JP2003149878A - Liquid developer for electrostatic photography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer excellent in dispersion stability, re- dispersing property and fixing property even in an electrophotographic plate making system including a fast developing-fixing process and using a large-size master plate. SOLUTION: The liquid developer for electrostatic photography is prepared by subjecting a dispersion liquid containing a monomer (A) which is soluble in a nonwater solvent and changes into insoluble by polymerization, a resin (P) for stabilization of dispersion, which is a polymer having at least a specified component and is dispersed in a colloidal state in the above nonwater solvent, and seed particles (CR) having 0.05 to 1.0 μm average particle size to the seed polymerization reaction to obtain dispersion resin particles (CSR) having a multilayered structure, and then dispersing the obtained particles in a nonwater solvent having >=10<9> Ω.cm resistivity and <=3.5 dielectric constant.

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 electrostatic photography, and more particularly to a liquid developer having excellent redispersibility, fixing property and resist property.

[0002]

2. Description of the Related Art A general electrophotographic liquid developer 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, which are petroleum-based. 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. For this reason, there is a drawback that the soluble dispersion stabilizing resin is desorbed from the insoluble latex particles due to long-term storage or repeated use, and the particles settle, aggregate, or accumulate, or the polarity becomes unclear. Further, the particles once aggregated and accumulated are difficult to re-disperse, so that the particles remain attached to various places of the developing machine, which leads to the failure of the developing machine such as dirt on the image area and clogging of the liquid feeding pump. As these improvements, a non-aqueous dispersion polymerization method for obtaining inert latex particles having a fine particle diameter and good monodispersity has been proposed and various studies have been made. For example, US Pat. No. 3,990,98
No. 0, 4,618, 557 and JP-A 1-25796.
No. 9, No. 2-74956, No. 1-282566, No.
No. 4,842,975, a method of improving with a resin for stabilizing soluble dispersion is disclosed in US Pat. No. 4,842,975.
JP-A-62-151868, JP-A-1-2376.
No. 68, No. 2-168276, No. 3-13964,
No. 3-20753 describes a method for modifying the surface of latex particles by allowing an insolubilizing monomer and another compound having a physicochemical interaction to coexist. It is disclosed that the dispersibility and storage stability can be improved.

[0003]

On the other hand, the practical application or development of a direct lithographic printing system to which an electrophotographic technique is applied has been actively carried out in recent years. These systems
After forming a toner image portion on the surface of an electrophotographic photosensitive material by an electrophotographic method, the toner image portion is processed to convert the non-image portion into a hydrophilic material to obtain a lithographic printing original plate. As a method for making the non-image portion hydrophilic, a method of utilizing the hydrophilicity of the surface of the support under the electrophotographic photosensitive layer by eluting the portion with a processing liquid, or a surface portion of the non-image portion of the photosensitive layer The main method is to modify the oil from lipophilic to hydrophilic.

In the latter case, as an improvement of the conventionally known method for desensitizing the photoconductive zinc oxide of the photosensitive layer,
JP-A-62-21669, JP-A-1-191157
No. 2,15,277 and the like disclose that hydrophilicity is improved by converting the binder resin used in the photosensitive layer into hydrophilicity by treatment. In these systems, it is important to maintain the image portion of the toner image portion without any change with respect to the treatment liquid in the hydrophilic treatment (hereinafter referred to as the resist property to the treatment liquid).

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, the resist property of the toner is not sufficient if the non-image area is sufficiently hydrophilized. In some cases, the image part was missing. In particular, this problem becomes remarkable at a place where the area of the toner image portion such as a thin line, a character or a halftone dot portion is small, and the characteristics of the printed matter are deteriorated. Further, insoluble latex particles having high durability to the treatment liquid (for example, styrene-based latex) have sufficient resist properties, but have poor charge stability and redispersibility as toner particles. Since the fixing property of the toner particles is inferior, sufficient fixing requires a high heat and a long fixing time, which is a problem in device design.

The present invention solves the problems of the conventional liquid developers described above. Therefore, an object of the present invention is to provide a liquid developer which has a rapid development-fixing process and is excellent in dispersion stability, redispersibility and fixing property even in an electrophotographic plate making system using a large plate size master plate. It is to be. Another object of the present invention is to provide a liquid developer which is excellent in dispersion stability, redispersibility, charge stability, fixability and hydrophilic treatment liquid resist property in an electrophotographic plate making system. Another object of the present invention is to
It is an object of the present invention to provide a liquid developer which enables the production of an original plate for offset printing having excellent oil sensitivity and printing durability by electrophotography. Still another object of the present invention is to provide a liquid developer suitable for image formation using various electrostatographic methods.

[0007]

It has been found that the above objects can be achieved by the following liquid developers for electrostatography.

(1) In a liquid developer for electrostatic photography, wherein at least resin particles are 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, the dispersed resin particles are In the non-aqueous solvent, at least one monofunctional monomer (A) that is soluble in the non-aqueous solvent and becomes insoluble by polymerization, and at least a polymerization component represented by the following general formula (I). A dispersion liquid containing at least one kind of dispersion-stabilizing resin (P) formed by colloidally dispersing in the non-aqueous solvent, and seed particles (CR) having an average particle diameter of 0.05 to 1.0 μm. Obtained by a seed polymerization reaction,
A liquid developer for electrostatic photography, which is a dispersion resin particle (CSR) having a multilayer structure.

[0009]

[Chemical 6]

In the general formula (I), V ⁰ is --COO-- or --O.
_{CO -, - (CH 2)} r COO -, - (CH 2) r OCO-,
-O- or

[0011]

[Chemical 7]

(Where X is a direct bond, -O-, -OCO
-Or-COO-) is represented. r represents an integer of 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. b ¹ and b ² may be the same as or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹ , or —COO-D ¹ via a hydrocarbon group ( Where D
¹ represents a hydrogen atom or an optionally substituted hydrocarbon group).

(2) The dispersion stabilizing resin (P) comprises a block containing at least the polymerization component represented by the general formula (I) and a block not containing the polymerization component represented by the general formula (I). A liquid developer for electrostatic photography according to (1) above, which is a block copolymer. (3) The non-aqueous solvent dispersion further contains at least one monofunctional monomer (B) represented by the following general formula (II), which is copolymerizable with the monomer (A). The liquid developer for electrostatic photography according to (1) or (2) above, which is characterized.

[0014]

[Chemical 8]

In the general formula (II), U ¹ is --COO-- or --C.
^{ONH -, - CON (E 2} ) - ( wherein, E ² represents a group represented by the aliphatic group or a group represented by the general formula (IIa)), -
OCO -, - CONHCOO -, - CH 2 COO -, -
(CH _{2) S} OCO- (wherein, s represents an integer of 1 to 4), - represents a -COO- O-or -C ₆ H _4. d ¹ and d ² may be the same or different and each is a hydrogen atom,
Alkyl group, a halogen atom, a cyano group, -COO-E ³
Alternatively, it represents —CH ₂ COO—E ³ (wherein E ³ represents an aliphatic group). E ¹ represents an aliphatic group having 8 or more carbon atoms or a total number of 8 or more atoms (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom) represented by the following general formula (IIa). Formula ^{(IIa) - (A 1 -B} 1) m - (A 2 -B 2) n -R 21 in the formula (IIa), R ²¹ is a hydrogen atom or a carbon atoms 1 to 1
8 represents an aliphatic group. B ¹ and B ² may be the same or different and each is —O—, —S—, —CO—, —CO ₂
-, - OCO -, - SO 2 -, - N (R 22) -, - CO
N (R ²² )-, -N (R ²² ) CO-, -N (R ²² ) SO
_{2 -, - SO 2 N (} R 22) -, - NHCO 2 - or -N
HCONH- (wherein R ²² has the same meaning as R ²¹ above). A ¹ and A ² may be the same or different and each represents a group represented by the following general formula (IIb) and a carbon number of 1 to 18
Represents at least one group selected from among the hydrocarbon groups of m and n may be the same or different and each represents an integer of 0 to 4. However, the sum of m and n never becomes zero.

[0016]

[Chemical 9]

In the general formula (IIb), B ³ and B ⁴ may be the same or different and have the same meanings as B ¹ and B ² , respectively,
A ⁴ represents a hydrocarbon group having 1 to 18 carbon atoms, R ²³ has the same meaning as R ²¹ , and p represents an integer of 0 to 4. (4) The non-aqueous solvent dispersion further comprises the following general formula (I
(1) to (3), which contains at least one monofunctional monomer (C) copolymerizable with the monomer (A) having an amino group represented by V). ) A liquid developer for electrostatic photography according to any one of 1) to 4) above.

[0018]

[Chemical 10]

In the general formula (IV), R¹And R²Is the same
They may be different, and each is a hydrogen atom or a carbon atom having 1 to 22 carbon atoms.
Represents a hydrogenated group or R¹And R²Combined with the nitrogen atom
May form a ring. (5) The non-aqueous solvent dispersion further contains -PO.₃H₂ 
Group, -SO₃H group and -SO ₂An acidic group selected from H groups
Copolymerizable with monomer (A) containing at least one
Contain at least one monofunctional monomer (D)
The liquid development for electrostatic photography according to (4) above,
Agent.

