JPH02208666A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve redispersibility, preservable property and stability by bringing an oligomer (B) having <=10<4> number average mol. wt. into polymn. reaction with a polymer consisting of specific repeating units in the presence of a resin for stabilizing dispersion. CONSTITUTION:A soln. contg. respectively at least 1 kind of monofunctional monomer (A) and the oligomer (B) formed by combining at least one kind of the polar groups selected from a carboxyl group, sulfo group, etc., only to one terminal of the main chain of the polymer consisting of the repeating units expressed by the formula II and having <=10<4> number average mol. wt. is brought into the polymn. reaction in the presence of the resin for stabilizing dispersion formed by combining the polymerizable double bond group copolymerizing with the monofunctional monomer (A) only to one terminal of the main chain of the polymer having at least one kind of the repeating unit expressed by the formula I. In the formulas I, II, X<1>, T1 respectively denote -COO-, OCO-, etc.; Y<1> denotes 6-32C hydrocarbon group ; a<1>, a<2> respectively denote a hydrogen atom, halogen atom, etc.; R<2> denotes 1 to 22C hydrocarbon group. The stability of dispersion, the redispersibility and the fixability are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 109Ω1 or more and a dielectric constant of 3.5 or less. In particular, the present invention relates to a liquid developer having excellent redispersibility, storage stability, stability, image reproducibility, and fixing properties.

(Prior art) General electrophotographic liquid developers are petroleum-based organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. It is dispersed in a liquid with high insulating properties and low dielectric constant, such as aliphatic hydrocarbon, and further contains a polarity control agent such as a polymer containing metallic fibers, lecithin, linseed oil, higher fatty acids, and vinylpyrrolidone. be.

In such a developer, the resin is dispersed as insoluble latex particles with a diameter of several nanometers to several hundred seconds, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and an insoluble latex are dispersed. Due to insufficient bonding with the particles, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, there is a drawback that the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, causing the particles to settle, aggregate, or accumulate, and the polarity to become unclear. Furthermore, since particles that have aggregated and accumulated are difficult to redisperse, they remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble Latinx particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. This has the disadvantage that redispersion stability is insufficient for practical use, such as solidification, making redispersion difficult, and furthermore causing equipment failure and smudging of copied images. In addition, in the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle size distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized; The particles had a wide particle size distribution containing a large amount of coarse particles, or the particles had a polydisperse particle size with two or more average particle sizes. or,
It was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 111 m or more or very fine particles of 0.1 u or less were formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more types of polar components are used. A method for improving the dispersity, redispersibility, and storage stability of particles by
It is disclosed in No. 62-151868 and the like.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing 5,000 or more sheets using an electrophotographic offset stamp opening master plate has been attempted, and in particular improvements have been made to the master plate. It has become possible to print more than 10,000 large-sized sheets. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixation process.

JP-A-60-179751 and JP-A No. 62-15186
Dispersed resin particles produced according to the method disclosed in No. 8, when the development speed increases, the dispersibility of the particles,
In terms of redispersibility, when the fixing time is shortened, or in the case of large-sized master plates (for example, A-3 size or larger), the performance is still not necessarily satisfactory in terms of rigidity resistance.

The present invention solves the problems of conventional liquid developers as described above.

An object of the present invention is to provide a liquid developer that can speed up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in an electrophotolithography system using a large-sized master plate. That's true.

Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of offset printing plates having excellent printing ink oil sensitivity and stiffness resistance.

Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various transfer applications in addition to the above-mentioned applications.

Still another object of the present invention is to provide a liquid developer that can be used in any system where a liquid developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. That's true.

(Means for Solving the Problems) The above aspects of the present invention provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 109Ω1 or more and a dielectric constant of 3.5 or less. A polymerization process in which the dispersed resin particles are copolymerizable with a monofunctional monomer (A) only at one end of the main chain of a polymer having at least one repeating unit represented by the following general formula (I). In the presence of a dispersion stabilizing resin comprising a double bond group, a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization and the following general formula ( ff)
A carboxyl group, a sulfo group, a hydroxyl group,
An oligomer (B) having a number average molecular weight of 104 or less, which is formed by bonding at least one polar group selected from formyl group, amino group, H or -OR' group (R1 represents a hydrocarbon group), This has been achieved by an electrostatic photographic liquid developer characterized by copolymer resin particles obtained by polymerizing a solution containing at least one of each.

General formula (I) %Formula% In the general formula (+), xl is -COO-1-OCO-1-c
otoco-5-CH, COO-1-〇- or -3Ot
- represents.

Yl represents an aliphatic group having 6 to 32 carbon atoms.

al and al may be the same or different from each other (respectively, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z', or a hydrocarbon group having 1 to 8 carbon atoms) 1-COO-Z', where Zl represents a hydrocarbon group having 1 to 22 carbon atoms.

General formula (Il) bt bt -←C-C← HT'-R atmosphere In general formula (II), TI is 1. coo-, -oco--
coioco-5-CHICOO-5-0--3ot-
1-CON Represents a hydrogen atom or a hydrocarbon group having 1-18 carbon atoms.

R1 represents a hydrocarbon group having 1 to 22 carbon atoms.

bl and b! may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-R', or -Coo via a hydrocarbon group having 1 to 8 carbon atoms. -R', where R4 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

Hereinafter, the liquid developer of the present invention will be explained in detail.

