unit represented by (PI). The component represented by the general formula (PI) is a component that becomes soluble in the dispersion medium used in the liquid developer.

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

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

P¹And p²Are the same or different from each other
Also, preferably, a hydrogen atom or a halogen atom (for example,
For example, fluorine atom, chlorine atom, bromine atom), cyano group,
An alkyl group having 1 to 3 carbon atoms, -COO-D³Or -C
H₂COO-D³(Where D³Is an aliphatic having 1 to 22 carbon atoms
Represents a group, for example, a methyl group, an ethyl group, a propyl group,
Butyl group, hexyl group, octyl group, decyl group, dodecyl group
Group, tridecyl group, tetradecyl group, hexadecyl group
Group, octadecyl group, docosyl group, pentenyl group, hex
Cenyl group, heptenyl group, octenyl group, decenyl group,
Dodecenyl group, tetradecenyl group, hexadecenyl group,
Octadecenyl group and the like, and these aliphatic groups are
L may have the same substituents as those represented by L)
You More preferably p¹And p²Is the hydrogen source
Child, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group,
Chill group, propyl group, etc.), -COO-D^FourOr -CH₂
COO-D ^Four(Where D^FourIs alkyl having 1 to 12 carbons
Represents a group or an alkenyl group, for example, a methyl group, ethyl group
Group, propyl group, butyl group, hexyl group, octyl group
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 a substituent similar to the above).

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

The other copolymerizable monomer may be any as long as it contains a polymerizable double bond group, and examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid; carbon. Unsaturated carboxylic acid ester derivatives or amide derivatives of 6 or less; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group, etc. . More specifically, the same compounds as the above-mentioned insolubilizing monomer (A) and the like can be mentioned.

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 60% by mass or more, based on the total amount of the polymer. , And more preferably 70% by mass or more. Further, in the dispersion stabilizing resin (P), another monomer (for example, insoluble in the dispersion medium, which is soluble in the dispersion medium used for the liquid developer and can be copolymerized with the copolymerization component represented by the general formula (PI)). The polymerization component corresponding to the resulting monomer (A)) may be either random copolymerization or block copolymerization. Block copolymerization is preferred. The dispersion stabilizing resin (P) of the present invention does not have a crosslinked structure between polymer main chains.

Further, as a preferred embodiment of the dispersion stabilizing resin (P) of the present invention, the above-mentioned general formula (PI) is contained in one end of the polymer main chain or in the substituent of the repeating component constituting the polymer.
It is formed by bonding a polymerizable double bond group represented by I) (hereinafter, also referred to as a dispersion stabilizing resin (PG)), and the polymerizable double bond group constitutes a dispersed resin particle. It may be any functional group that copolymerizes with the monomer (A).

In the formula (PII), A ² is --COO-- or --OC.
_{O -, - (CH 2)} b COO -, - (CH 2) b OCO -, -
_{O -, - SO 2 -,} - CONHCOO -, - CONHC
^{ONH -, - CONE 1 -,} - SO 2 NE 1 - ( wherein 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

[0091]

[Chemical 29]

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

Q ¹ and q ² may be the same or different and have the same meaning as p ¹ and p ² in the formula (PI). q
It is preferable that either ^{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, and a dodecyl group. Represents

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

[0096]

[Chemical 30]

In general formula (Pa), other than G, formula (PI)
And each symbol in (PII). G represents a bond directly linked to one end of the polymer main chain or a linking group via an optional linking group.

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

[0099]

[Chemical 31]

Z ¹ and z ² are each a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a cyano group, a hydroxyl group, an alkyl group (eg, methyl group, ethyl group, propyl group, etc.). ) Etc. are shown. z ³ and z ⁴ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, phenyl group, And a —Oz ⁵ (z ⁵ has the same meaning as the hydrocarbon group for 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 example,
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.

[0102]

[Chemical 32]

[0103]

[Chemical 33]

[0104]

[Chemical 34]

[0105]

[Chemical 35]

The dispersion stabilizing resin (PG) of the present invention in which a polymerizable double bond group is bonded to one end of the polymer main chain is a conventionally known radical polymerization (for example, iniferter method etc.), anion polymerization or cation. A living polymer obtained by polymerization is reacted with a reagent containing various double bond groups at the end, or a specific reactive group (for example, —OH, —COOH, —SO) is added to the end of the living polymer.
_{3 H, -NH 2, -SH,} -PO 3 H 2, -NCO, -NC
S,

[0107]

[Chemical 36]

--COCl, --SO ₂ Cl, etc.) is reacted, and then a polymerizable double bond group is introduced by polymer reaction (method by ionic polymerization method), or the above-mentioned specific in the molecule. After radical polymerization using a polymerization initiator and / or a chain transfer agent containing a reactive group of
It can be easily produced by a synthetic method such as a method of introducing a polymerizable double bond group by performing a polymer reaction using a specific reactive group bonded to only one end of the polymer main chain.

Specifically, Takayuki Otsu, Kogaku, 33 (No.
3), 222 (1984), P. Dreyfuss & RPQuirk, Encycl. P
olym. Sci. Eng., 7 , 551 (1987), Yoshiki Nakajo, 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.
The polymerizable double bond group can be introduced according to the methods described in the review articles such as plied Polymer Science, 285 , 97 (1984) and the references cited therein.

More specifically, i) at least one of the monomers corresponding to the repeating unit represented by the general formula (PI).
A method of polymerizing a mixture of a species and a chain transfer agent containing the specific reactive group in the molecule with a polymerization initiator (eg, azobis compound, peroxide, etc.), ii) without using the chain transfer agent A method of polymerizing using a polymerization initiator containing the specific reactive group in the molecule, or iii) a compound containing the specific reactive group in the molecule in both the chain transfer agent and the polymerization initiator Is used to synthesize a polymer in which a specific reactive group is bonded to only one end of the polymer main chain. Examples include methods for introducing a bond.

The chain transfer agent to be used is, for example, a mercapto compound containing a specific reactive group or a substituent capable of being derivatized into the 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, etc.} or a specific reactive group or a substituent capable of being induced into a specific reactive group Examples of the iodinated alkyl compound (eg, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid). Preferred are mercapto compounds.