[0020]

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 is a fluorocarbon solvent as a halogen-substituted hydrocarbon solvent, for example, perfluoroalkanes represented by C _n F _{2n + 2} such as C ₇ F ₁₆ and C ₈ F ₁₈ (“Fluorinate 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 are 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 Ω · cm, and the lower limit of the dielectric constant is preferably about 1.80.

The dispersed resin particles (CSR) (hereinafter sometimes referred to as latex particles) in the liquid developer of the present invention are present in a non-aqueous solvent in the presence of the dispersion stabilizing resin (P) containing a specific component. In addition, it is obtained by polymerizing and granulating at least a monofunctional monomer (A) and seed particles (CR) having an average particle diameter of 0.05 to 1.0 μm.

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 used in combination 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 resistance satisfies the condition of 10 ⁹ Ω · cm or more.

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 dispersion, and as described above, a linear or branched aliphatic hydrocarbon or alicyclic hydrocarbon. , Aromatic hydrocarbons, halogenated hydrocarbons and the like.

The dispersed resin particles (CSR) of the present invention are particles having a multilayer structure having a core layer composed of seed particles (CR) and a shell layer on the outside thereof, and are a monomer (A) and optionally used. The monomer (B), the monomer (C) and the monomer (D) are polymerized or copolymerized to form a resin that forms a shell layer insoluble in a non-aqueous solvent.

Monofunctional monomer (A) used in the present invention
May be any monofunctional monomer that is soluble in the non-aqueous solvent but is insolubilized by polymerization. Specific examples include monomers represented by the following general formula (V).

[0033]

[Chemical 11]

In the general formula (V), V ² 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 aliphatic group having 1 to 6 carbon atoms which may be substituted (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.).

A ¹ and a ² may be the same as or different from each other, and preferably each is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, and a carbon number of 1 to 3.
Alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), - COO-Q ² or -CH ^₂ -COO-Q ₂ [wherein Q ² is 1 hydrogen atom or a carbon atoms which may be substituted,
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, vinylthiazole and N-vinylmorpholine). The monomer (A) may be used in combination of two or more kinds.

Next, the seed particles (C
R) will be described. The seed particles are made of resin and have an average particle size of 0.05 to 1.0 μm, preferably 0.1.
~ 0.6 μm. By using such seed particles, resin particles having a core / shell structure of the present invention (CS having an average particle size of about 0.1 to 3 μm and good monodispersity) (CS
R) can be easily produced.

The binder resin forming the seed particles is a resin which is insoluble in the non-aqueous solvent to be dispersed, is solid at least at room temperature, and is more preferably solid at a temperature of 35 ° C. or lower and is hydrophobic. It is preferable. This resin has a glass transition point of −40 ° C. to 100 ° C. or a softening point of 30.
C. to 120.degree. C., more preferably a glass transition point of -10.degree. C. to 80.degree. C. or a softening point of 35 to 1
It is 00 ° C. By using a resin having such a glass transition point or a softening point, the fixability of an image is favorably maintained, which is preferable.

The mass average molecular weight (Mw) of the binder resin constituting the seed particles is preferably 3 × 10 ³ to 1 × 1.
It is 0 ⁶ , more preferably 5 × 10 ³ to 8 × 10 ⁵ , and further preferably 1 × 10 ^{4 to} 5 × 10 ⁵ .

As the binder resin, for example, Yuji Harazaki et al., "Latest Binder Technology Handbook", Comprehensive Technology Center Co., Ltd. (1985), Koichi Nakamura, "Practical Technology of Binder for Recording Materials," CMC Co., Ltd. (1985) ), Chubu Business Development Center-Publishing Department, "Synthesis and design of acrylic resin and new application development" published by CMC Co., Ltd. (1985), supervised by Koichi Nakamura "Recent development of electrophotographic development system and toner materials Practical use ”Each of the resins described in, for example, Japan Science Information Publishing Co., Ltd. (1985).

Specifically, olefin polymers and copolymers (for example, polyethylene, polypropylene, polyisobutylene, ethylene-vinyl acetate copolymer, ethylene-
Acrylate copolymer, ethylene-methacrylate copolymer, ethylene-methacrylic acid copolymer, etc.), vinyl chloride polymer and copolymer (for example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, etc.), vinylidene chloride copolymer Polymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, polymers and copolymers of styrene and its derivatives (e.g. butadiene-styrene copolymers, isoprene-styrene copolymers, Styrene-methacrylate copolymer, styrene-acrylate copolymer, etc.), acrylonitrile copolymer, methacrylonitrile copolymer, alkyl vinyl ether copolymer, acrylic acid ester polymer and copolymer, methacrylic acid ester polymer and Copolymer, itaconic acid diester polymer and Polymers, maleic anhydride copolymers, acrylamide copolymers, methacrylamide copolymers, phenolic resins, alkyd resins, polycarbonate resins, ketone resins, polyester resins, silicone resins,
Amide resin, hydroxyl group- and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, urethane resin, rosin resin, hydrogenated rosin resin,
Petroleum resin, hydrogenated petroleum resin, maleic acid resin, terpene resin, hydrogenated terpene resin, chroman-indene resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, nitrogen atom A copolymer containing a heterocycle that does not contain (for example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, a 1,3-dioxetane ring, etc.), Epoxy resin etc. are mentioned. These binder resins may be used alone or in combination of two or more kinds.

The seed particles used in the present invention can be produced by a conventionally known mechanical pulverization method, a method utilizing a difference in solubility or a polymerization granulation method. As a mechanical pulverization method, materials to be particles (binder resin and additives used if necessary) are mixed, melted and kneaded, and then directly pulverized by a conventionally known pulverizer to form fine particles, and a dispersion polymer is used in combination. Then, a method of further dispersing with a wet disperser (for example, a ball mill, a paint shaker, a kedy mill, a dyno mill, etc.), a material as a particle component and a dispersion-aiding polymer (or a coating polymer) are previously kneaded to form a kneaded product, which is then ground. ,
Next, there is a method in which a dispersion polymer is allowed to coexist and is dispersed. The method utilizing the difference in solubility is a method in which a material serving as a particle component is dissolved under heating in an insulating solvent mixed with a polar solvent which dissolves the material, and then the temperature is lowered to precipitate the material as particles.

Specifically, a method for producing a paint or a liquid developer for electrostatic photography can be used. Regarding these, for example, "Flow of paint and dispersion of pigments" translated by Kenji Ueki.
Kyoritsu Shuppan (1971), Solomon "Paint Science" Hirokawa Shoten (1969), Yuji Harasaki "Coating Engineering" Asakura Shoten (1971), Yuji Harasaki "Basic Science of Coating" Maki Shoten (1977), etc. Or Japanese Patent Laid-Open No. 61-180
248, Japanese Patent Nos. 2,684,378, and 2,
No. 614,070 and JP-A No. 6-256529.

A preferable mode for producing the seed particles used in the present invention is a method of synthesizing the particles by a polymerization granulation method. Examples of the polymerization granulation method used include conventionally known non-aqueous dispersion polymerization methods, and specifically,
Supervised by Soichi Muroi "Latest Technology of Ultrafine Polymers" Chapter 2,
CMC Publishing (1991), Koichi Nakamura, "Development and Practical Use of Recent Electrophotographic Development Systems and Toner Materials," Chapter 3 (1985, published by Japan Science Information Co., Ltd.), KEJ Barrett, "Dispers
ion Polymerization in Organic Media '' John Wiley (19
(75 years) etc.

The dispersion polymer used in the production of seed particles by the polymerization granulation method contains a polymerization component represented by the general formula (I) which is soluble in a non-aqueous solvent, like the dispersion stabilizing resin (P). Resin or an olefinic resin soluble in a non-aqueous solvent (for example, styrene-butadiene copolymer, α
-Olefin copolymer, vinyltoluene copolymer, etc.) and the like. The proportion of the dispersion polymer used is particle component 1
The amount is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 00 parts by mass. Within this range, the particle size distribution of the seed particles becomes sharp, and aggregation and precipitation of the particles are suppressed, which is preferable.

Next, in the present invention, the dispersion stabilizing resin (P) used for making the solvent-insoluble polymer produced by polymerizing the monomer in the non-aqueous solvent into a stable resin dispersion.
Will be described.

The dispersion stabilizing resin (P) of the present invention is a copolymer containing at least one polymerization component represented by the general formula (I) and colloidally dispersed in the non-aqueous solvent. The copolymer is a block composed of a block containing at least a polymerization component soluble in a non-aqueous solvent represented by the general formula (I) (hereinafter referred to as block A) and a block not containing it (hereinafter referred to as block B). It is a copolymer and has an AB block type (including ABA type and star type),
Graft type (also called comb type) is also included.
That is, the block A part is a part soluble in the non-aqueous solvent, the block B is an insoluble part in the non-aqueous solvent, and such a block copolymer of the soluble part and the insoluble part is used as the dispersion stabilizing resin (P). This makes it easy to disperse the dispersion stabilizing resin (P) in a colloidal form.

The dispersion stabilizing resin (P) of the present invention is preferably a resin which is dispersed in the non-aqueous solvent in a colloidal form having an average particle size of 0.15 μm or less, more preferably 0.1 μm or less. is there. The polymerization pattern of the block copolymer in the dispersion stabilizing resin (P) of the present invention is illustrated below.

[0051]

[Chemical 12]

Next, the repeating unit represented by the general formula (I), which is the main component in the block A of the dispersion stabilizing resin of the present invention, will be described. It is preferably -COO - - -V ⁰ in the general formula (I), - OCO- or an -O-. L
Preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
Examples include linolel groups.