The electrical resistance used in the present invention is 10'Ωcm or more, and the dielectric constant is 3.
Preferably, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, and halogen-substituted products thereof can be used as the carrier liquid. For example, octane, isooctane. , decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G1 Isopar H1 Isopar L (Isopar; trade name of Exxon), Sherzol 70 , Shellsol 71 (Shellsol; trade name of Shell Oil Company),
Amsco OMS, Amsco 4601 agent (Amsco; trade name of Spirif Co., Ltd.), etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are polymers containing at least one repeating unit represented by the general formula (I) in a non-aqueous solvent. In the presence of a dispersion stabilizing resin comprising a polymerizable double bond group copolymerizable with the monofunctional monomer (A) bound only to one end of the main chain of the monofunctional monomer, It is produced by copolymerizing the oligomer (A) and the oligomer (B) (so-called polymerization granulation method).

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

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic carbons. Examples include hydrogen and halogen-substituted products thereof, such as hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane,
Isododecane, isoparaffin-based petroleum solvent Isopar E1 Isopar G1 Isopar H1 Isopar L
1 Sherzol 70, Sherzol 71, Amsco OM
S, Amsco 460 Solvents etc. are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (for example, methyl alcohol,
ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.),
Carboxylic acid ester I! (e.g., methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers 11 (e.g., diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. , methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methyl chloroform, etc.).

It is preferable that the non-aqueous solvent used in the mixture be removed by heating or distillation under reduced pressure after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, it will not affect the liquid in the developer. There is no problem as long as the resistance is within a range that satisfies the condition of 10<9 >[Omega]C- or more.

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of resin dispersion production, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated Examples include hydrocarbons.

Monofunctional monomer (A) and oligomer (B) in a non-aqueous solvent
) The dispersion stabilizing resin according to the present invention, which is used to make a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing with Only at one end of the polymer main chain containing one type of
It is a polymer formed by bonding a polymerizable double bond group that can be copolymerized with a monofunctional monomer (A).

In the repeating unit represented by general formula (I), aliphatic groups and hydrocarbon groups may be substituted.

In the general formula (+), XI is preferably -C00-1
-OCO--CH5OCO-1-CHlCOO- or-
0-, more preferably -COO-5-cH*c
Represents oo- or -〇-.

Yl preferably has 8 to 22 carbon atoms and may be substituted,
represents an alkyl group, alkenyl group or aralkyl group,
Examples of the substituent include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-Z''-C
OO-Z"-0CO-Z"(Z" has 6 to 2 carbon atoms
(2) represents an alkyl group such as a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, and the like. More preferably, yt represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, such as an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a docosanyl group, an octenyl group,
Examples include decenyl group, dodecenyl group, tetradecenyl group, and octadecenyl group.

al and al may be the same or different from each other, preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a carbon number of 1 to
3 alkyl group, -Coo-Z' or cnxcoo-z
(Z' preferably represents an aliphatic group having 1 to 18 carbon atoms), more preferably al and al may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. (for example, methyl group, ethyl group, propyl group, etc.), -coo-z+ or -CHmCoo-Z' (
Z' more preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group,
Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, butenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, octadecenyl group These alkyl groups and alkenyl groups may have the same substituents as those represented by Yl above.

The polymerizable double bond group bonded to one end of the polymer main chain is a group that can be copolymerized with the monofunctional monomer (A), specifically, ■ coa O
CH-C1l-CONH-, CHt-CH-0-C- linking groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, Z3, z4 are hydrogen atoms, halogen atoms (e.g. fc) (Z3, z4 are hydrogen atoms, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g.
Methyl group, ethyl group, propyl group, etc.) ■ CHglICH-3Og-, CH*=C) I-C-1C
Ht-CH-OCH! , CH-5-, CHt-CI-5
CHt-CH-CHt-, etc. can be mentioned.

These polymerizable double bond groups have a chemical structure in which they are directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

-O-, -5-, -C-, -N-, -COO-, -3O
xs (ZS, Zk represents a hydrogen atom, a hydrocarbon group having the same meaning as Zl shown in the above general formula (I)), etc. Consisting of a single linking group or any combination selected from atomic groups such as and the like.

The polymer component of the dispersion/dispersion stabilizing resin of the present invention has the formula -M (I
) with other monomers that can be copolymerized with a homopolymer component or copolymer component selected from the repeating units represented by formula (I) or a monomer corresponding to the repeating unit represented by general formula (I). It is composed of a copolymer component obtained by polymerization.

Other monomers that can be used as a copolymer component together with the polymer component of general formula (I) include, for example, a compound represented by the following general formula (III).

General formula (III) In general formula (Ill), ul is -COO-1-OCO-5
-co! oco-1, where 21 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., 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-methoxyethyl group, 3-
methoxypropyl group, etc.).

zl is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2゜2-dichloroethyl group, 2,2 .2-) lyfluoroethyl group, 2-bromoethyl group, 2-glycidylethyl 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, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group , trimethoxysilylpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-pyridylethyl group, 2-
Morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

d+ and d3 may be the same or different from each other, and each represents the same content as al or a2 in the general formula (2).