Further, as the polymerization initiator containing a specific reactive group or a substituent capable of being induced to the specific reactive group,
For example, azobis compounds (for example, 4,4′-azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis (2-cyanopropanol), 2 , 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)}, thiocarbamate compound {eg, benzyl N
-Methyl-N-hydroxyethyldithiocarbamate,
2-carboxyethyl N, N-diethyldithiocarbamate, 3-hydroxypropyl N, N-dimethyldithiocarbamate} and the like can be mentioned.

The chain transfer agent or polymerization initiator is used in an amount of 0.05 to 100 parts by weight based on the total amount of all the monomers.
It is 10 parts by mass, preferably 0.1 to 5 parts by mass.

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

[0115]

[Chemical 37]

In the formula (Pb), p¹, P², A¹, L, q¹,
q²Is synonymous with the above. x component and y component are resin
You may contain 2 or more types in (P). t¹, T²Is each
The above p ¹, P²Is synonymous with. A³And A^FourIs each
A in formula (PII)²Is synonymous with. G⁰Is a linking group A
³And linking group A^FourA group connecting at least one carbon
Atom, oxygen atom, sulfur atom, silicon atom or nitrogen atom
Represents one consisting of.

As the bonding group, a carbon atom-carbon atom bond (single bond or double bond), a carbon atom-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom and the like), hetero An atom-heteroatom bond atomic group, a heterocyclic group and the like are arbitrarily combined. For example, as the atomic group,

[0118]

[Chemical 38]

[R ^{1 to} r ⁴ are each a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (eg, methyl group, ethyl group, propyl group) Etc.) etc. r ^{5 to} r ⁷ each represent a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) or the like. r ^{8 to} r ⁹ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, 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 is a heterocyclic ring containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom (eg, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring). ,
Pyrazine ring, pyrrole ring, piperazine ring, etc.) and the like.

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
It is preferable that the total number of atoms is 8 or more.
Here, the number of atoms in the connecting main chain means, for example, that A4 is -CO.
When representing O- or -CONH-, an oxo group (= O group) or a hydrogen atom is not included as the number of atoms, and a carbon atom, an ether-type oxygen atom, or a nitrogen atom constituting the connecting main chain is included as the number of atoms. Be done. Therefore, -COO- or -CONH
− Is counted as 2 atoms.

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

[0123]

[Chemical Formula 39]

[0124]

[Chemical 40]

[0125]

[Chemical 41]

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, -
SO ₂ Cl, epoxy group, etc.) is reacted with a monomer corresponding to the component x in the general formula (Pb), and then a reactive reagent containing a polymerizable double bond group is reacted. Then, a method of introducing a polymerizable double bond group by a polymer reaction can be mentioned.

Specifically, the polymerizable double bond group is prepared in accordance with the methods described in the above-mentioned review of the polymer (PG) containing a polymerizable double bond group at one end of the polymer main chain and the references cited therein. Can be introduced.

As another method, a difunctional monomer having different polymerization reactivity in radical polymerization reaction is used,
Examples thereof include a method described in JP-A-60-185962, in which a copolymer represented by the general formula (Pb) is synthesized by causing a polymerization reaction with a monomer corresponding to the component x to cause no gelation reaction.

In the resin represented by the general formula (Pb),
The abundance ratio of the x component and the y component is 90/10 to 99/1 mass ratio, and preferably 92/8 to 98/2 mass ratio. Within this range, there is no risk of gelation of the reaction mixture or coarsening of the generated resin particles during the polymerization granulation reaction.

The dispersion stabilizing resin (PG) used in the present invention may contain other repeating units as a copolymerization component in addition to the repeating units of the general formulas (Pa) and (Pb). Other copolymerizable components include those represented by 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 repeating unit of a) and (Pb). However, in order to obtain good dispersion stability of the dispersed resin particles, it is preferably used within a range of not more than 20 parts by mass based on 100 parts by mass of all polymer components.

The mass average molecular weight (Mw) of the dispersion stabilizing resin (P) of the present invention is preferably 2 × 10 ⁴ to 1 × 10 ⁶ .
It is more preferably 3 × 10 ⁴ to 2 × 10 ⁵ .

As described above, it is preferable to use the dispersion stabilizing resin (P) consisting of the block copolymer of the soluble component and the 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. Furthermore, it is preferable to use a dispersion stabilizing resin (PG) containing a polymerizable double bond group. In this case, the resin (PG) chemically bonds with the insoluble resin particles. It is considered that this causes a so-called steric repulsion effect by further improving the affinity of the soluble component of the dispersion stabilizing resin (P) sufficiently adsorbed or chemically bonded to the dispersed resin particles to the dispersion medium, and further improves 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), monomer (C), and macromonomer (MM) in a non-aqueous solvent benzoyl peroxide,
The heat polymerization may be carried out in the presence of a polymerization initiator such as azobisisobutyronitrile or butyllithium. In particular,
Method of adding polymerization initiator to mixed solution of dispersion stabilizing resin (P), monomer (A), monomer (B), monomer (C), and macromonomer (MM), dispersion stabilization Method in which the monomer (A), the monomer (B), the monomer (C), and the macromonomer (MM) are dropped together with the polymerization initiator into a solution in which the resin (P) for use is dissolved, or In a solution in which the dispersion stabilizing resin (P) is dissolved, a half amount of the monomer (A) and a mixture of the monomer (B) and a half amount of the monomer (A),
There is a method of dropping a mixture of the monomer (C), the macromonomer (MM) and the polymerization initiator at the same time, and the like, and any method can be used for production. The monomer (A), the monomer (B), the monomer (C), and the macromonomer (MM) used in the present invention are copolymerized by a polymerization reaction to be a resin insoluble in a non-aqueous solvent. .

The total amount of the monomer (A), the monomer (B), the monomer (C) and the macromonomer (MM) is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the non-aqueous solvent. It is about 10 parts by mass, and more preferably 10 to 80 parts by mass. The dispersion stabilizing resin (P) is preferably about 3 to 25 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of all the monomers used above. The amount of the polymerization initiator is appropriately about 0.1 to 10% by mass based on all monomers. The polymerization temperature is preferably about 40 to 180 ° C, more preferably 50 to 120 ° C. The reaction time is preferably about 3 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers and esters is used in combination in the non-aqueous solvent used in the reaction, or the unreacted product of the monomer to be polymerized and granulated is When it remains, it is preferably removed by heating it to a temperature above the boiling point of the polar solvent or monomer and distilling it off, or by distilling it off under reduced pressure.