B ¹ and b ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon atom 1 to
3 alkyl group (eg, methyl group, ethyl group, propyl group, etc.), —COO-Z ¹ or —CH ₂ COO-Z ¹ [Z ¹
Represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (for example, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.).

Z ¹ is specifically a hydrogen atom, and as a preferable hydrocarbon group, an alkyl group having 1 to 22 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group). Group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl 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 which may be substituted (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, linolel group, etc.), aralkyl group having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro) Benzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) and 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, etoxy Phenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group,
Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) To be

In the block A part, other repeating unit may be contained as a copolymerization component in addition to the repeating unit represented by the general formula (I). Other copolymerization components include
Any compound may be used as long as it is a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (I). However, preferably, it is preferable not to contain other components,
It is used in an amount of 20% by mass or less, more preferably 10% by mass or less, in Block A at most. If it exceeds 20% by mass, the dispersion stability of the colloidal dispersed resin particles deteriorates.
In the block A, the repeating unit represented by the general formula (I) may be used in combination of two or more kinds.

The polymer component constituting the block B of the dispersion stabilizing resin used in the present invention includes a polymer component corresponding to the monofunctional monomer (A), a phosphono group and a carboxyl group. Group, sulfo group, hydroxyl group, formyl group, amino group, -P (= O) (OH) R ³¹ group [R
³¹ represents -R ³² group or -OR ³² group, R ³² represents a hydrocarbon group], -CONR ³³ R ³⁴ group, -SO ₂ NR ³³ R ³⁴ group [R ³³ and R ³⁴ are each independently , A hydrogen atom or a hydrocarbon group] and a polymer component containing at least one polar group selected from cyclic acid anhydride-containing groups.

Each of the above hydrocarbon groups represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group for R ³² is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group). , A hexenyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, and the like, and an aromatic group which may be substituted (for example, a phenyl group, Tolyl group, xylyl group, mesityl group, chlorophenyl group,
Bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2.
-Dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, 2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride, and the like, These aliphatic dicarboxylic acid anhydrides may be substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. Further, examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride,
Naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride and the like, and these aromatic dicarboxylic acid anhydrides, for example,
Chlorine atom, halogen atom such as bromine atom, methyl group, ethyl group, propyl group, butyl group, alkyl group such as hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as the alkoxy group, for example, a methoxy group, Ethoxy group, etc.) and the like.

The block B part is preferably a polymer component corresponding to the monofunctional monomer (A). When the above-mentioned specific polar group-containing polymer component is contained, it is preferably not more than 30 parts by mass of the total polymer component in the block B part. If it exceeds 30 parts by mass, the ejection response of the ink containing the dispersed resin particle dispersion of the present invention may be adversely affected.

The weight average molecular weight (Mw) of the dispersion stabilizing resin (P) of the present invention is preferably 2 × 10 ⁴ to 1 × 10 ⁶ , and more preferably 3 × 10 ⁴ to 1 × 10 ⁵ . . The composition ratio of the block A part and the block B part in the dispersion stabilizing resin (P) of the present invention is preferably 30/70 to 90/10 (mass ratio), and more preferably 40/60 to 80 /.
20 (mass ratio).

The case where the dispersion stabilizing resin (P) of the present invention is a star block copolymer will be described in more detail. The star-type block polymer is formed by binding at least three polymer chains composed of block A and block B shown below.

[0062]

[Chemical 13]

Here, each polymer chain is composed of the same content, and the order of arrangement in the polymer chains of block A and block B is such that the end of the polymer main chain of block A which is connected to block B of the polymer main chain. It is formed by binding to an organic molecule at one end on the side opposite to.

In the above, X represents an organic molecule,
(A) represents block A, (B) represents block B,
(A)-(B) represents a polymer chain. Also, such AB
The upper limit of the type block polymer chains contained in the organic molecule is at most 15, usually about 10. The organic molecule formed by binding at least three polymer chains is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. Examples include the trivalent hydrocarbon residues described below.

[0065]

[Chemical 14]

[Here, each of r ^{1 to} r ⁶ represents a hydrogen atom or a hydrocarbon group. However, at least one of r ¹ and r ² is linked to the polymer chain, and at least one of r ^{3 to} r ⁶ is linked to the polymer chain. ]

These organic residues are constituted alone or in any combination thereof, and in the case of a combination, --O--,
^{-S -, - N (r 7} ) -, - COO -, - CON (r 7) -,
_{-SO 2 -, - SO 2 N} (r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO -, - NHCO
Heterocycles containing heteroatoms such as NH-, oxygen atom, sulfur atom, nitrogen atom (for example, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine A ring or the like) may be included in the binding unit.

Examples of other organic molecules that bond the polymer chains include those composed of a combination of the following bonding unit and the above bonding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0069]

[Chemical 15]

The block copolymer (P) can be synthesized by utilizing a conventionally known method for synthesizing a block copolymer of a monomer having a polymerizable dipolymerization bond group. For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morton, TE Helminiak et al.
“J. Polym. Sci.” 57, 471 (1962), B. Gordon III,
M, Blumenthal, JE Loftus et al “Polym. Bul
l. ”11, 349 (1984), RB Bates, WA Beavers et a
It can be synthesized according to the method described in “J. Org. Chem.” 44, 3800 (1979). However, when this reaction is used, the "specific polar group" of the present invention is used as a protected functional group to polymerize, and then the protective group is removed. The protection of the specific polar group of the invention with a protecting group and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above cited document, and further, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha Ltd. (1977), TM Greene "Pr.
otective Groups in Organic Synthesis ”(John Wiley
& Sons, 1981), JFW McOmic “Protective Gro
ups in Organic Chemistry ”(Plenum Press, 1973)
The method described in detail in the review article can be selected as appropriate.

As another method, a monomer of the present invention which does not protect a specific polar group is used, and a compound containing a dithiocarbament group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu "Polymer" 3
7, 248 (1988), Shunichi Hinomori, Ryuichi Otsu “Polym. Rep. Ja
p. "37, 3508 (1988), Japanese Unexamined Patent Publication No. 64-111, Japanese Unexamined Patent Publication No. 64-26619, Nobuyuki Azuma et al.," Polymer Preprints, "
Japan ”36 (6), 1511 (1987), M. Niwa, N. Higashi
et al “J. Macromol. Sci. Chem.” A24 (5), 567 (19
87) and the like.

Within the above range, the dispersion resin particles in the oil-based ink of the present invention are excellent in dispersion stability, redispersion stability and storage stability, and the rapid fixing property after image formation is good. In addition, it retains sufficient strength during printing and exhibits high printing performance. At the same time, it exhibits very stable dispersibility, and even if it is used repeatedly for a long time in the recording apparatus, it has good dispersibility and is easy to re-disperse, and it is completely adhered to each part of the apparatus to cause stains. unacceptable.

Further, when fixing was carried out by rapid processing such as heating after the formation of the ink image, a strong coating was easily formed on the surface of the lithographic printing plate support, and a good fixing property was exhibited. As a result, it is possible to print a large number of sheets (high printing durability) even in offset printing. The oil-based ink of the present invention which brings about the above effects is made possible by the insoluble latex provided by the present invention.

Such a remarkable effect of improving the performance of the present invention depends on the copolymer (P) which is composed of specific blocks as constituents and is dispersed in a non-aqueous solvent in a colloidal state. Is. That is, the dispersion stabilizing resin (P) of the present invention has a block A composed of a polymer component containing a linear aliphatic group having a high affinity for the non-aqueous solvent and an affinity for the non-aqueous solvent. Is a copolymer consisting of a polymer chain of a block bound to a block B composed of a polymerization component having a small affinity for the insoluble monomer (A) and being colloidal in a non-aqueous carrier liquid. It is characterized by being dispersed in. As a result, in the polymerization granulation reaction of the dispersed resin particles, the block B portion is sufficiently adsorbed by physicochemical interaction during the polymerization granulation, and the block portion having a large affinity for the non-aqueous dispersion medium is the solvent. On the other hand, since there is a polymer chain that is sufficiently solvated with respect to the polymer chain and sufficiently acts on the steric repulsion effect, the adsorption effect and the steric repulsion effect are sufficiently efficiently expressed, and thus the effect is exerted in the present invention. Presumed to be done.

On the other hand, in the conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, the component serving as the adsorbing portion is composed of a solvating component. Since they are randomly bonded in the polymer chain, they are not sufficiently adsorbed on the dispersed resin particles, and the adsorption pattern is looped, which also hinders the steric repulsion effect, resulting in insufficient dispersion stability. There wasn't. Furthermore, A composed of block A and block B
By using the -B type block copolymer, the effect of improving the dispersion stability was recognized as compared with the above random copolymer. However, the block copolymer (P) obtained by colloidally dispersing in the non-aqueous solvent of the present invention is more adsorbed on the dispersed particles than the dispersion stabilizing resin composed of the block copolymer soluble in the solvent. It was found to be excellent and the dispersibility was extremely excellent.

As described above, in the oil-based ink of the present invention, by using the block copolymer having a specific block bond together, the dispersion stability and the like can be improved and various problems can be solved. .

Next, a monofunctional monomer (B) containing a specific substituent represented by the above-mentioned general formula (II), which is copolymerizable with the monomer (A) and is used in a preferred embodiment of the present invention.
Will be described.