Specific monomers represented by general formula (DI) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, acetic acid, monochloroacetic acid, trifluoropropionic acid, etc.) Or allyl esters;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
C1-4 optionally substituted alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2- Bromoethyl group, 2
-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N, N-
dimethylamino)ethyl group, 2-(N,N-diethylamino)ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group base, 2
-Hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group 'J); Styrene derivatives (e.g. styrene, Vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, and nylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethyl styrene, vinylbenzenecarboxamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile; methacriconitrile ; Heterocyclic compound containing a polymerizable double bond group (specifically, for example,
Polymer Science Society Line “Polymer Data Handbook - Group TIIW”
A-J, p 175-184, Baifukan (published in 1986)
(eg, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

Two or more monomers represented by the general formula (I[[) may be used in combination.

The repeating unit represented by the above general formula (I) accounts for 30% by weight or more in the dispersion stabilizing resin polymer used in the present invention.
100% by weight is suitable, preferably 50% by weight - l
OO% by weight.

The dispersion stabilizing resin of the present invention, in which a polymerizable double bond group is bonded only to one end of the polymer main chain, is characterized by: Either by reacting a reagent containing a binding group, or by attaching “
Certain reactive groups'' (e.g. -OH, -COOH', -
3OsH, -Nlb, -SH.

etc.), and then introduce a polymerizable double bond group by polymer reaction (method using ionic polymerization method), or ■ Containing the above specific reactive group in the molecule. After radical polymerization using a polymerization initiator and/or chain transfer agent, "
It can be easily produced by a synthetic method such as a method in which a polymerizable double bond group is introduced by performing a polymer reaction using a specific reactive group.

Specifically, P, Dreyfuss & R,P,
Quirk + [! ncyc1. Polym, Sc1
．． [! ng,, l, 551 (I987), Yoshiki Nakajo, Tatsuya Yamashita, “Dye and Chemicals J, a, 232 (
I985), Akira Ueda, Susumu Nagai, "Science and Industry", Deaf.

57 (I986), P, F, Rempp
&! ! , Franta, Advance
esin Polymer 5science, ]+
1 (I984), Hiroshi Ito-r Polymer Processing J, 3
), 262 (I986), V, Percec.

^pplied Polymer 5science,
It can be produced according to the method described in the review article and the literature cited therein, such as Chu, 97 (I984).

The weight average molecular weight of the dispersion stabilizing resin used in the present invention is lX
Preferably 10' to 5X10', more preferably 2X1
0' to 2XiO'.

Specific examples of the dispersion stabilizing resin used in the present invention are shown below, but the present invention is not limited thereto.

CM.

CHl CM.

HI (I CH.

CH.

C.I.

1゜ CH.

α珀H sauce CH.

1B) CI+.

R:C, Yu~C! alkyl group of wealth (+-21) CM.

XneyOH, -Cj, -Br, -(:N, -C
The monomers used to produce the ON8g non-aqueous dispersion resin are a monofunctional caramer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a monomer (A) that coexists with the monomer (A). A distinction can be made into oligomers (B) that undergo polymerization.

The monomer (A) in the present invention may be any monofunctional monomer that is soluble in a nonaqueous solvent but becomes insolubilized by polymerization. Specifically, for example, the monomer (A) has the general formula (
Examples include monomers represented by rV).

General formula (IV) H-C T*-Rs In general formula (IV), 7i is -COO-1-OCO- an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group , propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl L2-cyanoethyl group, 2-
Hydroxyethyl group, benzyl group, chlorobenzyl group,
methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenyJl/7'robyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3-methoxypropyl group, etc.).

RS is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2゜2-dichloroethyl group, 2,2 .2-) dichloroethyl group, 2-bromoethyl group, 2-glycidylethyl 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, N,N-dimethylaminoethyl L N,N-diethylaminoethyl group , trimethoxysilylpropyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group,
2-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

e' and el may be the same or different, and each represents the same content as bl or bf in the general formula (II).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. C1-C4 optionally substituted alkyl esters or amides of acids (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group) ,
Trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylamino )
Ethyl group, 2-(N,N-diethylamino)ethyl group,
2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3
-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl L2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.)
; Styrene derivatives (e.g. styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, (N,N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfamide, etc.); Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid: cyclic anhydrides of maleic acid and itaconic acid ? Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, Polymer Science Yoshin, "Polymer Data Handbook - Group Mem-J, p175-18
4. Compounds described in Baifukan (published in 1986), for example,
N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N
-vinylmorpholine, etc.).

Two or more types of monomers (A) may be used in combination.

Oligomer (B) is an oligomer with a number average molecular weight of 104 or less, which is formed by bonding the above-mentioned specific scratching group only to one end of the main chain of a polymer consisting of repeating units represented by general formula (II). It is.

In general formula (If), the hydrocarbon groups contained in bI, bRSTl, and R have the number of carbon atoms shown (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted. .

In general formula (II), R in the substituent represented by T-
3 is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 18 carbon atoms (e.g.
Methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group,
Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-
bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl alt, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group) , 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), carbon number 5 ~8 optionally substituted alicyclic groups (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group,
dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusoylamidophenyl group, etc.) It will be done.

Examples of substituents that may have a substituent include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group). etc.).

R: preferably represents a hydrocarbon group having 1 to 18 carbon atoms, and specifically represents the same content as described for R3 above.

bl and bz may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -
COO-R' or -CH1COOR' (R4 preferably represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted) , specifically, represents the same content as that described for R3 above).

bl and b of general formula (II)! It is more preferable that either one of them is a hydrogen atom.