The non-aqueous dispersion resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution. The average particle size is preferably 0.15
˜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 show positive chargeability due to the action of the polymerization components corresponding to the monomer (B) and the monomer (C).

The weight average molecular weight (M
w) (polystyrene conversion value by GPC method) is preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 8 × 1.
It is 0 ^{3 to} 5 × 10 ⁵ . As the thermophysical properties, the glass transition point is 0 ° C to 80 ° C or the softening point is 35 ° C to 12 ° C.
0 ° C is preferable, and more preferably the glass transition point is 10 ° C.
˜70 ° C. or softening point is 38 ° C. to 90 ° C.

The liquid developer of the present invention is excellent in dispersibility, storability, stability and redispersibility 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 the developing device, the dispersibility is good even after repeated use for a long time, and the redispersion is easy, and it is not observed that it adheres to each part of the device and causes stains.

Further, due to its good fixing property, a strong coating can be easily formed on the surface of the lithographic printing original plate when fixing is carried out by rapid processing such as heating after image formation. As a result, even in offset printing, printing on a large number of sheets (high printing durability) becomes possible. The liquid developer of the present invention which brings about the above effects is made possible by the non-aqueous latex provided by the present invention.

The liquid developer of the present invention contains a charge control agent (C
D) is used. Charge control agents are well known in the technical field of liquid developers for electrostatic photography, and specifically, "Development and practical use of recent electrophotographic development systems and toner materials" 139-1
48 pages, “The Basics and Applications of Electrophotographic Technology” edited by The Institute of Electrophotography 49
The compounds described on pages 7 to 505 (Corona Publishing, 1988), Yuji Harazaki “Electrophotography” 16 (N0.2), 44 (1977) and the like can be used. Preferred charge control agents include
Examples thereof include metal soaps, organic phosphoric acid 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-ethylhexynoic acid, 2-
Ethylcaproic acid, lauric acid, palmitic acid, elaidic acid, linoleic acid, ricinoleic acid, oleic acid, stearic acid, enanthic acid, naphthenic acid, ethylenediaminetetraacetic acid, etc.), resin acid, dialkylsuccinic acid, alkylphthalic acid, alkylsalicylic acid Metal salt 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, Japanese Patent Publication No. 49
-27707, JP-A-51-37651, JP-A-52-
38937, 52-107837, 53-12.
3138, etc.).

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

As the amphoteric surface active compound, lecithin,
Phospholipids such as kephalin (for example, Japanese Examined Patent Publication No. 51-470)
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,
Japanese Patent Publication No. 6-19596, No. 6-19595, No. 6-
No. 23865).

The charge control agents can be used alone or in combination of two or more kinds. The charge control agent is added in an amount of 0.001 to 1,000 parts by mass of the non-aqueous solvent that is a carrier liquid.
It is preferable to use about 1.0 part by mass.

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

As a result, in the liquid developer of the present invention, the charge amount of the dispersed particles is selectively increased, and the particles quickly and electrically correspond to the electrostatic latent image on the electrostatic recording body. It migrates and adheres to form a high-definition image. By the way, even if the total charge amount of the liquid developer is high, if the charge amount of the carrier liquid is large, these soluble ionic components adhere to the electrostatic latent image, and the adhesion of charged particles that should originally adhere is hindered. Or, the adhesion of particles is reduced due to the reduction of the charge of the latent image, and as a result, the reproduction of the fine dots becomes insufficient, or the edge portion of the image portion bleeds or flows, resulting in an image defect. Further, the liquid developer of the present invention is almost selectively and strongly retained on the particles, so that it is hardly affected by moisture due to a change in humidity, and the plate making environment changes from low humidity to high humidity. Even in this case, it is possible to stably form an image with good reproducibility.
Furthermore, the liquid developer of the present invention may be stored for a long period of time or under high temperature / high humidity (for example, 35 ° C./80% RH).
Even if plate making is carried out, the performance is completely the same as the case of using a fresh product immediately after the production of the liquid developer. This is because the charge characteristics of the liquid developer of the present invention, particularly the chargeability of positively charged particles, are stably maintained, and sufficient dispersibility is maintained without causing aggregation or precipitation between dispersed particles. It is believed that

If desired, various additives may be added to the liquid developer of the present invention, and the upper limit of the total amount of these additives is restricted by the electric resistance of the liquid developer. That is, the electric resistance of the ink with the dispersed particles removed is 10
^If it is lower than ⁹ Ωcm, it becomes difficult to obtain a good quality continuous tone image. Therefore, it is desirable to control the addition amount of each additive within this limit.

In the liquid developer of the present invention, it is preferable to include a coloring material as a coloring component together with the above-mentioned dispersed resin particles in order to inspect the plate after plate making. As the color material, any pigment and dye conventionally used in oil-based ink compositions or liquid developers for electrostatic photography can be used.

As the pigment, regardless of whether it is an inorganic pigment or an organic pigment, those 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 pigments, phthalocyanine pigments. , Quinacridone pigments, isoindolinone pigments, dioxazine pigments, slene pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, etc. Can be used without.

As the dyes, azo dyes, metal complex salt 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 preferable.

These pigments and dyes may be used alone or in an appropriate combination, but they are contained in the range of 0.05 to 5% by mass with respect to the entire liquid developer. Is desirable.

These color materials may be dispersed in the non-aqueous solvent as the color material itself as the dispersion particles in addition to the dispersion resin particles, or may be contained in the dispersion resin particles. As one of the methods for incorporating it, there is a method of dyeing a dispersed resin material with an appropriate dye as described in JP-A-57-48738. As another method, JP-A-53-54
As disclosed in No. 029, there is a method of chemically bonding a dispersion resin and a dye. Also, Japanese Patent Publication No.
As described in No. 2955 and the like, there is a method in which a dye-containing copolymer is prepared by using a dye-containing monomer in advance in the production by the polymerization granulation method. The production of a printing plate by the electrophotographic method using the liquid developer for electrostatic photography of the present invention can be carried out by a conventional method. Further, the liquid developer of the present invention,
It can also be used for ordinary electrostatographic copying.