First, the case where E ¹ represents an aliphatic group having 8 or more carbon atoms in the general formula (II) will be described in detail. Examples of the aliphatic group having 8 or more carbon atoms of E ¹ include preferably an alkyl group having 10 or more total carbon atoms and optionally substituted, or an alkenyl group having 10 or more total carbon atoms and optionally substituted.

U ¹ is preferably --COO--, --CON.
^{H -, - CON (E 2} ) - ( wherein, E ² is preferably aliphatic group (the aliphatic group of 1 to 32 carbon atoms, such as alkyl groups, and the like alkenyl group or an aralkyl group) Or represents a substituent represented by the general formula (IIa)), —OCO—, —CH ₂ OCO—, or —O—.

D ¹ and d ² may be the same or different, and preferably each is a hydrogen atom, a fluorine atom, a chlorine atom,
A bromine atom, a cyano group, a methyl group, -COO-E ³ or an -CH ₂ COO-E ³ (where E ³ is preferably an alkyl group having 32 or less carbon atoms, an alkenyl group, an aralkyl group or cycloalkyl group ).

In the formula (II), U ¹ is --COO-- or --CONH.
- or -CON (E ²⁾ - represents, it is d ¹ and d ^2,
They may be the same or different, and each is a hydrogen atom, a fluorine atom,
More preferably, it represents a chlorine atom, a cyano group or a methyl group.

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

In the monomer (B) represented by the general formula (II), E ¹ has a total number of atoms of 8 or more (excluding a hydrogen atom directly bonded to a carbon atom or a nitrogen atom).
The case where the group represented by a) is represented will be described in detail.

A¹And A² Can be the same or different
A group represented by the general formula (IIb) and a carbon number of 1 to 1
At least one selected from eight hydrocarbon groups
Represents a group. Here, when two or more groups are selected,
Two selected from these groups of formula (IIb) and hydrocarbon groups
It represents a combination of the above groups. Specifically, A¹Oh
And A² Is, for example, -C (R^{twenty four}) (R^{twenty five})-(Where
R^{twenty four}, R^{twenty five}May be the same or different and each
Child, alkyl group, halogen atom, etc.),-(CH =
CH)-, cyclohexylene group (hereinafter referred to as cyclohexyl group
Group to "-C₆ H _Ten"-C", "-C₆H_Ten− ”
1,2-cyclohexylene group, 1,3-cyclohexylene
Group, including 1,4-cyclohexylene group),
Arbitrary combination of atomic groups such as groups represented by general formula (IIb)
It is composed of garnish.

When E ¹ represents a substituent represented by the general formula (IIa) having a total number of atoms of 8 or more, the bonding group (-U ^{1
_{- (A 1 -B 1) m}} - (A 2 -B 2) in _n -R ^21), from U ¹ R ^{21 (i.e., U 1, A 1, B} 1, A 2, B 2
And the R ²¹ ), the “connecting main chain” preferably has a total number of atoms constituting the connecting main chain of 8 or more.

Here, the number of atoms constituting the "linking main chain" means, for example, when U ¹ represents -COO- or -CONH-, the oxo group (= O group) or hydrogen atom is the number of atoms. It is meant that carbon atoms, ether type oxygen atoms, and nitrogen atoms, which are not included but constitute the linked main chain, are included as the number of atoms. Therefore, -COO- and -CONH- have 2 atoms.
Is counted as Also, if R ²¹ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included. Therefore, in this case, it is counted as 9 atoms.

U ¹ represents —CON (E ² ) —, and E ² represents a substituent represented by the general formula (IIa), that is, (— (A ¹ -B ¹ ) _m — (A ² -B ²⁾ when it represents an _n -R ^21), also connected backbone consists of E ² contained in the "binding main chain". Further, in the case where A ¹ and A ² each have a group represented by the general formula (IIb), (-B ^3- (A ⁴ -B ⁴ ) p-
R ²³⁾ group are also included in the "binding main chain".

Specific examples of the monomer (B) represented by the above general formula (II) in which E ¹ represents the substituent represented by the above general formula (IIa) include the following compounds. However, the present invention is not limited to these.

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

[0090]

[Chemical 16]

[0091]

[Chemical 17]

[0092]

[Chemical 18]

By using the monomer (B), the dispersion stability and redispersibility of the dispersed resin particles (CSR) are further improved. This is because the copolymerization component corresponding to the monomer (B) is highly lyophilic with the dispersion medium and is oriented on the particle surface portion, and as a result, the lyophilization of the surface of the particle itself with the dispersion medium is achieved. It is presumed that this is because the activity of the particles increases and the aggregation and precipitation of the particles are suppressed. The amount of the monomer (B) used is preferably 0.5 to 20% by mass based on all monomers constituting the shell layer.
More preferably, it is 1 to 15 mass%.

The resin insoluble in the non-aqueous solvent which constitutes the shell layer of the resin particles used in the liquid developer of the present invention preferably has a glass transition point of 0 to 80 ° C or a softening point of 35 to 100 ° C. The range of the point 35 to 70 ° C or the softening point 45 to 80 ° C is more preferable. The monomer (A), and optionally the monomer (B), the monomer (C) and the monomer (D) may be selected so that the polymer exhibits such thermal properties. it can.

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

In the formula (IV), R ¹ and R ² may be the same or different and each is 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.

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 amino group include a morpholino group, a piperidino group, a pyridyl group, an imidazolyl group, a quinolyl group, and the like.
A plurality of amino groups may be contained in the molecule of the monomer (C). In the dispersed resin particles (CSR) of the present invention, by using the amino group-containing monomer (C) as a copolymerization component, the particles become positively charged, and when combined with a charge control agent, the charge amount of the particles is increased. Will increase. Furthermore, changes in positive 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 period of time.
The formed image has stable image quality. The monomer (C) is preferably used in an amount of 1 to 30% by mass, more preferably 5 to 25% by mass, based on the total amount of all monomers in the shell layer.

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

[0100]

[Chemical 19]

Next, in the present invention, the monofunctional monomer (D) preferably used together with the monofunctional monomer (C).
Will be described. Monofunctional monomer (D) is, -PO ₃
It is a monomer copolymerizable with the monomer (A), containing at least one acidic group selected from H ₂ group, —SO ₃ H group and —SO ₂ H group. The monomer (D) may contain a plurality of the above acidic groups in the molecule. By allowing the monomer (D) to coexist with the monomer (C), the charging characteristics of the resin particles are further improved and stably maintained, and an image with excellent image quality can be stably obtained. When the monomer (D) is used, the molar ratio of monomer (C) / monomer (D) is preferably 0.2 to 2.5, more preferably 0.5 to 2. It is 0.

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

[0103]

[Chemical 20]

[0104]

[Chemical 21]

To produce the dispersed resin particles (CSR) of the present invention, generally, the dispersion stabilizing resin (P) as described above,
Monomer (A), and optionally monomer (B), monomer (C) and monomer (D), in a non-aqueous solvent containing seed particles (CR), benzoyl peroxide, The heat polymerization may be carried out in the presence of a polymerization initiator such as azobisisobutyronitrile or butyllithium. Specifically, the dispersion stabilizing resin (P), the monomer (A), and if necessary, the monomer (B), the monomer (C), the monomer (D), and the seed particles (CR) are used. A method in which a polymerization initiator is added to the mixture, the dispersion stabilizing resin (P) is dissolved, and the monomer (A) and, if necessary, the monomer (A) are added to the mixture in which the seed particles (CR) are dispersed. B), the monomer (C) and the method of dropping the monomer (D) together with the polymerization initiator, or the dispersion stabilizing resin (P) was dissolved and the seed particles (CR) were dispersed. In the mixture, half amount of the monomer (A), if necessary, a mixture of the monomer (B) and / or monomer (C) and half amount of the monomer (A), and if necessary, a single amount There is a method in which the mixture of the body (D) and the polymerization initiator are added dropwise at the same time, and any method can be used for production.

The use ratio of the seed particles (CR) and the total amount of the monomers ((A), (B), (C) and (D)) constituting the shell layer is calculated as follows: seed particles (CR) / single amount The mass ratio of the total body weight is preferably 5/95 to 95/5, more preferably 10/90 to 80/20. The total amount of the seed particles (CR) and all the monomers is preferably 10 to 150 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the non-aqueous solvent.

The amount of the dispersion stabilizing resin (P) used is preferably 3 to 40 with respect to 100 parts by mass of all the monomers used.
It is a mass part, More preferably, it is 5-30 mass parts.
The amount of the polymerization initiator is appropriately 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 5 to 20 hours.

When a polar solvent such as the alcohols, ketones, ethers and esters described above is used together with the non-aqueous solvent, or when unreacted monomer remains, the boiling point of the polar solvent or monomer It is preferable to remove by heating and distilling off or distilling under reduced pressure.

The non-aqueous dispersion resin particles (CSR) obtained as described above are present as fine particles having a uniform particle size distribution. The average particle size is preferably 0.1-3.
It is 0 μm, and more preferably 0.15 to 2.0 μm.
This particle size is measured by a centrifugal sedimentation type particle size distribution measuring device (for example, CAP
A-700, manufactured by Horiba, Ltd.) or a laser diffraction / scattering type particle size distribution measuring device (for example, LA-920, manufactured by Horiba, Ltd.). In the liquid developer of the present invention, the resin particles (CSR) are 0.5 to 10 with respect to 1000 parts by mass of the non-aqueous solvent which is a carrier liquid.
It is preferable to use about 0 parts by mass.