A scratching hydrogen group or -〇R' group that is bonded only to one end of the polymer main chain having a number average molecular weight of 1Xl0' or less and containing at least one type of repeating unit represented by the general formula (II) described above. The hydrocarbon group represented by R11 is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl L2-10 loethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group bromobenzyl group, etc.), or an optionally substituted aromatic group (e.g., phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.) .

When Ro represents an -OR' group, R1 preferably represents the same content as the hydrocarbon group of Ro.

Moreover, among the polar groups of the present invention, the amino group is -NH,, prime number 1
-18 hydrocarbon group, preferably carbon number 1-8
represents a hydrocarbon group, and specifically represents the same content as the hydrocarbon group of Ro described above.

Even more preferably, the hydrocarbon groups of R@, R7, R1 and R9 are an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, or an optionally substituted phenyl group. Examples include groups.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group. The group connecting the component of general formula (It) and the polar group includes a carbon-carbon bond (-multiple bond or double bond),
It is composed of any combination of atomic groups such as carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and heteroatom-heteroatom bonds.

Among the oligomers (B) of the present invention, preferred are those represented by general formula (Va) or general formula (vb).

General formula (Va) 71 R1 General formula (vb) bl bl -(CH-CH1-Q T' -R rich In general formulas (Va) and (vb), bl, b!T1 and R
8 represents the same content as the symbol in general formula (If).

Q represents the aforementioned polar group bonded to one end of general formula (II).

IOW is a simple bond or IC)-(I1", R"R
The eyes are hydrogen atoms, halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms, etc.), cyano groups, hydroxy groups, alkyl groups (e.g. methyl groups, ethyl groups, Si-(R",
RI3 each independently represents a hydrogen atom, a single linking group selected from a hydrogen atom, a hydrocarbon group, etc. representing the same content as R3 above, or a linking group composed of an arbitrary combination. represent

If the upper limit of the number average molecular weight of the oligomer (B) exceeds 1×10 4 , printing durability will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so it is preferably lXl0'' or more.

The oligomer (B) of the present invention is a homopolymer component or a copolymer component selected from repeating units represented by general formula (II) or monomers corresponding to repeating units represented by general formula (II). It is composed of a copolymer component obtained by polymerizing the monomer and other monomers that can be copolymerized with the monomer. General formula (
Examples of other monomers that become copolymer components together with the polymer component II) include acrylonitrile, methacrylonitrile, and heterocyclic compounds containing polymerizable double bond groups (specifically, monomers such as compounds similar to the heterocyclic compounds described in (A)), compounds containing a carboxamide group or sulfamide group and a polymerizable double bond group (e.g., acrylamide, methacrylamide, diacetone acrylamide, 2-carboxamide ethyl methacrylate, vinylbenzenecarboxamide, vinylbenzene sulfamide, 3-sulfamidopropyl methacrylate, etc.).

The repeating unit represented by the general formula (■) described above is 30% by weight to 10% by weight in the oligomer (B) used in the present invention.
0% by weight is suitable, preferably 50% to 100% by weight
It is a weighted percentage.

In addition, the main chain of the polymer contains phosphono groups, carboxyl groups, sulfo groups, hydroxyl groups, formyl groups, amino groups, -P
Those containing no co-electronically synthesized H component containing a polar group of the -R' group are preferred.

The oligomer (B) of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by: (1) reacting various reagents with the ends of living polymers obtained by conventionally known anionic or cationic polymerization; method (ionic polymerization method), radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (radical polymerization method), or 0 or more ions. It can be easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by a polymerization method or a radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss l R, P, Ω
u+rL[! ncyc1. Po1y+w, Sci,
Eng., 7, 551 (I987), Yoshiki Nakajo, Yuya Yamashita, Dyes and Chemicals, 30.232 (I
985), Akira Ueda, Susumu Nagai “Science and Industry” 1.57 (I
986) and the literature cited therein.

More specifically, the oligomer (B) of the present invention can be exemplified by the following compounds. However, the scope of the present invention is not limited to these.

(blank space below) n-1 to lO integer, p: integer from 1 to 4 B)
What is important is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, for the monomer (A) to be insolubilized, general formula (II)
It is preferable to use the oligomer (B) represented by 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.

Even more preferably it is 0.3 to 3%. Further, the molecular weight of the dispersion resin of the present invention is 10' to 101, preferably 10' to 5×10'.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and oligomer (B) are mixed in a non-aqueous solvent with benzoyl peroxide, azo The polymerization may be carried out by heating in the presence of a polymerization initiator such as bisisobutyronitrile or butyllithium.
) A method of adding a polymerization initiator to a mixed solution of (2) a method of dropping monomer (A) and an oligomer (B) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved; A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing the entire amount of the dispersion stabilizing resin and a part of the mixture of monomer (A) and oligomer (B); There is a method of optionally adding a mixed solution of a dispersion stabilizing resin, monomer (A), and oligomer (B) together with a polymerization initiator to a non-aqueous solvent, and any method can be used for production. Can be done.

The total amount of monomer (A) and oligomer (B) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent.

The soluble resin which is the dispersion stabilizing resin is 1 to 100 parts by weight based on 100 parts by weight of the total monomers used above,
Preferably it is 5 to 50 parts by weight.