[0153]

EXAMPLES Macromonomers used in the present invention are described below.
The present invention will be described in more detail by showing production examples and examples of resin particles, but the present invention is not limited thereto. Production Example 1 of Macromonomer (MM) 1: Macromonomer (MM-1) While stirring a mixed solution of 100 g of the monomer (M-1) having the following structure, 2 g of 3-mercaptopropionic acid and 200 g of toluene under a nitrogen stream. The temperature was raised to 70 ° C.
2,2'-azobis (isobutyronitrile) (abbreviation:
A. I. B. N. ) Was added and reacted for 4 hours. I. B. N. Was added for 3 hours, and A. I.
B. N. 0.3 g was added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 10 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight (Mw) of the polymer was 1 × 10 ⁴ (the weight average molecular weight is
G. P. The polystyrene conversion value by the C method is shown. same as below).

[0154]

[Chemical 42]

Production Examples 2-1 of Macromonomer (MM)
3: Macromonomer (MM-2) to (MM-13) In Production Example 1 of macromonomer (MM), only monomer (M-1) was replaced with each compound corresponding to the following Table-a. , And reacted in the same manner as in Production Example 1 to synthesize macromonomers (MM-2) to (MM-13). The mass average molecular weight of each obtained macromonomer is 9 × 10 ³ to 1 × 1.
It was in the range of 0 ⁴ .

[0156]

[Table 1]

[0157]

[Table 2]

Production Example 14 of Macromonomer (MM): Macromonomer (MM-14) While stirring a mixed solution of 100 g of the monomer (M-2) having the following structure, 2 g of thioethanol and 20 g of toluene under a nitrogen stream. The temperature was raised to 70 ° C. A. I. B. N. 1.0 g was added and reacted for 4 hours. In addition, A. I. B. N.
0.5 g was added for 3 hours, and then A. I. B.
N. 0.3 g was added and reacted for 3 hours. This reaction solution
Cooled to room temperature, 2-carboxyethyl acrylate 8g
Was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as D.C.C.) and 60 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butyl hydroquinone was added, and the mixture was stirred as it was for 4 hours. The precipitated crystals were filtered off and the obtained filtrate was reprecipitated in 2 liters of methanol. The oily substance that precipitated was collected by decantation, dissolved in 150 ml of methylene chloride, and reprecipitated again in 1 liter of methanol. The oily matter was collected and dried under reduced pressure to obtain a polymer having a yield of 60 g and an Mw of 8 × 10 ³ .

[0159]

[Chemical 43]

Production Examples 15 to 1 of Macromonomer (MM)
7: Macromonomer (MM-15) to (MM-17) In Production Example 14 of macromonomer (MM), monomer (M-2) and unsaturated carboxylic acid (corresponding to 2-carboxyethyl acrylate) were each Instead, in the same manner as in Production Example 14, the macromonomers shown in Table b below were each produced. The yield was 60 to 70 g, and the mass average molecular weight of each macromonomer obtained was in the range of 7 × 10 ^{3 to} 9 × 10 ³ .

[0161]

[Table 3]

Production Example 18 of Macromonomer (MM): Macromonomer (MM-18) A mixed solution of 100 g of a monomer (M-3) having the following structure, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was placed under a nitrogen stream at a temperature of 75. Warmed to ° C. 4,4 '
-Azobis (4-cyanovaleric acid) (abbreviation: AC).
V. ) Is added and reacted for 5 hours. C. V.
1.0 g was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liter of methanol, the oily matter was collected by decantation, and dried under reduced pressure. The yield was 85g. 50 g of this oil, 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine,
A mixture of 1.0 g of 2,2′-methylenebis (6-t-butyl-p-cresol) and 100 g of toluene was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in 1 liter of petroleum ether to give 63 g of white powder.
Got The mass average molecular weight was 7 × 10 ³ .

[0163]

[Chemical 44]

Production Example of Resin Particles (L) 1: Resin Particles (L)
-1) A mixture of 12 g of a dispersion stabilizing resin (P-1) having the following structure and 280 g of Isopar G was heated to 70 ° C while stirring under a nitrogen stream. Methyl methacrylate 15
g, 25.8 g of methyl acrylate, 4 g of macromonomer (MM-1), 6 g of 2- (N, N-dimethylamino) ethyl methacrylate and 2,2-azobisisovaleronitrile (abbreviation: AIVN) .), A mixture of 1.5 g of methyl methacrylate, a mixture of 15 g of methyl methacrylate, 30.2 g of methyl acrylate, 4 g of 3-sulfopropyl methacrylate and 10 g of ethanol were added dropwise at the same time in 1 hour and the mixture was stirred for 2 hours as it was.

Next, in A. I. V. N. Was added to 1.0 g, and the mixture was heated to a temperature of 75 ° C. and stirred for 4 hours. I. B.
N. 0.8 g was added and the mixture was heated to a temperature of 80 ° C. and stirred for 4 hours. Then raise the temperature to 100 ° C and reduce the pressure to 200mm.
The mixture was stirred under Hg for 2 hours, and ethanol and unreacted monomers were distilled off. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion had a polymerization rate of 99% and an average particle size of 0.1.
It was a 25 μm latex. Particle size is CAPA-50
0 (manufactured by HORIBA, Ltd.). A part of the white dispersion was centrifuged (rotation speed 1 × 10 ⁴ rpm,
The rotation time is 1 hour), and the settled resin particles are collected,
When dried and the mass average molecular weight (Mw) and glass transition point (Tg) of the resin particles were measured, Mw was 2 × 10 5.
⁵ (polystyrene equivalent value by G.P.C., the same below), Tg was 41 ° C.

[0166]

[Chemical formula 45]

Production Example 2 of Resin Particles (L): Resin Particles (L)
-2) A mixture of 16 g of a dispersion stabilizing resin (P-2) having the following structure and 283 g of Isopar G was heated to 70 ° C while stirring under a nitrogen stream. Methyl methacrylate 20
g, 26 g of ethyl acrylate, macromonomer (MM
-14) 3 g, 2- (N, N-diethylamino) ethyl methacrylate 8 g and A.I. I. V. N. , 1.5 g of a mixture and 15 g of methyl methacrylate, 23.6 g of methyl acrylate, 4.4 g of 3-sulfopropyl acrylate, and 10 g of ethanol were added dropwise at the same time in 1 hour, and the mixture was stirred for 2 hours as it was. Then A.
I. V. N. 1.0g and warm to a temperature of 75 ° C for 3
Stir for a period of time and then I. B. N. 0.8 g was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Then set the temperature to 1
The temperature was raised to 00 ° 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 2
The resulting white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.23 μm. The resin particles had Mw of 3 × 10 ⁵ and Tg of 41 ° C.

[0168]

[Chemical formula 46]

Production Examples 3 to 5 of Resin Particles (L): Resin Particles (L-3) to (L-5) In Production Example 1 of resin particles (L), 12 g of the resin (P-1) for dispersion stabilization and In place of 6 g of 2 (N, N-dimethylamino) ethyl methacrylate, 18 g of a dispersion stabilizing resin (P-3) having the structure shown below and 6 g of each monomer (B) shown in Table A below were used, and the above Production Example 1 was used. Each particle was manufactured in the same manner as in. The average particle size of the obtained particles is 0.20
It was a latex in the range of 0.25 μm. The resin particles had an Mw of 1 × 10 ^{5 to} 3 × 10 ⁵ and a Tg of 40 to 50 ° C.

[0170]

[Chemical 47]

[0171]

[Table 4]

Production Example 6 of Resin Particles (L): Resin Particles (L)
-6) A mixture of 14 g of a resin (P-4) for dispersion stabilization having the following structure and 280 g of Isopar G was heated to a temperature of 75 ° C while stirring under a nitrogen stream. To this, methyl methacrylate 1
5 g, methyl acrylate 22 g, macromonomer (M
M-6) 3 g, 4- (N, N-dimethylamino) methylstyrene 8 g and A.I. I. B. N. , 1.5 g of a mixture and 10 g of methyl methacrylate, 35.4 g of methyl acrylate, 6.6 g of 4-sulfomethylstyrene and 15 g of ethanol were added dropwise at the same time in 1 hour, and the mixture was stirred for 2 hours as it was. Then A. I. B. N. 1.0 g was added and the mixture was stirred for 3 hours. I. B. N.
0.8 g was added, and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Next, the temperature is raised to 100 ° C and the pressure reduction degree is 200 mmH.
The mixture was stirred under g for 2 hours, and ethanol and unreacted monomers were distilled off. After cooling, pass a 200 mesh nylon cloth,
The obtained white dispersion has a polymerization rate of 98% and an average particle size of 0.22.
It was a μm latex. Mw of resin particles is 9 × 1
0 ⁴ and Tg were 42 ° C.

[0173]

[Chemical 48]

Production Examples 7 to 20 of Resin Particles (L): Resin Particles (L-7) to (L-20) In Production Example 6 of resin particles (L), instead of the macromonomer (MM-6), Each particle was produced in the same manner as in Production Example 6 except that the macromonomer (MM) shown in Table B below was used. The average particle size of the obtained particles is 0.20
It was a latex in the range of 0.25 μm. The resin particles had a Mw of 8 × 10 ⁴ to 2 × 10 ⁵ and a Tg of 38 to 42 ° C.

[0175]

[Table 5]

Production Examples 21 to 26 of Resin Particles (L): Resin Particles (L-21) to (L-26) In Production Example 6 of resin particles (L), instead of 6.6 g of 4-sulfomethylstyrene. , 0.028 mol of each monomer (C) in the following Table-C (monomer (B) / monomer (C)
= 1.8 mol ratio), each particle was produced in the same manner as in Production Example 6 above. The average particle size of the obtained particles was latex in the range of 0.20 to 0.28 μm.
Mw of resin particles is 9 × 10 ⁴ to 2 × 10 ⁵ , and Tg is 40.
Each range was ˜48 ° C.

[0177]

[Table 6]

Production Example 27 of Resin Particles (L): Resin Particles (L-27) A mixture of 10 g of a dispersion stabilizing resin (P-5) having the following structure and 380 g of Isopar G was stirred at a temperature of 75 ° C. under a nitrogen stream. Heated. To this, vinyl acetate 42g, 2-
7 g of (N, N-dimethylamino) ethyl crotonate,
5 g of macromonomer (MM-15), and A. I. B.
N. , 1.5 g of the mixture and 40 g of vinyl acetate, 6 g of 3-sulfopropyl crotonate and 10 g of ethanol were added dropwise at the same time over 30 minutes, respectively, and then 3.
Stir for 5 hours. Then A. I. B. N. 1.0 g was added and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. I.
B. N. Of 0.8 g was added and the mixture was heated to a temperature of 85 ° C. and stirred for 3 hours. Next, the temperature is raised to 100 ° C. and the pressure reduction degree is set to 200.
The mixture was stirred under mmHg for 2 hours, and ethanol and unreacted monomers were distilled off. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 90% and an average particle size of 0.20 μm. The resin particles thus obtained had Mw of 8 × 10 ⁴ and Tg of 45 ° C.

[0179]

[Chemical 49]

Production Examples 28 to 32 of Resin Particles (L): Resin Particles (L-28) to (L-32) In Production Example 6 of resin particles (L), 14 g of the dispersion stabilizing resin (P-4) was used. Instead of using 12 g of the dispersion stabilizing resin (P-6) having the following structure and 8 g of 4- (N, N-dimethylamino) methylstyrene, 0.04 mol of each compound shown in Table D below was used. Each particle was produced in the same manner as in Production Example 6 above. The average particle size of the obtained particles is 0.2.
It was a latex in the range of 0 to 0.30 μm. Mw of resin particles is 1 × 10 ^{5 to} 3 × 10 ⁵ , and Tg is 40 to 50.
Each range was ° C.

[0181]

[Chemical 50]

[0182]

[Table 7]

Production Example 33 of Resin Particles (L): Resin Particles (L-33) 20 g of a dispersion stabilizing resin (P-7) having the following structure, 85 g of vinyl acetate, 2- (N, N-dimethylamino) ethyl croto Nate 6 g, 3-phosphonomethylstyrene 7 g, macromonomer (MM-1) 2 g and Isopar H 280 g
The mixture was heated to 75 ° C. with stirring under a nitrogen stream. A. I. V. N. 1.8 g was added and stirred for 4 hours. Next, A. I. B. N. 1.0 g was added and stirred for 3 hours. Then, the temperature is raised to 100 ° C.
The mixture was stirred under mmHg for 2 hours to distill off unreacted monomers. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 95% and an average particle size of 0.24 μm. Mw of resin particles is 8 × 10 ⁴ ,
The Tg was 41 ° C.

[0184]

[Chemical 51]

Production Example of Comparative Resin Particles 1: Resin Particles (L
L-1) In Production Example 1 of resin particles (L), 15 g of methyl methacrylate and 4 g of 3-sulfopropyl pyrmethacrylate
Particles were produced in the same manner as in Production Example 1 of resin particles (L), except that was changed to 19 g of methyl methacrylate. The white dispersion obtained had a polymerization rate of 99% and an average particle size of 0.24 μm.
m latex. Mw of resin particles is 2 × 10
⁵ , Tg was 41 ° C.

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

Production Example 3 of Resin Particles for Comparison: Resin Particles (L
L-3) In Production Example 2 of resin particles (L), 15 g of methyl methacrylate and 4.4 of 3-sulfopropyl 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 19.4 g of methyl methacrylate. The obtained white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.23 μm. Mw of 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 20 g of methyl methacrylate and 8 g of 2- (N, N-diethylamino) ethyl acrylate were changed to 28 g of methyl methacrylate in Production Example 2 of resin particles (L). The particles were produced in the same manner as in. The obtained white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.23 μm. The resin particles had Mw of 3 × 10 ⁵ and Tg of 42 ° C.

Example 1 and Comparative Examples A to B <Preparation of printing original plate> 200 g of photoconductive zinc oxide, 2 g of resin (B-1) having the following structure, and resin (B-2) having the following structure.
18 g, 0.018 g of the 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.) to rotate at a rotation speed of 6 ×.
A photosensitive layer-forming composition was prepared by dispersing at 10 ³ rpm for 10 minutes, and the composition was coated on a support for ELP master 2X type (manufactured by Fuji Photo Film Co., Ltd.) so that the dry adhesion amount was 20 g /
As a m ^2, it was coated by a wire bar, 1 at 110 ° C.
A printing original plate was prepared by drying for 0 seconds and then leaving it in the dark at 20 ° C. and 65% RH for 24 hours.

[0190]

[Chemical 52]

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

Production of Resin Particles (L) Resin Particles (L
-1) 6 g (as solid content), 2.5 of the above blue dispersion
g (as solid content), tetradecyl alcohol (FO
C-1400, manufactured by Nissan Kagaku Co., Ltd., and 15 g of zirconium naphthenate and 0.09 g of zirconium naphthenate were diluted to 1 liter of Isopar G to obtain a liquid developer for electrostatic photography (LD-).
1) was produced.

<Production of Comparative Developers A and B> In the production of the above liquid developer (LD-1), resin particles (L-
Comparative liquid developers A and B 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 charge characteristics, image reproducibility, printability, etc. of these liquid developers were examined, and the results are shown in Table-E.

[0194]

[Table 8]

The evaluations shown in Table-E were carried out as follows. Note 1) Charging characteristics / AC electric conductivity AC electric conductivity (pS / c)
m) is an LCR meter (Ando Electric Co., Ltd. AG-431)
It was 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 through a test lead (Ando Electric Co., Ltd. AG-4912). It is connected to a special electrode (LP-05 manufactured by Kawaguchi Electric Co., Ltd., electrode constant 198), conductance is measured at an applied voltage of 5 V and a measurement frequency of 1 kHz, and the value is divided by the electrode constant to be converted into electric conductivity. did. At the time of measurement, the measurement parameter of the LCR meter was set to capacitance, and the circuit mode was set to parallel mode.

Particle Charge Fraction As shown by the following equation, it represents the ratio of the charge amount of dispersed particles in the liquid developer.

[0197]

[Equation 1]

Here, the charge amount of the supernatant was determined by centrifugation of the liquid developer (condition: 1 × 10 ⁴ rpm 2 hours).
Represents the AC electric conductivity of a transparent liquid which is a supernatant obtained by allowing the particles to settle.

Conditions I and II show that the aging condition after the liquid developer is manufactured is changed, and condition I means that the liquid developer obtained by mixing all the components is kept at room temperature and normal humidity ( 25 ° C,
65% RH) aged for 1 week (fresh product)
On the other hand, the condition II is that the fresh product is stored under conditions of high temperature and high humidity (35 ° C., 85% RH) for 1 month,
It is a product that has been forcibly aged (aged product).

Note 2) Image reproducibility The above printing original plate was charged at -6 kV and 2.8 as a light source.
A mW-output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) was used to irradiate 6.4 μjoul / cm ² on the surface of the printing original plate, exposed at a pitch of 25 μm and a scanning speed of 300 m / sec, and then a liquid developer. Is developed using each of the liquid developers described above, and Isopar G (Esso Chemical Co., Ltd.), which is an isoparaffinic solvent, is used.
After rinsing with a rinsing solution (1), the image was formed by fixing at a plate surface temperature of 70 ° C. for 10 seconds. Fogging, image quality of the image and the like of the obtained plate-making image were visually evaluated. Note 3) Printability The original plate on which an image was formed according to the method of image reproducibility described above was used as a desensitizing solution ELP-E2 (Fuji Photo Film Co., Ltd.).
(Manufactured by K.K.) was used to make a printing plate by passing through an etching machine once. The printing plate thus obtained was printed using a solution of ELP-E2 (manufactured by Fuji Photo Film Co., Ltd.) diluted 20 times with water as fountain solution, and neutral paper as the base paper for printing. Printing was performed by using a Hamada Star 800SX type (manufactured by Hamada Star Co., Ltd.) as a machine, and the quality of the printed matter of the 10th printed sheet and the number of printed sheets in which there was no omission in the image portion of the printed matter 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 total charge amount and the particle charge fraction. . On the other hand, in Comparative Example A, the change amount of the total charge amount with time was relatively small, but the change of the charge fraction of the particles was large. In Comparative Example B, the total charge amount and the particle charge fraction were low, and further decreased with time. When an image was actually formed, the liquid development of the present invention was good under both conditions I and II. In Comparative Example A, the occurrence of background fog was observed under Condition II, and in Comparative Example B, image smearing occurred on the entire surface. When printed as a printing plate, when the liquid developer of the present invention was used, clear printed matter of 10,000 sheets or more was obtained even under the condition II.
On the other hand, Comparative Examples A and B could not be put to practical use as printed matter after 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 Paint shaker (Toyo Seiki Co., Ltd.)
Manufactured) and dispersed for 6 hours to obtain a fine dispersion of nigrosine. 6 g of resin particles (L-2) (as solid content),
Liquid for electrostatic photography by diluting 3 g of the above nigrosine dispersion (as solid content), 0.11 g of cobalt octenoate salt and 10 g of branched hexadecyl alcohol (FOC-1600, manufactured by Nissan Kagaku Co., Ltd.) into 1 liter of Isopar G. A developer (LD-2) was produced. <Production of Comparative Developers C and D> The liquid developer (LD
-2), except that the resin particles (L-2) are replaced with the following resin particles, the liquid developer C for comparison is similarly used.
And D were made. 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 liquid developer is fully automatic plate-making machine ELP58.
ELP, which is an electrophotographic light-sensitive material, is used as a developer of 0RX (manufactured by Fuji Photo Film Co., Ltd.) and a desensitizing solution ELP-PEX (manufactured by Fuji Photo Film Co., Ltd.) is used.
A master 2X type (manufactured by Fuji Photo Film Co., Ltd.) was exposed, developed and desensitized. Blackening rate (image area)
A 35% original was used. The plate making speed was 6 plates / minute. After processing 10,000 sheets of the ELP master 2X type, the presence or absence of toner adhesion stains on the developing device was observed. The results are shown in Table-F.

[0203]

[Table 9]

A plate made using the liquid developer of the present invention,
Even after 10,000 plates, the developing device did not become dirty. Comparative Example C
In D and D, stains on the developing device due to adhesion of toner dust were observed. Further, printing was carried out by a conventional method using the 10,000th printing plate for offset obtained by plate-making, and the number of printed sheets until the occurrence of character loss in the image of the printed matter, scraping of the solid portion, etc. was examined. The printing plate obtained 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 the printed matter occurred after printing. Further, a developer (LD-2) aged under the condition II of the example (stored at 35 ° C./85% RH for 1 month) was subjected to the same test as above, and the performance almost equivalent to that of the fresh product was obtained. showed that. From the above results, it is understood that the liquid developer of the present invention does not stain the developing device at all, and at the same time, the printing plate obtained has excellent printing durability.

Example 3 <Preparation of printing original plate> The following photoconductive layer coating solution was applied on a grained and positively oxidized aluminum plate with a bar coater and dried at 120 ° C. for 10 minutes to form a film. Thickness 3.
An original plate for printing 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 the above composition was added at a high speed. It was dispersed for 2 hours with a dispersion mixer Dynamill (KDL-5, manufactured by WABACHOFEN) to obtain a coating liquid for a photoconductive layer.

<Production of Liquid Developer (LD-3)> 9 g of resin particles (L-1) of Production Example 1 of resin particles (L) (as solid content), tetradecyl alcohol (FOC140).
0) 10 g and 0.15 g of octene-semi-maleic acid dodecylamide copolymer were adjusted to 1 liter with Isopar H to prepare a liquid developer (LD-3). When the charge characteristics were measured by the same method as described in Example 1,
The results shown in Table G below were obtained.

[0208]

[Table 10]

[0209] Even after the passage of time under harsh conditions, it showed a charge characteristic almost equivalent to that of the fresh product and extremely stable.

The printing plate having the above-mentioned 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 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, the liquid developer (LD-3) of the present invention was used to perform reversal development under the condition of a bias voltage of +180 V, and then the image was fixed by heating at a temperature of 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 were mixed with 900 parts of water.
A non-image area was removed by immersing in a diluted etching solution for 10 seconds, washed sufficiently with water and dried to prepare a printing plate. When this printing plate was visually evaluated with a magnifying glass of 60 times (manufactured by PEAK Co., Ltd.), no fine lines or fine characters in the image area were observed and the image was extremely clear. Next, this printing plate
After gumming treatment, offset printing machine (Oliver 52
The pattern was printed on 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 observed. Further, when the liquid developer under the condition II was used to carry out plate making, etching treatment and printing in the same manner as described above, the same result as that of the fresh product was obtained.

[0211] Furthermore, when the printing plate precursor was made into a 5000 plate and examined for stains on the developing section, no stain such as adhesion of toner dust was found, and the liquid developer had very good redispersibility. showed that. In addition, when the image on the printing plate after the 5000th plate was etched 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 stable charging characteristics even when aged under severe conditions in an electrophotographic plate making system in which a non-image area is eluted to form a printing plate, and has excellent dispersibility. , Showed redispersibility. Further, the printing durability was also satisfactory.

Examples 4 to 21 Each liquid was prepared in the same manner as in Example 1 except that resin particles shown in Table H below were used in place of the resin particles (L-1) in Example 1. A developer was prepared. The AC electric conductivity of the obtained developer was 95 to 100 (pS / cm), and the charge fraction of the particles was 90 to 95%. Also, in the case of condition II, almost no change occurred.

[0213]

[Table 11]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1, and its performance was examined. Each liquid developer exhibits the same performance as in Example 1,
The image reproducibility, dispersibility, and printability were good. Also,
Under the condition II, all the developers exhibited the same performance and were good.

Examples 22 to 34 Each liquid was prepared in the same manner as in Example 2 except that resin particles shown in Table I below were used instead of the resin particles (L-2) in Example 2. A developer was prepared.

[0216]

[Table 12]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 and its performance was examined. Each liquid developer exhibits the same performance as in Example 2,
The image reproducibility, dispersibility, and printability were good. Further, the developing device did not stain as in the second embodiment. Further, each developer exhibited the same performance even under the condition II and was good.

Example 35 A photosensitive drum made of amorphous silicon was rotated at a peripheral speed of 10 mm / sec and the dispersion liquid described below was supplied to the surface of the photosensitive member using a slit electrodeposition apparatus, while the photosensitive member side was grounded and slit voltage was applied. A voltage of +200 V was applied to the electrode side of the deposition device to electrodeposit the resin particles. Then, the dispersion liquid was removed by air squeeze and the film was melted and filmed by an infrared line heater to form a thermoplastic resin transfer layer having a film thickness of 1.5 μm on the photoconductor. <Transfer Layer Forming Dispersion> Dispersion stabilizing resin [octadecyl methacrylate / acrylamide (97/3 mass ratio) copolymer, mass average molecular weight: 4 × 10 ⁴ ] 12 g, vinyl acetate 98 g, stearyl methacrylate 2 g and Isopar H384 g The mixed solution was heated to 70 ° C. with stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation A.I.V.N.) was added as a polymerization initiator and reacted for 3 hours. Add the initiator 2
A cloudiness occurred after 0 minutes, 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 stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, pass through a 200-mesh nylon cloth to give a white dispersion (polymerization rate 90%, average particle size 0.23μ
m) was obtained. 10 g of the thermoplastic resin dispersion (as a solid content) and 0.001 g of zirconium naphthenate were added to 1 liter of Isopar H to prepare a positively charged resin particle dispersion liquid. An electrophotographic process was immediately performed while maintaining the surface temperature of the photoconductor at 40 ° C. First, after corona charging this photoreceptor to + 700V in the dark, read it from the original document in advance and expose it with 780 nm light using a semiconductor laser based on the information stored in the hard disk in the system as digital image data. did. The potential of the exposed portion was + 220V and that of the unexposed portion was + 660V. Then, after pre-bathing with 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. At this time, a developing bias voltage of +500 V was applied to the developing unit side to carry out reversal development so that the toner was electrodeposited on the unexposed portion. Then, rinsed in a bath of Isopar H alone to remove stains on the non-image area, the liquid was drained by an air squeeze, passed through an infrared line heater and dried. <Preparation of liquid developer (LD-4)> Blue pigment (Linol Blu
e FG-7350, manufactured by Toyo Ink Co., Ltd./Octadecyl methacrylate-methacrylate (7/3 mass ratio) Isopar G dispersion 4 g consisting of 1/1 mass ratio of block copolymer
(As solid content), 8 g (as solid content) of resin particles (L-21) and 0.06 g of octadecyl vinyl ether-semi-maleic acid dodecylamide copolymer were diluted to 1 liter of Isopar G to prepare a liquid developer (LD).
-4) was produced. Next, let it pass under the infrared line heater and measure the surface temperature with a radiation thermometer to measure about 80
After preheating to ℃, superimpose the coated paper on the photoreceptor with the transfer layer, and contact it with a pressure of 10 kgf / cm ² (980 kPa). Was passed at a speed of 15 mm / sec. Then, when the coated paper was peeled off after passing through a cooling roller to cool it, 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 color image obtained was extremely clear and no fog was observed in the non-image area. or,
Even when the liquid developer (CD-4) was forcibly aged as in Example 1 (condition II), no difference from the fresh product was observed,
It was clear.

[0219]

INDUSTRIAL APPLICABILITY The liquid developer of the present invention accelerates the developing-fixing process by using specific resin particles, and stabilizes the charge of particles even in an electrophotographic plate making system using a large plate master plate. It is possible to provide an offset printing plate having excellent properties, dispersion stability, redispersibility, and fixability, and having excellent printing ink oil sensitivity and printing durability.

Claims (2)

[Claims] 1. A liquid developer for electrostatic photography 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, wherein the dispersed resin particles are A monomer (A containing at least one monofunctional monomer (A) which is soluble in a non-aqueous solvent and becomes insoluble by polymerization, and an amino group represented by the general formula (I). ) and at least one copolymerizable monofunctional monomer (B), -PO ₃ H ₂ group, -SO ₃ H group and -SO ₂ H
At least one monofunctional monomer (C) copolymerizable with the monomer (A), containing at least one acidic group selected from the group, and having a substituent containing a fluorine atom and / or a silicon atom. A monomer having a mass average molecular weight of 2 × 10 ⁴ or less, in which a polymerizable double bond group represented by the following general formula (MI) is bonded to only one end of a main chain of a polymer composed of repeating units. At least one monofunctional macromonomer (MM) copolymerizable with (A), and the following general formula (P
Electrostatically characterized by being copolymer resin particles obtained by polymerizing and granulating a solution containing at least one dispersion stabilizing resin (P) which is a polymer containing the component I). Liquid developer for photography. [Chemical 1] In formula (I), 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 each other to form a ring together with a nitrogen atom. May be formed. [Chemical 2] In formula (MI), J ¹ is -COO-, -OCO-,-(C
_{H 2) d COO -, -} (CH 2) d OCO -, - O -, - SO
_2- , -CONHCOO-, -CONHCONH-,-
CON (K ¹ )-, -SO ₂ N (K ¹ )-, or a phenylene group (wherein K ¹ is a hydrogen atom or 1 to 2 carbon atoms).
2 represents an alkyl group, and d represents an integer of 1 to 4). m
¹ and m ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, —COO—K ² , or —COO— via a hydrocarbon group. represents a K ² (where K ² is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). [Chemical 3] In formula (PI), A ¹ is -COO-, -OCO-,-.
(CH ₂ ) _a COO-,-(CH ₂ ) _a OCO-, -O-,
Or [Chemical 4] (Where E is a direct bond, -O-, -OCO- or -CO
Represents O-). a represents the integer of 1-12. 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 as or different from each other, and each is 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. Represents D ¹ (where D ¹
Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms). 2. The dispersion stabilizing resin (P) has a polymerizable double bond group represented by the following general formula (PII) bonded to one end of its polymer main chain or a substituent of a polymer repeating component. The liquid developer for electrostatic photography according to claim 1, wherein [Chemical 5] In general formula (PII), A ² is -COO-, -OCO-,-.
_{(CH 2) b COO -,} - (CH 2) b OCO -, - O-,
_{-SO 2 -, - CONHCOO -,} - CONHCONH
^{-, - CON (E 1)} -, - SO 2 N (E 1) - ( wherein E ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, b is an integer of 1 to 4) Or [Chemical 6] (Here, E ² is a direct bond, —O—, —OCO— or —COO.
-Indicates). q ¹ and q ² may be the same as or different from each other and have the same meaning as p ¹ and p ^{2 in} formula (PI).