The liquid developer of the present invention is excellent in chargeability, dispersion stability, redispersibility and storage stability of dispersed resin particles, and
High-definition image reproducibility and rapid fixing property after image formation are excellent. Further, even when an image is formed on a plate material surface capable of offset printing to form a printing plate and the offset printing is performed, sufficient image strength is maintained and high printing durability is exhibited. That is, it has very stable dispersibility, and even if it is used repeatedly for a long time in the recording apparatus, the dispersibility and chargeability are good, and the re-dispersion is good, which may cause aggregation and precipitation of particles. Absent. Further, due to its good fixability, a strong coating can be easily formed on the surface of the lithographic printing plate precursor by fixing after image formation by rapid processing such as heating. By that,
Even in offset printing, printing a large number of sheets (high printing durability)
Is 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 dispersed resin particles (CSR) of the present invention are characterized by being core / shell particles composed of different resin component layers. Due to the presence of the shell layer in this way, while satisfying the above-mentioned many performances required as a liquid developer while maintaining a sufficient film strength as an image part after originally forming and fixing an image. It becomes possible. For example, the dispersed resin particles in the liquid developer spontaneously settle when they are allowed to stand, but it is necessary to easily redisperse them by stirring in a developing device and shaking in container storage. For that purpose, it is important that the particles do not stick to each other even if they come into contact with each other, but by slightly changing the thermophysical properties of the resin component of the core layer and the resin component of the shell layer, sufficient film strength is obtained even with quick fixing. It is possible to obtain dispersed resin particles which can be maintained at a high temperature and have good redispersibility. Specifically, the glass transition point or curing point of the resin forming the shell layer is preferably 1 to 8 ° C., more preferably 2 to 5 ° C., higher than that of the resin forming the core layer.
Make it higher Furthermore, by adjusting the composition of the shell layer,
The performance of the particles can be increased without compromising the good fixability / film strength of the whole particles.

In the liquid developer of the present invention, a charge control agent is used in order to clearly control the electroscopic property of the resin particles (CSR) dispersed in the non-aqueous solvent. As the charge control agent of the liquid developer of the present invention, conventionally known charge control agents can be used. For example, metal salts of fatty acids such as naphthenic acid, octenoic acid, oleic acid and stearic acid, metal salts of sulfosuccinic acid ester, JP-B-45-556, JP-A-52-
No. 37435, No. 52-37049, etc., oil-soluble metal salts of sulfonic acid, metal salts of phosphoric acid ester shown in Japanese Patent Publication No. 45-9594, Japanese Patent Publication No. 48-
No. 25666, metal salts of abietic acid or hydrogenated abietic acid, metal salts of alkylbenzene sulfonic acids shown in JP-B No. 55-2620, JP-A Nos. 52-107837 and 52-38937.
Nos. 57-90643 and 57-139753, metal salts of aromatic carboxylic acids or sulfonic acids, nonionic surfactants such as polyoxyethylated alkylamines, lecithin, linseed oil, etc. Oils and fats,
Polyvinylpyrrolidone, organic acid esters of polyhydric alcohols, phosphoric acid ester-based surfactants described in JP-A-57-210345, and sulfonic acid resins described in JP-B-56-24944 are used. be able to. Further, JP-A-60-21056 and 61-5095.
The amino acid derivatives described in No. 1 can also be used. Furthermore, JP-A-59-30917 and 59-299.
38, 59-38264, maleic anhydride or itaconic anhydride copolymers with primary or secondary amines, maleic acid half-acylamide and N shown in JP-A-59-36787. -A copolymer containing a substituted maleimide, and further JP-A-54-31739.
And the quaternized amine polymers shown in JP-B-56-24944 and the like. The charge control agents can be used alone or in combination of two or more. The charge control agent is preferably used in an amount of 0.001 to 1.0 part by mass with respect to 1000 parts by mass of the non-aqueous solvent which is the carrier liquid. In the liquid developer of the present invention, a colorant may be used if desired. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used. For example, metal powders such as aluminum, magnetic iron oxide, zinc oxide, titanium oxide, metal oxides such as silicon dioxide, metal salts such as powdered cadmium selenium chromate, Hansa Yellow (C.I. 11680), Benzidine Yellow G (C.I. 21090), benzidine orange (C.I. 21110), fast red (C.I.
I. 37085), Brilliant Carmine 3B (C.
I. 16015-Lake), Phthalocyanine Blue (C.I.
I. 74160), phthalocyanine green (C.I.
74260), Victoria Blue (C.I. 42595)
-Lake), Spirit Black (CI.5041)
5), oil blue (C.I.74350), alkali blue (C.I. 42770A), fast scarlet (C.I. 12315), rhodamine 6B (C.I.
I. 45160), Fast Sky Blue (C.I.
74200-Lake), nigrosine (C.I. 5041)
5), carbon black and the like. Surface-treated pigment,
For example, carbon black dyed with nigrosine, graft carbon obtained by graft polymerizing a polymer, and the like can also be used. The colorant may be dispersed as a particle in the non-aqueous solvent separately from the dispersed resin particles, or may be contained in the dispersed resin particles. When the dispersed resin particles are colored, for example, a method of physically dispersing in the resin using a pigment or a dye is used. In addition, JP-A-57-
There is a method of dyeing dispersed resin particles with a preferable dye as described in 48738 and the like. Further, as disclosed in JP-A-53-54029, there is a method of chemically bonding dispersed resin particles and a dye. Further, as described in JP-B-44-22955 and the like, there is also a method in which a monomer containing a dye in advance is used to produce a resin particle containing a dye when the polymer granulation method is used.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, "Electrophotography" Vol. 16, Vol. No. 2, page 44 is used. Specific examples include higher alcohols, fluoroalcohols, polyethers, olefin waxes, silicone oils, and heterocyclic compounds. However, it is not limited to these. The upper limit of the total amount of the additives is regulated by the electric resistance of the liquid developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a good quality continuous tone image. Therefore, the addition amount of each additive should be controlled within this limit. Is desirable.

The liquid developer of the present invention can be used in combination with any electrophotographic photosensitive member. The photoconductor used may be a known organic photoconductor or inorganic photoconductor. A derivative charged by a charging needle can also be used. Organic photoconductors include a wide range of well known organic photoconductors. A specific example is "Research Disclosure", No.109.
38 (May 1973, p. 61 and subsequent pages, there are substances described in "Electrophotographic Elements, Materials and Processes", etc. Examples of practically used substances include poly-N.
-Vinylcarbazole and 2,4,7-trinitrofluoren-9-one electrophotographic photoreceptor (US Pat. No. 3,484,237), poly-N-vinylcarbazole sensitized with pyrylium salt dye What was done (Sho 48)
No. 25658), an electrophotographic photoreceptor containing an organic pigment as a main component (JP-A-49-37543), and an electrophotographic photoreceptor containing a eutectic complex of a dye and a resin as a main component (JP-A-47).
No. -10735), an electrophotographic photoconductor in which copper phthalocyanine is dispersed in a resin (Japanese Patent Publication No. 52-1667), and the like. Others, The Electrophotographic Society of Japan, Vol. 25, No. 3 (19
86) and pages 62-76. RMSc as the inorganic photoconductor used in the present invention
Haffert "Electrophotography" (Electro
Photography) Focal Press (London) Publishing (1975)
The various inorganic compounds disclosed on pages 260 to 374 are typical. Specific examples include zinc oxide, titanium oxide, α-silicon, zinc sulfide, cadmium sulfide, selenium-tellurium alloy, selenium-arsenic alloy, and selenium-tellurium-arsenic alloy.

[0115]

EXAMPLES The present invention will be described in more detail below with reference to production examples and examples of resin particles used in the present invention, but the present invention is not limited thereto.

Synthesis Example of Dispersion Stabilizing Resin (P) 1: Resin (P-1) Methyl Methacrylate 50 g, Ethyl Acrylate 50
g, a mixture of 7.8 g of an initiator (I-1) having the following structure and 100 g of tetrahydrofuran under a nitrogen stream at a temperature of 50 ° C.
Warmed to. 10c of this solution with 400W high pressure mercury lamp
Light was irradiated from a distance of m through a glass filter for 8 hours to perform photopolymerization. The polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Next, the above polymer 5
A mixed solution of 5 g, 45 g of stearyl methacrylate and 100 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream. Next, in the same manner as above, after performing light irradiation for 16 hours, the obtained reaction product was treated with methanol 1.5
It is reprecipitated in liter, the precipitate is collected, dried and the weight average molecular weight [Mw: Mw is a value by polystyrene conversion GPO method (GPC: size exclusion chromatography)] is 6 × 10 ⁴ at a yield of 80 g. A polymer of Moreover, 5% by mass of the obtained resin and Isopar H (manufactured by Exxon)
After thoroughly stirring the mixture, the mixture became a bluish-white liquid. A sample was prepared from this solution, and fine particles with an average particle size of 0.14 μm were observed from a scanning electron microscope (hereinafter referred to as SEM) photograph.