The appropriate amount of the polymerization initiator is 0.1 to 5% by weight based on the total monomer amount.

Further, the polymerization temperature is about 50 to 180°C, preferably 60 to 120°C. The zero reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers, and esters is used in combination with the nonaqueous solvent used in the reaction, or when unreacted monomers (A) to be polymerized and granulated are If it remains, it is preferably removed by heating to a temperature above the boiling point of the solvent or monomer or distilling it off under reduced pressure.

The non-aqueous dispersion resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and at the same time exhibits extremely stable dispersibility, and can be used repeatedly for a long time, especially in a developing device. Even if the developing speed is increased, the dispersibility is good, and even if the developing speed is increased, redispersion is easy, and no stains are observed on various parts of the device.

Furthermore, when fixed by heating or the like, a strong film was formed and exhibited excellent fixing properties.

Furthermore, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-sized master plate is used.

Although the details of the reason why the redispersion and toner image fixing properties are significantly improved as described above when the resin particles of the present invention are used as a liquid developer are unknown, in the polymerization granulation method of the resin particles of the present invention, Even when oligomer (B) was added as a post-addition after polymerization granulation without using oligomer (B), the above-mentioned effect was not observed. This is considered to be because the oligomer (B) used in the resin particles of the present invention modifies the surface of the resin particles.

In other words, because the polar group is specifically bonded to only one end of the polymer main chain and is polymerized and granulated in a non-aqueous solvent, it is bonded to the resin particle by an anchor effect, and the polar group is bonded to only one end of the polymer main chain. One of the main factors is presumed to be that the moiety modifies the surface of the resin particles and improves the affinity with the dispersion medium.

If desired, a coloring agent may be used in the liquid developer of the present invention, but the coloring agent is not particularly limited; various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. Examples of such materials include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hanzai Elo, quinacridone red, and phthalocyanine blue.

Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
There is a method of dyeing the dispersed resin with a preferred dye, as described in No. 8 and others. Alternatively, as another method, there is a method of chemically bonding a dispersion resin and a dye, as disclosed in JP-A No. 53-54029, or as described in JP-B No. 44-22955, etc. There is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance during production by a polymerization granulation method.

If desired, various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics.
No., page 44, those specifically described are used.

For example, di-2-ethylhexyl sulfosuccinate metal salt,
Examples include naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), and copolymers containing half-maleic acid amide components.

The amounts of each main component of the liquid developer of the present invention are explained below.

The toner particles mainly composed of a resin and an optional colorant are used in an amount of 0.00 parts by weight based on 1000 parts by weight of the carrier liquid.
5 parts by weight to 50 parts by weight are preferred. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fogging will tend to occur in non-image areas. Furthermore, the carrier liquid soluble resin for dispersion stabilization described above may be used as desired, and the carrier liquid 10
About 0.5 parts by weight to 100 parts by weight can be added to 00 parts by weight. The above-mentioned birch charge control agent is preferably used in an amount of 0.001 to 1.0 parts by weight per 11 parts of carrier liquid, and various additives may be added as desired.
The upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developing side with toner particles removed becomes lower than 109 ΩCm, it becomes difficult to obtain a high-quality continuous tone image, so it is necessary to control the amount of each additive added within this limit. is necessary.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

l: A mixed solution of 100 g of p-octadecyl methacrylate, 150 g of toluene, and 50 g of isopropanol,
The mixture was heated to 75°C while stirring under a nitrogen stream.

2.2'-azobis(4-cyanovaleric acid) (abbreviation A, C
, V,) was added and reacted for 8 hours. After cooling, it was reprecipitated into methanol 21, and a white powder was collected by filtration and dried. Obtained white powder 50g, vinyl acetate 3.3g, acetic acid water 11
．． A mixture of 0.025g of hydroquinone, 0.2g of hydroquinone, and 100g of toluene was heated to a temperature of 40°C and reacted for 2 hours.Then, the temperature was raised to 70°C, and 100% sulfuric acid 3.
8×10-'d was added and reacted for 10 hours. Cool to 25°C and add 0.02 g of sodium acetate trihydrate.
After stirring for 0 minutes, the mixture was reprecipitated into 1 ffi of methanol, and the slightly discolored powder was collected by filtration and dried. The yield was 41 g and the weight average molecular weight was 38,000.

In Production Example 1, each dispersion stabilizing resin was produced in exactly the same manner as in Production Example 1, except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate.

A polymerization reaction was carried out in the same manner as in Production Example 1, except that a mixed solution of 100 g of P-10 dodecyl methacrylate, 150 g of ) toluene, and 50 g of isopropanol was used.

After cooling, it was reprecipitated in methanol 21, and a colorless and transparent viscous substance was obtained by decantation, and then dried.

50 g of the resulting viscous material, 1 glycidyl methacrylate
．． 5 g, 2.2'-methylenebis-(6-L-butyl-
A mixture of 1.0 g (p-cresol), 0.5 g of N-dimethyldodecylamine, and 100 g of toluene was heated at a temperature of 1
The mixture was heated to 00°C and stirred for 12 hours. This reaction mixture was mixed with 1 ml of methanol. A pale yellow viscous substance was obtained by the decane silane method, and then dried. The yield was 39 g and the weight average molecular weight was 37,000.

of: 100 g of P-octadecyl methacrylate and 3 toluene
00g of the mixed solution was heated to 70°C while stirring under nitrogen flow.
It was heated to 5 g of 4.4'-azobis(4-cyanopentanol) was added and reacted for 8 hours.

Next, after cooling this reaction product, methacrylic anhydride 6.2
g, 0.8 g of t-butylhydroquinone and 1 drop of concentrated sulfuric acid were added, stirred at a temperature of 30"C for 1 hour, and further heated to a temperature of 50"C.
Stirred at °C for 3 hours. After cooling, it was reprecipitated in methanol 21, and the white powder was filtered and dried. The yield was 88 g and the weight average molecular weight was 38.000.

A mixed solution of 100 g of P-octadecyl methacrylate and 200 g of tetrahydrofuran was heated to 70° C. with stirring under a nitrogen stream. 4.4g of 4'-azobis(4-cyanopentanol) was added and reacted for 5 hours. Furthermore, 1.0 g of the above azobis compound was added and reacted for 5 hours. The reaction mixture was cooled in a water bath to a humidity of 20°C and added with 3.2 g of pyridine and 2.2'-methylenebis-(6-1-
1.0 g of butyl-p-cresol) was added and stirred. 4.2 g of methacrylic acid chloride was added dropwise to this mixed solution over 30 minutes while keeping the reaction temperature from exceeding 25°C. After stirring at a temperature of 20° C. to 25° C. for 4 hours, the reaction product was reprecipitated in a mixture of 1.51 parts methanol and 0.51 parts water, and the white powder was filtered and dried. The yield was 86 g and the weight average molecular weight was 33.000.

In Production Example 12, each dispersion stabilizing resin was produced in exactly the same manner as in Production Example 12, except that the acid chloride shown in Table 2 below was used instead of methacrylic acid chloride.

22: A mixed solution of 98.5 g of P-22 dodecyl methacrylate, 1.5 g of thioglycolic acid, and 200 g of toluene was heated to 70°C under a nitrogen stream.
It was heated to 1.1'-azobis(cyclohexane-1
-Carbonitrile) was added and reacted for 5 hours, and further 0.5 g of the above azobis compound was added and reacted for a further 5 hours. Glycidyl methacrylate 3. Qg,
1.0 g of t-butylhydroquinone and 0.6 g of N,N-dimethylaniline were added and reacted at a temperature of 110'C for 8 hours.

After cooling, the mixture was reprecipitated into 2N methanol, and a pale yellow viscous substance was obtained by decantation, followed by drying. The yield was 80 g and the weight average molecular weight was 33,000.

No. 23: A mixed solution of 98.5 g of P-23 hexadecyl methacrylate, 1.5 g of 2-mercaptoethylamine, and 200 g of tetrahydrofuran was heated to a temperature of 80° C. under a nitrogen stream. 1.1'-azobis(cyclohexane-1-carbonitrile) at 0.
Added 3g and reacted for 5 hours, then added 0.3g of the above azobis compound.
g was added and reacted for 5 hours. To this reaction mixture, 2.5 g of acrylic anhydride and 1.0 g of 2°2'-methylenebis-(6-t-butyl-p-cresol) were added and stirred at a temperature of 40°C for 5 hours. After cooling, the reaction product was reprecipitated into methanol 21 to obtain a colorless viscous substance. The yield was 82 g and the weight average molecular weight was 20.000.

No. 4: P-4 A mixed solution of 100 g of dodecyl methacrylate and 200 g of tetrahydrofuran was heated to 65° C. under a nitrogen stream. 6 g of 2.2'-azobis(4-cyanovaleric acid chloride) was added and stirred for 10 hours.

The reaction solution was cooled to a temperature below 25°C in a water bath, and 2.4 g of allyl alcohol was added. Add 2.5 g of pyridine dropwise without exceeding the reaction temperature of 25°C.
Stir for hours. After further stirring for 2 hours at a temperature of 40°C, the mixture was reprecipitated into 2Il of methanol. A pale yellow viscous substance was obtained with Decanticillon and then dried. The yield was 80 g and the weight average molecular weight was 38.000.

100 g of black sesame (Nio sesame B-methyl methacrylate), 5 g of thioglycolic acid, 15 toluene
A mixed solution of 0 g and 50 g of methanol was heated to a temperature of 70'C while stirring under a nitrogen stream. 2.2'-azobis(isobutyronitrile) (abbreviation A, 1.B, N,)
1.5 g of was added and reacted for 4 hours. Furthermore, A.1. B,
0.4 g of N was added and reacted for 4 hours. After cooling, this reaction solution was reprecipitated into a 2N mixed solution of methanol/water (volume ratio (4/l)), the methanol solution was separated with decanethiolone, the viscous substance was dried, and a colorless viscous substance was obtained. The number average molecular weight of 75 g of the 0 polymer obtained was 2,800.

In Production Example 1 of 2-12 second sesame-B-2 Fudan-nihii oligomer, 5 g of thioglycolic acid
Each oligomer B-2 to
B-12 was manufactured. The number average molecular weight of the obtained oligomer was 2,500 to 3,500.

Table 3 In Production Example 1 of 13-23 Nio Sesame B-3 oligomer, the same procedure as in Production Example 1 was used except that the monomers in Table 4 were used instead of methyl methacrylate. Each oligomer B-13 to B-23 was manufactured. The number average molecular weight of the obtained oligomer was 2,500 to 3.
,500.

While stirring a mixed solution of 150 g of toluene and 50 g of ethanol under a nitrogen stream,
It was heated to a temperature of 75°C. 8 g of 2.2'-azobis(cyanovaleric acid) (abbreviation ^, C, V) was added and reacted for 5 hours, and further 2 g of A, C, V were added and reacted for 4 hours. After cooling the obtained reaction solution, methanol/water ((4/1)
Volume ratio] After reprecipitation in a mixed aqueous solution and separating the methanol aqueous solution by decantation, the viscous substance was dried. Yield 70
The number average molecular weight of the polymer was 2,600.

O Goma 25-33: 1st Goma B-25~
B-33 In Oligomer Production Example 24, polymerization initiators A, C,
Each oligomer B-25 to
B-33 was manufactured. The number average molecular weight of the obtained oligomer was 2,000 to 4,000.

Table-5 R-N-N-R: Azobis compound (continued) Table-6 --Su's: --14 g of Cus D-1 dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1.0 g of oligomer B-1. A mixed solution of 380 g of 0 g and Isopar H was heated to 70° C. while stirring under a nitrogen stream. 2.2'-azobis(valeronitrile) (abbreviation A,
0.8 g of B, V, N,) was added and reacted for 6 hours. 20 minutes after the starting addition, white turbidity occurred and the reaction temperature rose to 88°C. The temperature was raised to 100°C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate.

After cooling, the resulting white dispersion was passed through 200 meshes of nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 88% and an average particle size of 0.244.

In production example 1 of latex particles, oligomer B-1
A white dispersion was obtained in the same manner as in Production Example 1, except that the oligomer shown in Table 6 below was used instead. The polymerization rate of each white dispersion was 85 to 90%. Moreover, the average particle size of each latex was in the range of 0.23 to 0.274.

Table 6 (continued) In production example 1 of latex particles, dispersion stabilizing resin P
A white dispersion was obtained in the same manner as in Production Example 1, except that the dispersion stabilizing resins and oligomers listed in Table 7 below were used in place of Oligomer B-1 and Oligomer B-1. The polymerization rate of the obtained dispersion was 85 to 90%.

Table - 362 - Cus D-3
6 12g of dispersion stabilizing resin P-24 100% vinyl acetate
g1 Crotonic acid 5g, oligo? A mixed solution of 1.0 g of -B-3 and 468 g of Isopar E was heated to 70°C while stirring under a nitrogen stream. A, B, V, N.

After 6 hours of reaction, the temperature was raised to 100'C and the mixture was stirred for 1 hour to distill off the remaining vinyl acetate. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth, with a polymerization rate of 85% and an average particle size of 0.23.
- latex.

°-Cus No. 3: -A mixed solution of 14g of Cus D-3 dispersion stabilizing resin P-1, 100g of vinyl acetate, 6.0g of 4-pentenoic acid, 0.8g of Oligomer B-15, and 380g of Isopar G. was heated to a temperature of 70''C while stirring under a nitrogen stream.

0.7 g of benzoyl peroxide was added and reacted for 4 hours, and further 0.5 g of benzoyl peroxide was added and reacted for 2 hours.

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.244.

--S 38: --A mixed solution of 18 g of Cus D-3 dispersion stabilizing resin P-2, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of oligomer B-9, and 380 g of n-decane was heated with nitrogen. The mixture was heated to a temperature of 75° C. while stirring under a stream of air.

A.1. Add 7g of B and N, react for 4 hours, and then add ^, 1
．． B.N.

0.5g of was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.22.

-15g of 39Nix D-39 dispersion stabilizing resin P-22, 10 methyl methacrylate
0 g, 1.0 g of oligomer B-19. g and n-decane 4
70 g of the mixed solution was heated to a temperature of 70° C. while stirring under a nitrogen stream. ^, 1. B, N, 1. Add Og,
It reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.32.

-- In Production Example 1 of OA latex particles, oligomer B-1
The procedure was the same as in Needlework Example 1 except for the following. The obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.25.

-- In Example 1 of producing 4B latex particles, dispersion stabilizing resin P-1
The procedure was the same as in Production Example 1, except that a mixed solution of 14 g of vinyl acetate, 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate, and 385 g of Isopar H was used.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.22.
- latex.

In production example 1 of 42C latex particles of
The procedure was carried out in the same manner as in Production Example 1, except for using the mixed solution of g.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.24.
- latex.

Monomer (+) Example 1 Dodecyl methacrylate/acrylic acid copolymer [copolymerization ratio (95/5) weight ratio) 10 g, nigrosine 10 g
and 30 g of Shell Silua 1 were placed in a paint shaker (Tokyo Seiki ■) with glass beads, and dispersed for 4 hours.
A fine dispersion of nigrosine was obtained.

30g of latex D-1 of latex particle production example 1
A liquid developer for electrostatic photography was prepared by diluting 2.5 g of the above nigrosine dispersion and 0.08 g of the octadecene-half-maleic acid octadecylamide copolymer to 11 of Shell Sila 1.

(Comparative Developer A-C) In the manufacturing example of the liquid developer described above, latex D-1 was replaced with the following latex, and comparative liquid developers A, B,
Three types of C were produced.

Comparative liquid developer A Latex of Nilatex particle production example 40 Comparative liquid developer B Latex of Nilatex particle production example 41 Comparative liquid developer C Latex of Nilatex particle production example 42 These liquid developers Fully automatic plate making machine! ! Using this as a developer for LP404V (manufactured by Fuji Photo Film ■), an electrophotographic light-sensitive material, ELP Master ■ type (manufactured by Fuji Photo Film ■), was exposed and developed.

The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. Darkening rate of copied image (
(image area) was performed using 20% of the manuscript. The results are shown in Table-8.

Table 8 When each developer was plate-made under the above-mentioned plate-making conditions, the developer of the present invention was the only one that did not cause staining of the developing device and provided a clear image on the 2000th plate-making plate.

On the other hand, offset printing master plates (ELP masters) obtained by plate making using each developer were printed using a conventional method, and the number of prints was compared until the printed image showed missing characters, fading in solid areas, etc. However, in the master plates obtained using the developers of the present invention, Comparative Example A, and Comparative Example C, the problem did not occur even after 10,000 sheets or more, but in the mask plate using Comparative Example B, the problem occurred after 8,000 sheets.

As can be seen from the above results, only the developer made from the resin particles of the present invention caused no staining of the developing device and at the same time significantly increased the number of master plates printed.

That is, in the case of Comparative Example A, there was no problem with the number of prints, but the developing device was extremely dirty and could not withstand continuous use.

In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 5.
When used at high plate-making speeds such as sheets/minute (conventionally, the plate-making speed was 2 to 3 sheets/minute), the developing device (especially on the back electrode plate) becomes dirty, and after 2,000 sheets, the plate becomes dirty. The image quality of the copied images has been affected (decreased Dmax, fading of thin lines, etc.). The number of master plates printed was not a problem in Comparative Example C, but decreased in Comparative Example B.

These results demonstrate that the resin particles of the present invention are clearly superior.

Example 2 White dispersion 100 obtained in latex particle production example 2
A mixture of 1.5 g of Sumikaron Black and 1.5 g of Sumikaron Black was heated to 1.
The mixture was heated to 00°C and stirred for 4 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.20.

32g of the above black resin dispersion 1 zirconium naphthenate 0
．． A liquid developer was prepared by diluting 15 g of higher alcohol FOC-1400 (manufactured by Nissan Chemical Company) to 1N of Shell Silua 1.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 3 White dispersion lo obtained in latex particle production example 36
ng and Victoria Blue B at a temperature of 70
The mixture was heated to 80°C to 80°C and stirred for 6 hours. After cooling to room temperature 2
The remaining dye was removed by passing it through a 0.00 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.16-.

32g of the above blue resin dispersion, zirconium naphthenate o
, os g , and a liquid developer was prepared by diluting 15 g of higher alcohol F OC-1600 (manufactured by Nissan Chemical Co., Ltd.) to 1N of Isopar H.

When this was developed using the same device as in Example 1, 20
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 4 32 g of white resin dispersion obtained in latex particle production example 3
A liquid developer was prepared by diluting 2.5 g of the nigrosine dispersion obtained in Example 1 and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 11 of Isopar G.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Furthermore, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were both very clear.

After this developer was left for 3 months, the same treatment as above was carried out, but there was no difference in appearance from before.

Example 5 Poly (decyl methacrylate) 10g, Isopar H
and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

30 g of white resin dispersion D-13 obtained in latex particle production example 13, and the above alkali blue dispersion 4.2.
A liquid developer was prepared by diluting 0.06 g of a semi-docosanylamidate of a copolymer of octadecyl vinyl ether and maleic anhydride, and 15 g of higher alcohol F OC-1400 to 12 of Isopar G.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Moreover, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were very clear.

Examples 6 to 26 Each liquid developer was produced in the same manner as in Example 5, except that resin particles shown in Table 9 below were used instead of resin particles D-13.

Table 9 (Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device did not become contaminated, and both the image quality of the obtained offset printing master plate and the image quality of the printed matter after printing 10,000 sheets were very clear. Ta.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, little or no toner adhesion was observed on the device.

Furthermore, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were very clear.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: A monofunctional monomer (
A monofunctional monomer that is soluble in the nonaqueous solvent but becomes insolubilized by polymerization in the presence of a dispersion stabilizing resin bonded with a polymerizable double bond group that can be copolymerized with A). A carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and a ▲mathematical formula, There are chemical formulas, tables, etc. ▼ group [R^0 is a hydrocarbon group or -O
R^1 group (R^1 represents a hydrocarbon group)] At least one type of oligomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding at least one type of polar group selected from R^1 group (R^1 represents a hydrocarbon group) 1. A liquid developer for electrostatic photography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing the developer. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), X^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O- or -SO_2-. Y^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
represents a hydrocarbon group, -COO-Z^1 or -COO-Z^1 via a hydrocarbon group having 1 to 8 carbon atoms, where Z
^1 represents a hydrocarbon group having 1 to 22 carbon atoms. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), T^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O-, -
SO_2-, -CON-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, R^3 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. R^2 represents a hydrocarbon group having 1 to 22 carbon atoms. b^1 and b^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
represents a hydrocarbon group, -COO-R^4 or -COO-R^4 via a hydrocarbon group having 1 to 8 carbon atoms, where:
R^4 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.