[0117]

[Chemical formula 22]

Synthesis Example 2 of dispersion stabilizing resin (P): A mixture of 50 g of resin (P-2) octadecyl acrylate, 10.0 g of an initiator (I-2) having the following structure and 50 g of tetrahydrofuran was heated under a nitrogen stream at a temperature. Warmed to 50 ° C. This solution was irradiated with light from a high pressure mercury lamp of 400 W at a distance of 10 cm through a glass filter for 8 hours to perform photopolymerization. The polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Next, a mixed solution of 30 g of the above polymer, 36 g of methyl acrylate, 4 g of acrylic acid and 70 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream. Next, after performing light irradiation for 8 hours in the same manner as above, the obtained reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. Furthermore,
A mixed solution of 35 g of this polymer, 15 g of octadecyl acrylate and 50 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream. Next, in the same manner as above, after irradiation with light for 8 hours, the obtained reaction product was reprecipitated in 1.5 liters of methanol, the precipitate was collected and dried, and the yield was 42 g and Mw6 was used. A polymer of 0.5 × 10 ⁴ was obtained. In the same manner as in Synthesis Example 1, particles having an average particle size of 0.13 μm were found by SEM photograph observation of a sample of the Isopar H mixture.

[0119]

[Chemical formula 23]

Synthesis Example 3 of dispersion stabilizing resin (P): Resin (P-3) 22 g of methyl methacrylate, 33 of methyl acrylate
g and a mixture of 45 g of a macromonomer (MM-1) having the following structure and 185 g of toluene at a temperature of 80 ° C. under a nitrogen stream.
Warmed to. 1.5 g of 2,2-azobisisobutyronitrile (abbreviation AIBN) was added to this mixed solution and reacted for 3 hours. Furthermore, 0.8 g of AIBN was added and reacted for 2 hours, and subsequently 0.5 g of AIBN was added, and then the temperature was raised to 85 ° C. and reacted for 3 hours. The resulting reaction product was a pale white, bright mixture. The reaction product was reprecipitated in 2 liters of methanol, and the precipitate was collected and dried to obtain a yield of 85 g.
Thus, a polymer having Mw of 4.5 × 10 ⁴ was obtained. Synthesis example (P-
As a result of SEM observation of the colloidal dispersion in the same manner as in 1), it was a particle of 0.10 μm.

[0121]

[Chemical formula 24]

Synthesis Examples 4 to 14 of Dispersion Stabilizing Resin (P):
Resin (P-4) to (P-14) Methyl methacrylate 35 g, methyl acrylate 55
A mixture of 0.01 mol of each initiator (I) shown in Table-A and 100 g of tetrahydrofuran was heated to 50 ° C under a nitrogen stream with respect to all monomers using g. This solution was irradiated with light for 12 hours to carry out a polymerization reaction in the same manner as in Synthesis Example 1. Next, 55 g of each polymer obtained, 45 g of tridecyl methacrylate and 12 g of tetrahydrofuran
The mixed solution containing 0 g was again heated to a temperature of 55 ° C. under a nitrogen stream.
Warmed to. Next, after performing light irradiation for 16 hours in the same manner as above, the obtained reaction product was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. Yield 60 ~
80 g of each polymer having Mw of ⁴ × 10 ^{4 to} 7 × 10 ⁴ was obtained.

As a result of SEM observation of the colloidal dispersion of each polymer, particles of each polymer in Isopar H were 0.10.
Was about 0.15 μm.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

Dispersion Resin Particles (CSR) Production Example 1: Dispersion Resin Particles (CSR-1) <Seed Particle (CR) Production Example 1: Seed Particles (CR-)
1)> Dispersion stabilizing resin (DSP-1) 12 having the following structure
g, 100 g vinyl acetate and 386 g Isobar H
The mixed solution of was heated to 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, 1.5 g of 2,2-azobisisovaleronitrile (AIVN) was added and the reaction was carried out for 4 hours. Furthermore, 1.0 g of this initiator was added, and the temperature was raised to 75 ° C.
After reacting for an hour, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, pass through a 200-mesh nylon cloth, and the white dispersion obtained had a polymerization rate of 93%.
It was a latex having an average particle size of 0.21 μm and good monodispersity. The particle size is CAPA-700 (manufactured by Horiba, Ltd.)
Was measured (the same applies hereinafter). A part of the above white dispersion was subjected to a centrifuge (rotation speed 1 × 10 ⁴ rpm, rotation time 1 hour), and the precipitated resin particles were collected and dried to obtain a mass average molecular weight (Mw) (GP. The polystyrene conversion value according to C. The same applies hereinafter) and the glass transition point (Tg) were measured. As a result, the Mw was 2 × 10 ⁵ , and the Tg was 38 ° C.

<Production of Dispersed Resin Particles (CSR-1)> 75 g of the above white dispersion (as solid content), 5 g of the dispersion stabilizing resin (P-1) having the above structure and 50 g of Isopar H.
The mixture of 1 was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. A mixture of 15 g of benzyl methacrylate, 10 g of benzyl acrylate, 0.8 g of AIVN, and 25 g of Isopar H was added dropwise thereto over 1 hour, and the mixture was stirred for 2 hours as it was. Then add 1.0 g of AIVN to a temperature of 75
The mixture was heated to ℃ and stirred for 3 hours. Then, 0.8 g of 2,2-azobisisobutyronitrile (AIBN) was added and the temperature was adjusted to 8
The mixture was heated to 0 ° C. and stirred for 3 hours. Then the temperature is 100 ℃
The mixture was stirred under a reduced pressure of 200 mmHg (about 26.6 kPa) for 2 hours to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting dispersion had a polymerization rate of 9
The latex was 9% and had an average particle size of 0.22 μm. A sample of the resin component corresponding to the shell layer was prepared by the following operation, and its Tg was measured and found to be 41 ° C. The Mw was 1 × 10 ⁵ . In the production of the dispersed resin particles (CSR-1), seed particles (C
A white dispersion was obtained in the same manner except that the white dispersion of R-1) was removed, and a part of the white dispersion was subjected to the same centrifugation operation as described above to collect and dry the particles.

[0129]

[Chemical 25]

Dispersion Resin Particles (CSR) Production Example 2: Dispersion Resin Particles (CSR-2) <Seed Particle (CR) Production Example 2: Seed Particles (CR-)
2)> 16 g of dispersion stabilizing resin (DSP-2) having the following structure
And a mixture of 384 g of Isobar H were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 30g of methyl methacrylate, 70g of methyl acrylate, and AI
A mixture of VN and 1.5 g was added dropwise over 1 hour, and 2
Stir for hours. Then add 1.0 g of AIVN to a temperature of 75
Warm up to ℃ and stir for 3 hours, then add 0.8 g of AIBN
In addition, the temperature was raised to 80 ° C. and the mixture was stirred for 3 hours.

Then, the temperature is raised to 100 ° C., and the pressure reduction degree is set to 20.
The mixture was stirred under 0 mmHg (about 26.6 kPa) 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 99% and an average particle size of 0.17 μm. Tg of resin particles
Was 36 ° C. and Mw was 1 × 10 ⁵ .

<Production of Dispersed Resin Particles (CSR-2)> 50 g of the above white dispersion (as solid content), 5 g of the dispersion stabilizing resin (P-2) of the above structure and 68 g of Isopar H.
The mixture of 1 was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. To this, 20 g of methyl methacrylate, 48 g of methyl acrylate, 8 g of 2- (N, N-diethylamino) ethyl methacrylate, 4 of octadecyl acrylate
A mixture of g, AIVN, 0.9 g and Isopar H 68 g was added dropwise over 1 hour, and the mixture was stirred for 2 hours as it was. Next, 1.0 g of AIVN was added and heated to a temperature of 75 ° C. and stirred for 3 hours, and 0.8 g of AIBN was further added and heated to a temperature of 80 ° C. and stirred for 3 hours. Then the temperature is 100
2) under reduced pressure of 200 mmHg (about 26.6 kPa)
After stirring for an hour, unreacted monomer was distilled off. After cooling 200
The resin particle dispersion obtained was passed through a mesh nylon cloth, and the polymerization rate was 99% and the average particle diameter was 0.24 μm.
The physical properties of the resin component constituting the shell layer were measured in the same manner as in Production Example 1, and the Mw was 1.5 × 10 ⁵ and the Tg was 39 ° C.

[0133]

[Chemical formula 26]

Dispersion Resin Particles (CSR) Production Example 3: Dispersion Resin Particles (CSR-3) <Seed Particle (CR) Production Example 3: Seed Particles (CR-)
3)> Dispersion stabilizing resin (DSP-3) 16 having the following structure
g, 100 g vinyl acetate and 386 g Isobar H
The mixed solution of was heated to 70 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2-azobisisovaleronitrile (AIVN) was added as a polymerization initiator and the reaction was carried out for 4 hours. Furthermore, 1.0 g of this initiator was added, and the temperature was raised to 75 ° C.
After reacting for an hour, the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, it was passed through a nylon cloth of 200 mesh and the white dispersion obtained had a polymerization rate of 94%.
It was a latex having an average particle size of 0.20 μm and good monodispersity.

<Production of Dispersed Resin Particles (CSR-3)> 65 g (as solid content) of the above white dispersion, vinyl acetate 3
A mixture of 0 g, 5 g of dodecyl methacrylate, 5 g of a dispersion stabilizing resin (P-15) having the following structure and 50 g of Isopar H was heated to a temperature of 75 ° C while stirring under a nitrogen stream. To this, add AIBN, 1.0g and react for 3 hours,
Further, 0.8 g of this initiator was added and the reaction was carried out at a temperature of 80 ° C. for 4 hours, then the temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted monomers. After cooling, it was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 93% and an average particle size of 0.22 μm and good monodispersity. The resin component of the shell layer has Mw of 8 × 10 ⁴ , T
g was 38 ° C.

[0136]

[Chemical 27]

Production Examples 4-8 of Dispersed Resin Particles (CSR): Dispersed Resin Particles (CSR-4) to (CSR-8) In Production Example 2 of dispersed resin particles (CSR), the dispersion stabilizing resin (P-2 ) 5 g and 2- (N, N-diethylamino) ethyl methacrylate 8 g instead of the following Table-B.
A particle dispersion was produced in the same manner as in Production Example 1 except that 6 g of the dispersion-stabilizing resin (P) in 3) and 3 g of each monomer (C) in Table B below were used. Each of the obtained dispersions was a latex having an average particle size of 0.20 to 0.24 μm. The resin component of the shell layer has Mw of 1 × 10 ^{6 to} 3
× 10 ⁵ , Tg was in the range of 40 ~ 42 ℃.

[0138]

[Table 4]

Production Examples 9-18 of Dispersed Resin Particles (CSR):
Dispersion Resin Particles (CSR-9) to (CSR-18) In Production Example 2 of the dispersion resin particles (CSR), instead of 5 g of the dispersion stabilizing resin (P-2), the dispersion stabilizing resin of the following Table-B 'is used. A particle dispersion was prepared in the same manner as in Production Example 2 above, except that 5.5 g of (P) was used and 3 g of each monomer (B) shown in the following Table-B ′ was used instead of 3 g of octatecyl methacrylate. Manufactured. Each of the obtained dispersions was a latex having an average particle size of 0.22 to 0.24 μm. Mw of the resin component constituting the shell layer is 8 × 10 ⁴ to 2
× 10 ⁵ , Tg was in the range of 44 ~ 46 ℃.

[0140]

[Chemical 28]

[0141]

[Table 5]

Production Example 19 of Dispersed Resin Particles (CSR): Dispersed Resin Particles (CSR-19) 70 g (as solid content) of seed particles (CR-2), 6 g of a dispersion stabilizing resin (P-17) having the following structure and A mixture of 119 g of Isopar G was heated to a temperature of 70 ° C. with stirring under a nitrogen stream. To this, 7 g of cyclohexyl methacrylate, 10 g of methyl acrylate, 3 g of octadecyl methacrylate, 2- (N, N-diethylamino)
Ethyl methacrylate 3.3g and AIVN, 0.4g
And 6.3 g of cyclohexyl methacrylate,
A mixture of 10 g of methyl acrylate, 2.2 g of 2-phosphonoethyl methacrylate and 5 g of ethanol was simultaneously added dropwise over 1 hour, and the mixture was stirred as it was for 2 hours.
Next, 0.3 g of AIVN was added and heated to a temperature of 75 ° C. and stirred for 3 hours. Further, 0.3 g of AIBN was added and heated to a temperature of 80 ° C. and stirred for 3 hours. Then the temperature is 100
2) under reduced pressure of 200 mmHg (about 26.6 kPa)
After stirring for an hour, 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 0.24μ.
m latex. The resin component constituting the shell layer had an Mw of 3 × 10 ⁵ and a Tg of 45 ° C.

[0143]

[Chemical 29]

Production Examples 20-26 of Resin Particles (CSR): Colored Resin Particles (CSR-20)-(CSR-26) In Production Example 19 of resin particles (CSR), 2- (N,
Instead of 3.3 g of N-diethylamino) ethyl methacrylate, 0.018 mol of each monomer (C) in the following Table-C,
Each of the colored resin particles (CSR) in the same manner as in Production Example 19 described above except that 0.010 mol of each monomer (P) shown in the following Table-C was used instead of 2.2 g of 2-phosphonoethyl methacrylate. ) Was manufactured. The average particle size of the obtained colored particles was latex in the range of 0.20 to 0.30 μm.

[0145]

[Table 6]

Dispersion Resin Particles (CSR) Production Example 27: Dispersion Resin Particles (CSR-27) <Seed Particle (CR) Production Example 4: Seed Particles (CR-)
4)> ethylene / dodecyl methacrylate (95/5)
A mixture of 50 g of a molar ratio copolymer (Mw: 7 × 10 ⁴ ) and 200 g of Isopar H was dispersed together with glass beads in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 2 hours, and then the glass beads were filtered off. Next, pressure filtration was performed using a 2 μm size filter to obtain a dispersion from which coarse particles were removed. The average particle size of the obtained white dispersion is 0.35μ.
It was m.

<Production of Dispersed Resin Particles (CSR-28)> 50 g of the above white dispersion (as solid content), 10 g of a dispersion stabilizing resin (P-18) having the following structure, 47 g of vinyl acetate,
Hexadecyl methacrylate 3g and Isopar H 1
40 g of the mixture was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. To this, 1.8 g of AIVN was added and stirred for 4 hours. Next, 1.0 g of AIBN was added, the temperature was raised to 80 ° C., and the reaction was carried out for 3 hours.
8 g was added and stirred for 3 hours. Next, the temperature was raised to 100 ° C., and the unreacted monomer was distilled off by stirring under a reduced pressure of 200 mmHg for 2 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 94% and an average particle size of 0.40 μm. The resin component constituting the shell layer had an Mw of 6 × 10 ⁴ and a Tg of 39 ° C.

[0148]

[Chemical 30]

Example 1 and Comparative Example A <Preparation of liquid developer (LD-1)> Tetradecyl methacrylate / acrylic acid (95/5 mass ratio) copolymer 10
g, Alkali Blue 10 g and Isopar G 30 g together with glass beads, paint shaker (Toyo Seiki Co., Ltd.)
Manufactured) and dispersed for 6 hours to obtain a fine dispersion of alkali blue. 7 g of dispersed resin particles (CSR-1) (as solid content), 1 g of the above alkali blue dispersion (as solid content), 0.02 g of cobalt naphthenate salt and branched hexadecyl alcohol (FOC-1600, manufactured by Nissan Kagaku Co., Ltd.) ) 10 g was diluted to 1 liter of Isopar G to prepare a liquid developer for electrostatic photography (LD-1).

<Production of Comparative Developer A> In the production of the above liquid developer (LD-1), dispersed resin particles (CSR-
A liquid developer A for comparison was prepared in the same manner except that 1) was replaced with the following resin particles. Comparative liquid developer A: Seed particles (CR-1) produced in Production Example 1 of dispersed resin particles (CSR)

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 8 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-D.

[0152]

[Table 7]

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 A
Then, the developing device was significantly contaminated due to the adhesion of the toner residue. 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, Comparative Example A
Produced an image defect of the printed matter after printing. Furthermore, the same test as above was conducted using the developer (LD-1) aged under the condition II of the following Example 2 (stored under 35 ° C./85% RH for 3 months). It showed almost the same performance. 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 2 and Comparative Examples B to C <Preparation of printing 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 × 1.
A photosensitive layer forming composition was prepared by dispersing at 0 ³ rpm for 10 minutes, and the dry adhesion amount was 20 g / m ^{2 on} a support for ELP master 2X type (manufactured by Fuji Photo Film Co., Ltd.). Similarly, apply with a wire bar, dry at 110 ° C. for 10 seconds, and then in the dark at 20 ° C. and 65% RH for 24 hours.
An original plate for printing was prepared by leaving it for a period of time.

[0155]

[Chemical 31]

<Production of Liquid Developer (LD-2)> 10 g of dodecyl methacrylate / acrylic acid (95/5 mass ratio) copolymer, 10 g of methanesulfonylated modified nigrosine.
And 30 g of Isopar H were put into a paint shaker (manufactured by Toyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine black dispersion of nigrosine.

6 g of dispersed resin particles (CSR-2) (as solid content), 1.0 g of the above black dispersion (as solid content), 15 g of tetradecyl alcohol (FOC-1400, manufactured by Nissan Chemical Industries, Ltd.) and octadecyl vinyl ether. A liquid developer for electrostatic photography (LD-2) was prepared by diluting 0.01 g of maleic acid half-decylamide copolymer into 1 liter of Isopar G.

<Production of Comparative Developers B and C> In the production of the liquid developer (LD-2), the dispersed resin particles (C
Comparative liquid developers B and C were prepared in the same manner except that SR-2) was replaced with the following resin particles. Comparative liquid developer B: Seed particles (CR-2) produced in Production Example 2 of dispersed resin particles (CSR-2) Comparative liquid developer C: In Production Example 2 of dispersed resin particles (CSR-2) , Seed particle (CR-2) dispersion 50g
Resin particles (resin particles composed of a resin component that constitutes the shell layer) obtained under conditions excluding (as solid content) were examined for the charge characteristics, image reproducibility, printability, etc. of these liquid developers, and the results are shown. It is shown in Table-E.

[0159]

[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.

[0162]

[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.

The conditions I and II are those in which the aging state after the liquid developer is manufactured is changed, and the condition I is that the liquid developer obtained by mixing all the components is subjected to normal 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 3 months,
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 plate surface temperature was fixed at 60 ° C. for 10 seconds to form an image. 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 above-mentioned image reproducibility method 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-F, the charging characteristics of the liquid developer of the present invention and Comparative Example C were as follows even when stored under severe conditions.
The total charge amount and charge fraction of particles hardly change,
It was extremely stable. On the other hand, in Comparative Example B, the change amount of the total charge amount with time was relatively small, but the change in the charge fraction of the particles was large. When an image was actually formed, the liquid developer of the present invention and Comparative Example C were good under both conditions I and II. In Comparative Example B, flow generation was observed in the image portion under the condition I, and flow occurred in the entire condition II. Further, 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 Example B was not practically usable as a printed matter after printing. Further, in Comparative Example C, the image was missing about 1,000 sheets after the printing, and the printing became defective. As described above, only the developer of the present invention has stable image reproducibility, is sufficiently fixed even under rapid fixing conditions, and has good 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.
A printing original plate 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 high speed dispersion mixer It was dispersed for 2 hours with Dynamill (KDL-5, manufactured by WABACHOFEN) to obtain a coating liquid for the photoconductive layer.

<Production of Liquid Developer (LD-3)> Dispersion Resin Particles (CSR) Production Example 19 Dispersion Resin Particles (CSR)
-19) 9 g (as solid content), tetradecyl alcohol (FOC1400) 10 g, and vinyl acetate-semi-maleic acid tridodecylamide copolymer 0.012 g were mixed with Isopar H to a volume of 1 liter to prepare a liquid developer. (LD-3) was produced. When the charging characteristics were measured by the same method as in Example 2, the results shown in Table F below were obtained.

[0170]

[Table 9]

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.

Further, the printing plate precursor was made into a 5000 plate, and the development area was examined for stains. 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 19 Similar to Example 2 except that the dispersed resin particles (CSR) shown in Table G below were used in place of the dispersed resin particles (CSR-2) in Example 2. By operation, a liquid developer was prepared. The AC electric conductivity of each of the obtained liquid developers is 95-
100 (pS / cm), particle charge fraction is 90-95%
Met. Also, in the case of condition II, almost no change occurred.

[0174]

[Table 10]

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 exhibited a performance equal to or higher than that of Example 1, and the image reproducibility, dispersibility, and printability were good. In addition, each of the developers exhibited the same or better performance even under the condition II and were good.

Examples 20 to 31 In the same manner as in Example 1, except that the dispersed resin particles (CSR) shown in Table H below were used in place of the dispersed resin particles (CSR-1). By operation, a liquid developer was prepared.

[0177]

[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. Further, the developing device did not stain, as in the first embodiment. Further, each developer exhibited the same performance even under the condition II and was good.

Example 32 A photosensitive drum made of amorphous silicon was rotated at a peripheral speed of 10 mm / sec to supply the following dispersion liquid to the surface of the photosensitive member by using a slit electrodeposition apparatus, while the photosensitive member side was grounded and slit electrode 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.

<Dispersion liquid for forming transfer layer> Dispersion stabilizing resin [octadecyl methacrylate / acrylamide (97/3
Mass ratio) copolymer, mass average molecular weight: 4 × 10 ⁴ ] 12
g, vinyl acetate 98g, stearyl methacrylate 2g
And a mixed solution of 384 g of Isopar H were heated to a temperature of 70 ° C. with stirring under a nitrogen stream. 2, as a polymerization initiator
2'-azobis (isovaleronitrile) (abbreviation AI
V. N. ) Was added and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. Further, 0.5 g of the above initiator was added and reacted for 2 hours, then the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, it was passed through a 200-mesh nylon cloth to obtain a white dispersion (polymerization rate: 90%, average particle size: 0.23 μm). 10 g of the above thermoplastic resin dispersion
(As solid content) and zirconium naphthenate 0.0
01 g was added to 1 liter of Isopar H to obtain a positively charged resin dispersion liquid.

An electrophotographic process was carried out immediately while maintaining the surface temperature of the photosensitive member 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 Blue FG-7350, manufactured by Toyo Ink Co., Ltd.) / Octadecyl methacrylate-methyl methacrylate (5
/ 5 mass ratio) 6 g of Isopar G dispersion (as solid content) consisting of 1/1 mass ratio of the block copolymer, 8 g of dispersed resin particles (CSR-26) (as solid content) and dodecyl vinyl ether-octadecyl maleate. A liquid developer (LD-4) was prepared by diluting 0.01 g of the amide copolymer with 1 liter of Isopar G.

Next, after passing under an infrared line heater to measure the surface temperature with a radiation thermometer and preheat to about 80 ° C., the coated paper is superposed on the photoconductor having a transfer layer, and 10 kgf. It was passed at a speed of 15 mm / sec under a heated rubber roller whose surface temperature was controlled at 120 ° C. at a pressure of / cm ² (980 kPa). 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. Also, when the liquid developer (LD-4) was forcibly aged as in Example 2 (condition II), no difference was seen from the fresh product and it was clear.

[0184]

INDUSTRIAL APPLICABILITY The liquid developer of the present invention is excellent in charge stability, dispersion stability, redispersibility and fixing property of particles by using specific resin particles, and the development-fixing step It is possible to provide an offset printing plate having excellent printing ink oil sensitivity and printing durability even in an electrophotographic plate making system that is speeded up and uses a large plate size master plate.

Claims (5)

[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 In a water solvent, at least one monofunctional monomer (A) that is soluble in the non-aqueous solvent and becomes insoluble by polymerization, and at least a polymerization component represented by the following general formula (I) are contained. Seed the dispersion containing at least one of the dispersion stabilizing resin (P) formed by colloidally dispersing in the non-aqueous solvent, and seed particles (CR) having an average particle diameter of 0.05 to 1.0 μm. Obtained by polymerizing,
A liquid developer for electrostatic photography, which is a dispersion resin particle (CSR) having a multilayer structure. [Chemical 1] In the general formula (I), V ⁰ is -COO-, -OCO-,-.
_{(CH 2) r COO -,} - (CH 2) r OCO -, - O- or ## STR2 ## (Where X is a direct bond, -O-, -OCO- or -CO
Represents O-). r represents an integer of 1 to 12. L
Is an alkyl group having 8 to 32 carbon atoms or 8 to 32 carbon atoms
Represents an alkenyl group. b ¹ and b ² may be the same as or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹ , or —COO-D ¹ via a hydrocarbon group ( Here, D ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 2. The dispersion stabilizing resin (P) has the general formula (I):
A block containing at least a polymerization component represented by
The liquid developer for electrostatic photography according to claim 1, which is a block copolymer comprising a block containing no polymerization component represented by the general formula (I). 3. The non-aqueous solvent dispersion further comprises the monomer (A).
3. The liquid developer for electrostatic photography according to claim 1, further comprising at least one monofunctional monomer (B) represented by the following general formula (II) copolymerizable with . [Chemical 3] In the general formula (II), U ¹ is -COO -, - CONH -, -
CON (E ² )-(wherein E ² represents an aliphatic group or a group represented by general formula (IIa) below), -OCO-,-
_{CONHCOO -, - CH 2 COO -} , - (CH 2) S O
CO- (wherein, s represents an integer of 1 to 4), - O-or -C ₆ H ₄ represents a -COO-. d ¹ and d ² may be the same or different and each is a hydrogen atom, an alkyl group, a halogen atom, a cyano group, —COO—E ³ or —CH ₂ CO.
Represents O—E ³ (wherein E ³ represents an aliphatic group). E ¹ is an aliphatic group having 8 or more carbon atoms or 8 or more total atoms (however,
A hydrogen atom directly bonded to a carbon atom or a nitrogen atom is excluded), and a group represented by the following general formula (IIa) is represented. Formula ^{(IIa) - (A 1 -B} 1) m - (A 2 -B 2) n -R 21 in the formula (IIa), R ²¹ is a hydrogen atom or a carbon atoms 1 to 1
8 represents an aliphatic group. B ¹ and B ² may be the same or different and each is —O—, —S—, —CO—, —CO ₂
-, - OCO -, - SO 2 -, - N (R 22) -, - CO
N (R ²² )-, -N (R ²² ) CO-, -N (R ²² ) SO
_{2 -, - SO 2 N (} R 22) -, - NHCO 2 - or -N
HCONH- (wherein R ²² has the same meaning as R ²¹ above). A ¹ and A ² may be the same or different and each represents a group represented by the following general formula (IIb) and a carbon number of 1 to 18
Represents at least one group selected from among the hydrocarbon groups of m and n may be the same or different and each represents an integer of 0 to 4. However, the sum of m and n never becomes zero. [Chemical 4] In formula (IIb), B ³ and B ⁴ may be the same or different and have the same meanings as B ¹ and B ² , respectively, and A ⁴ represents a hydrocarbon group having 1 to 18 carbon atoms, and R ²³ Has the same meaning as R ²¹ above, and p represents an integer of 0 to 4. 4. The monomer (A), wherein the non-aqueous solvent dispersion further has an amino group represented by the following general formula (IV).
4. The liquid developer for electrostatic photography according to claim 1, containing at least one kind of a monofunctional monomer (C) copolymerizable with [Chemical 5] In the general formula (IV), 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 nitrogen atom. You may form a ring. 5. The non-aqueous solvent dispersion further comprises —PO ₃ H
_At least one monofunctional monomer (D) copolymerizable with the monomer (A), which contains at least one acidic group selected from _two groups, —SO ₃ H group and —SO ₂ H group. The liquid developer for electrostatic photography according to claim 4, further comprising: