JPH0219856A - Liquid developing agent to be used in electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain a liquid developing agent to be used for electrostatic photography having improved dispersion stability and redispersibility by constituting dispersed resin particles contained in the developing agent of a copolymer resin obtd. by copolymerizing a monofunctional monomer with a specified macromonomer, both being contained in a soln., in the presence of a specified dispersing resin. CONSTITUTION:Dispersed resin particles contained in the title developing agent are constituted of a copolymer resin obtd. by copolymerizing a monofunctional monomer, which is soluble in a nonaqueous solvent but becomes insoluble by polymerization, with a monofunctional macromonomer having >=1X10<4> number average mol.wt. and being formed by bonding a polymerizable double bond group expressed by the formula III to only one terminal of principal chain of a polymer comprising recurrent units expressed by the formula II, in a soln. contg. at least one kind of each monomer in the presence of a dispersing resin having <=1X10<4> weight average mol.wt. and being bonded with a polar group selected from COOH group, sulfo group, etc. to only one terminal of a principal chain of a polymer contg. recurrent units expressed by the formula I. In the formulas I to III, X is a -COO- group, etc.; Y is an aliphatic group; each a1, a2 is a cyano group, etc.; each V, V' is a -OCO- group, etc.; W is a hydrocarbon group; each b1, b2, c1, c2 is a halogen atom. Thus a liquid developing agent to be used for electrostatic photography having improved dispersion stability and redispersibility is obtd.

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 109 Ωcm or more and a dielectric constant of 3.5 or less. , especially redispersibility, storage stability,
It relates to a liquid developer with excellent 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 an aliphatic hydrocarbon, and further contains a polarity control agent such as a metal soap, lecithin, linseed oil, higher fatty acid, or a polymer containing vinylpyrrolidone. In such developers, the resin is dispersed as insoluble latex particles in the form of particles with a diameter of several ni1 to several hundred nanometers, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, there has been a drawback that the soluble dispersion stabilizing resin is desorbed from the insoluble Latinx particles due to long-term storage or repeated use, causing the particles to settle, aggregate, or accumulate, and the polarity to become unclear.

In addition, particles that have aggregated and accumulated are difficult to redisperse, so they remain attached to various parts of the developing machine, leading to developing machine malfunctions such as blurring 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 latex particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, these liquid developers
Although the dispersion stability 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 hardens into a film and is difficult to redisperse. In addition, there is a further drawback that the redispersion stability is insufficient for practical use, such as causing equipment failure and staining of copied images. In the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle distribution, there are significant restrictions on the combination of the stabilizer used and the monomer to be insolubilized. ,
In general, particles with a wide particle size distribution containing a large amount of coarse particles or polydisperse particles with two or more average particle sizes were obtained. In addition, it is difficult to obtain a desired average particle size with monodispersed particles with a narrow particle size distribution, and large particles of 1 μ or more or 0.
．． Very fine particles of less than 1% were formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a manufacturing process that is frequent and takes a long time.

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 of improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A-60-179751 and JP-A-62-151868.

(Problems to be Solved by the Invention) On the other hand, in recent years, attempts have been made to print a large number of 5,000 or more sheets using an electrophotographic offset printing master plate. It has become possible to print more than 10,000 sheets in plate size. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixing 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 aims to improve 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-size master plate. That's true.

Another object of the present invention is to provide a liquid developer that enables the production of an offset printing original plate having excellent printing ink fat resistance and stiffness resistance by electrophotography.

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) An object of the present invention is to provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 109ΩC11 or more and a dielectric constant of 3.5 or less. The dispersed resin particles contain at least a carboxyl group, a sulfo group, a hydroxyl group, an amino group, and a phosphor group at one end of the main chain of the polymer containing the repeating unit shown in (1) in the membrane below. In the presence of a dispersing resin with a weight average molecular weight of 1 x 104 or more, which is formed by bonding a type of polar group,
One end of the main chain of a polymer consisting of a monofunctional monomer (A) that is soluble in non-aqueous solvents but becomes insolubilized by polymerization and a repeating unit represented by the following catalytic formula (II) Only in the following - monofunctional macro-7mer (B) having a number average molecular weight of 1 x 104 or less, which is formed by bonding a polymerizable double bond group represented by (I[I), is added in a small amount (both It has been found that this can be achieved by an electrostatographic liquid developer characterized by copolymer resin particles obtained by polymerizing a solution containing one type of developer.

-In the film (1) In formula (1), X is -coo--oco -CHzOCO
C3ICo.

〇-or-SO! - Was.

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

a and a 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-Z, or a hydrocarbon group having 1 to 8 carbon atoms. -C00-Z (Z represents a hydrocarbon group having 1 to 22 carbon atoms).

-In the membrane (n) 1I V-W In formula (n), V is -coo--oc.

CHxOCOCHzCOOOSow (R11 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

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

b, 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-Q, or a COO-RO via a hydrocarbon group having 1 to 8 carbon atoms. (Q represents a hydrocarbon group having 1 to 18 carbon atoms).

-In the membrane (III) In formula 1, V' has the same meaning as ■ in formula (n).

CI and C1 may be the same or different, and each has the same meaning as b or b2.

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

The electrical resistance used in the present invention is 1090 cm or more, and the dielectric constant is 3.
Preferably, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons and their halogen-substituted products 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 E1 Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon), Cielzol 70. Sherzoll 7
1 (Shellsol; a trade name of Shell Oil Co.), Amsco OMS, Amsco 460 solvent (Amsco; a trade name of Spirits Co.), etc. are used alone or in combination.

The non-aqueous dispersed resin particles (hereinafter also referred to as latex particles), whose quantity is also an important component in the present invention, are made by bonding a polar group only to one end of the polymer main chain in a non-aqueous solvent. The monomer (A) and the macromonomer (B) are copolymerized and granulated in the presence of a dispersion stabilizing resin having a weight average molecular weight of 1×10 4 or more.

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 hydrocarbons. and halogen-substituted products thereof. For example, hexane, octane, isooctane,
Decane, Isodecane, Decalin, Nonane, Dodecane, Isododecane, Isopar E, Isopar G, Isopar H1 Isopar L1 Scherzol 70, Scherzol 7
1. Amsco OMS, Amsco 460 solvent, etc. are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.) , carboxylic acid esters (e.g. methyl acetate, ethyl acetate,
propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. methylene dichloride, chloroform, carbon tetrachloride, etc.) , dichloroethane, methylchloroform, 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 109Ωc1 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.

The dispersion stabilizing resin of the present invention, which is used to make a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing monomers in a non-aqueous solvent, polymerizes with the monomers. It is a resin that does not contain a graft group, and only at one end of the polymer main chain containing at least one type of repeating unit indicated by ([) in the membrane, there is a carboxy group, sulfo group, phospho group, hydroxyl group, or amino group. It is a polymer formed by bonding at least one kind of polar group selected from the following.

In the repeating unit represented by general formula (1), aliphatic groups and hydrocarbon groups may be substituted.

- In the film (1), X is preferably -COO-1O
COCHzOCOC1 (represents zcOo- or 0-,
More preferably it represents -C00CIl□COO- or -〇-.

Y preferably represents an optionally substituted alkyl group, alkenyl group, or aralkyl group having 8 to 22 carbon atoms. As a substituent, a position other than the polar group bonded to one end of the main chain of the polymer mentioned above may be used. ! 5 may be used, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), OZ, , COOZz, OCOZz (Zl,
Z2 represents an alkyl group having 6 to 22 carbon atoms, 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, Y has 8 to 22 carbon atoms.
represents an alkyl group or an alkenyl group. Examples include octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, and the like.

alSa! 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, an alkyl group having 1 to 3 carbon atoms, -coo-z or HCl1ICOOZ (Z represents an aliphatic group having 1 to 22 carbon atoms). More preferably, al and a2 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -coo-z or -CLCOOZ (Z more preferably has 1 to 1 carbon atoms
8 represents an alkyl group or an alkenyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group,
Examples include tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups may have the same substituents as shown for Y above). represent.

Further, a polar group bonded only to one end of the polymer main chain has a chemical structure in which it is bonded directly to one end of the polymer main chain or bonded via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. Consisting of any combination of atomic groups of atomic bonds, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), cyano groups, hydroxyl groups, alkyl groups (e.g., methyl groups, ethyl groups, propyl groups) ←fjl=CH←, ←fjl=CH←, ←, or a hydrocarbon group having the same meaning as Z shown in (1) in the above-mentioned membrane]. or a linking group constituted by any combination thereof.

The polymer component of the dispersion resin of the present invention is a homopolymer component or a copolymer component selected from repeating units represented by the -C formula (1), or a general formula (corresponding to the repeating unit represented by N). It is composed of a copolymer component obtained by polymerizing a monomer that can be copolymerized with another monomer that can be copolymerized.-In the membrane (
Other monomers that can be used as a copolymer component together with the polymer component 1) include, for example, a compound represented by the general formula (rV) described below.

The repeating unit represented by the above general formula (summer) accounts for 30% by weight to 10% by weight in the dispersing resin polymer used in the present invention.
0% by weight is appropriate, preferably 50% to 100% by weight.
Weight%.

Further, it is preferable that the main chain of the polymer does not contain a copolymer component containing a polar group such as a carboxyl group, a sulfo group, a hydroxyl group, an amino group, or a sulfo group.

The dispersion stabilizing resin of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents with the ends of living polymers obtained by conventionally known anionic or cationic polymerization. (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 the above ionic polymerization method or 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 radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, 0reyfuss, R, P, Qu
irk+ encycle.

Po1y*, Sci, Eng+7.551 (1987
), Yoshiki Nakajo, Yuya Yamashita “Dye and Medicine”, Zeni, 232 (
1985), Akira Ueda, Susumu Nagai, “Science and Industry”, Utsubo, 57
(1986) and the literature cited therein.

The dispersion stabilizing resin of the present invention has a weight average molecular weight of 1 x 104~
lXl0' is preferred, more preferably 1.5X10
If the zero weight average molecular weight, which is '~8X10', is less than 1X10', the average particle diameter of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.54) and the particle size distribution becomes wide. Moreover, when it exceeds lXl0', the average particle diameter of the resin particles obtained by polymerization granulation becomes large, and 0.
It may become difficult to align the average particle size within the preferred range of 2 to 0.4.

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

(I-2) H3 1(ZNCH2CH2-5-+CFh-C→-cooc
, □H29 lh HOOC-CHzCHz-3-←CHz-c→-(!O
OC, Mt.

(I lh 1(00C-CHz-3-(-CHz-C→-C00C
+J,y (I CI.

CH3 CH3 (■ CI(3 CH.

CH3 CH3 N C00C+zHzs N C00C+J33 CH3 H(hP-CHzCHz S-+-CHz~C→-O
OC @H37 (■ In the formula, T is -COO 0CO -CH20CO cozcoo-1-〇-1-CON-1-5O, N- or U. The monomer used in producing the non-aqueous dispersion resin is Monofunctional monomers (A) are soluble but become insolubilized by polymerization, and monofunctional macromonomers (B) are copolymerized with monomer (A).

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 general formula (I
Examples include monomers represented by V).

General formula (TV) ■ -R 1 to 18 optionally substituted aliphatic groups (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,
23-phenyl 7'ovir group, dimethylbenzyl group, fluorohensyl group, 2-methoxyethyl group, 3-methoxypropyl group, etc.] R is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms Groups (e.g. methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl 75.2.2-dichloroethyl group, 2.2.2-) +J fluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group , 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxyethyl 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-fluoroethyl group, 4-hydroxybutyl group , 2 furfuryl ethyl 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-carboxamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group,
cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

dl and d2 may be the same or different, and each is a or a! in (1) in the above-mentioned film. represents the same content as .

As a specific monomer (A), for example, a carbon number of 1 to 6
unsaturated vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, acetic acid, monochloroacetic acid, trifluorobucopionic acid, etc.), acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Alkyl esters or amides having 1 to 4 carbon atoms of carboxylic acids (alkyl groups such as methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl) basis,
Trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethyl amino,)
Ethyl group mi-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 group, 2-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), unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, or cyclic anhydrides of maleic acid and itaconic acid , acrylonitrile, methacrylonitrile, heterocyclic compounds containing a polymerizable double bond group (specifically, for example, edited by the Society of Polymer Science [Polymer Data Handbook-Group v1 edition-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.

- The functional macromonomer CB) can be copolymerized with the monomer (A) only at one end of the main chain of the polymer consisting of the repeating unit of (II) in the membrane, and has the general formula (III). )
It is a macromonomer having a number average molecular weight of 104 or less, which is formed by bonding a polymerizable double bond group represented by:

General formula (II) and (Ill) Niite b, , b2, V
, W, C1, C2 and ν' each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted. formula(
In n), in addition to a hydrogen atom, R11 in the substituent represented by
18 optionally substituted alkyl groups (for example, 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 (for example, 2-methyl -1-prohenyl L2-
7'tenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, ■-pentenyl L l-hexenyl group,
2-hexenyl L4-methyl-2-hexenyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group)↓netyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group group, ethylbenzyl group, methoxyhensyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2
-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, flobylphenyl group, butyl Phenyl 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, dobushilo ylamidophenyl group, etc.).

Examples of the substituent which may have a substituent include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group, etc.) ) etc.

W preferably represents a hydrocarbon group having 1 to 18 carbon atoms,
Specifically, it represents the same content as that described for R11 above.

b and b2 may be the same or different from each other,
Each is preferably a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.)
, -COO-Q or -CH,C00Q (Z 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,
These may be substituted, specifically, the above R1
represents the same content as that described for ).

In II (III), V' has the same meaning as ■ in formula (IT), and +C1 and C2 may be the same or different from each other, and have the same meaning as ``su'' or ``b'' in formula (■) above. ll
Preferred ranges of V', cl, and C2 are the same as those explained for v, b, and b2 above.

It is more preferable that either one of Su and Su in formula (It) or C2 and ct of Formula (III) is a hydrogen atom.

The macromonomer provided in the present invention is as described above: - only at one end of the polymer main chain consisting of the repeating unit represented by (n) in the membrane; It has a chemical structure in which the heavy bond groups are directly bonded or bonded by an arbitrary linking group. formula(
The group connecting the component II) and the component of formula (III) is,
carbon-carbon bond (-double bond or double bond), carbon-
It is composed of any combination of atomic groups such as a heteroatom bond (heteroatoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.) and a heteroatom-heteroatom bond.

Among the macromonomers (B) of the present invention, preferred are those represented by formula (V).

Formula (V) ) IV - In formula (V), b3, b2, C15e! , V, W, and V' represent the same contents as explained in formula (■) and formula (III), respectively.

represents a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (e.g., 1, methyl group, ethyl group, propyl group, etc.)], N)ICONll z ■ −5+ t3 (Rxs represents a hydrogen atom or a hydrocarbon group having the same content as R1 above) Represents a single linking group or a linking group composed of any combination selected from atomic groups such as .

The upper limit of the number average molecular weight of the macromonomer (B) is lXl0
If it exceeds ', the stiffness resistance will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so it is preferably 1 x 104 or more.

Particularly preferable examples of each of ν, village, υ, b5, byo, dl, and d2 in (n), (I[[), or (V) in the above-mentioned film are shown below.

V is -coo --oco --.

-CH, COO- or -C)ItOCO-, - is an alkyl group or alkenyl group having 18 or less carbon atoms, and V' is all of the above (provided that R8 is a hydrogen atom), b2 , b2, C6 and C2 include a hydrogen atom or a methyl group.

The macromonomer (B) of the present invention can be produced by a conventionally known synthesis method. Polymerization method Oligomers with terminal reactive groups bonded by radical polymerization using a polymerization initiator and/or chain transfer agent containing reactive groups such as capoxyl groups, hydroxyl groups, and amino groups in the molecule. and various reagents to form a macromer, and polyaddition, in which a polymerizable double bond group is introduced into an oligomer obtained by polyaddition or polycondensation reaction, in the same manner as the radical polymerization method described above. Examples include a method using a condensation method.

Specifically, P, Dreyfuss & R, P, mouth u
irk, EncyclePolym, Sci, Eng
, , 7.551 (1987), P.F.Remp.
p, E, Franta.

Adu, Polym, Sci, 58.1 (19
84), V. Percec, Appl.

Polym, Sci., 285.95 (1984)
, R, Asami, M, TakaRi.

Makvamol, Chew, 5upp1.12.
163 (1985), P, Re5pp.

etal, Makvamol, Chew, 5upp
1. 8+3 (1984), Yuji Yogami, Chemical Industry, 56 (1987), Yuya Yamashita, Polymer,
31.988 (1982), Shibe Kobayashi, Polymer, Plate 6
25 (1981), Toshinobu Higashimura, Japan Adhesive Association Journal 153
6 (1982), Hiroshi Ito-1 Polymer Processing, Co., Ltd., 262
(1986), Higashi Takashibe, Tsuda Takashi, Functional Materials, 1987
Review articles such as No. 10, '5, etc. and references cited therein.
It can be synthesized according to methods described in patents and the like.

Specific examples of the macromonomer (B) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

(n-1) (II-2) ■ C00C1L (n-3) C11゜ (If-7) (n-4) Hs C00C)l.

■ 0OCH3 (■ H3 0OCJs (n-6) C00CJth (■ CI+3 CH 0OCJt (II-13) Hi COOCzHs (II-15) CH3 (■ CII+ CH CI+ C11゜ C11゜ C00CII□C-(-CI-!2-C→-N C00C4119 (■ (■ shi41'19 (■ COOC2H3 COOCI(s (n-19) COOC2H.

(■ CH.

C00C112CL+CII□-〇-Lu C00CI+
.

(II-25) CI+□ 1l CH.

C00CII□CIl□-C+CHz -Cll→-N 0COCzHs (II-27) CH.

1l CHl C00CHzC1lCHzOOCCII□SbeCH2-
C→-0■ C00C+all+t (Il-28) C113 (■ CIl□=CHC113 COOCR2C) ICH2S (CIl□-C→-01
1C00C+aHzt (It-33) CN coc z tl 25 (n-34) COOC,Hq CL=C1l CI++1 SO2NHCHzCIIzS-(C1b-C〇-COO
CalLt COOC+5lht (It-35) CL=C)l cHz OCOCH2CH2C+Cll2-C)I→-CN
C00C+ellztThe dispersion resin of the present invention contains at least 1 each of the monomer (A) and the macromonomer (B).
The important thing 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, the ratio of the macromonomer (B) to the monomer (A) to be insolubilized is 0.1-1.
It is preferable to use 0% by weight, more preferably 0% by weight.
．． It is 2 to 5% by weight. Even more preferably 0.3 to 3
Weight%. Further, the molecular weight of the dispersion resin of the present invention is 103~
10h, preferably 104 to 5X10'.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and macromonomer (B) are mixed in a non-aqueous solvent with benzoyl peroxide, The polymerization can be carried out by heating in the presence of a polymerization initiator such as azobisisobutyronitrile or butyllithium. Specifically, a mixed solution of a dispersion stabilizing resin, a monomer (A), and a macromonomer (B) can be used. A method of adding a polymerization initiator to the solution, a method of dropping monomer (A) and a macromonomer (B) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved, or a method of adding a polymerization initiator to a solution of a dispersion stabilizing resin, or a method of adding a polymerization initiator to a solution of a dispersion stabilizing resin A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing part of the mixture of monomer (A) and macromonomer (B), and furthermore, a method of adding the remaining monomer mixture to a non-aqueous solvent. , a method of optionally adding a mixed solution of a dispersion stabilizing resin and a monomer together with a polymerization initiator, etc., and production can be achieved using any of these methods.

The total amount of monomer (A) and macromonomer (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 amount of polymerization initiator is 0.1 to 5% (weight) of the total monomer amount
is appropriate.

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 the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the non-aqueous solvent used in the reaction, or when the 411 body (A) or macromonomer (B) is polymerized and granulated. If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than the boiling point or distilling them 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 the 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-size master plate is used.

If necessary, a coloring agent may be used in the liquid developer of the present invention.

The coloring agent is not particularly specified; 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. There is. Examples 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 necessary, various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics.
Those specifically described in No. 2, page 44 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 amount of toner particles mainly composed of a resin and optionally a colorant is preferably 0.5 to 50 parts by weight based on 1000 parts by weight of the carrier liquid, and if it is less than 0.5 parts by weight, the image density will decrease. If it is insufficient and exceeds 50 parts by weight, fogging tends to occur in non-image areas. Furthermore, the carrier liquid soluble resin for dispersion stabilization is also used as required, and can be used in an amount of about 0.5 parts by weight to 100 parts by weight per 1000 parts by weight of the carrier liquid. Charge 1 as described above! The moderating agent is preferably used in an amount of 0.001 to 1.0 parts by weight based on 1000 parts by weight of the carrier liquid. Furthermore, various additives may be added as necessary, and 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 developer with toner particles removed becomes lower than 10'ΩC1, it becomes difficult to obtain a high-quality continuous tone image, so the amount of each additive added is controlled within this limit. It is necessary.

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

Production Example 1 of Dispersion Stabilizing Resin A mixed solution of 100 g of octadecyl methacrylate, 150 g of toluene, and 50 g of isopropanol was heated to 70° C. with stirring under a nitrogen stream. 2,2゛-Azobis(cyanovaleric acid) (abbreviation a, C, V) 5.0g
was added and reacted for 8 hours. After cooling, it was reprecipitated into 2N methanol, and a white powder was collected by filtration and dried to obtain a powder with a yield of 85 g and a weight average molecular weight (hereinafter referred to as 26,000).

Production example 2 of resin for dispersion stabilization Dodecyl methacrylate 100g, ) Luene 150
A polymerization reaction was carried out in the same manner as in Production Example 1, except that a mixed solution of 50 g and 50 g of isopropanol was used. After cooling, it was reprecipitated into methanol 22 to obtain 83 g of a colorless and transparent viscous substance. ff11 was 27,000.

Production example 3 of resin for dispersion stabilization Octadecyl methacrylate long and toluene 30
0g of mixed solution was heated to 70°C while stirring under nitrogen flow.
It was heated to 4.6 g of 4°-azobis(4-cyanopentanol) was added and reacted for 8 hours. After cooling, it was reprecipitated into methanol 21 to obtain 86 g of white powder.

- was 28,000.

Production example 4 of resin for dispersion stabilization: 70 g of dodecyl methacrylate, 30 g of butyl methacrylate, 150 g of luene, and 50 g of Impropatool
The mixed solution was heated to 70°C while stirring under a nitrogen stream. ^, C, V, 6 g was added and reacted for 8 hours.

The h of the copolymer was 23,000.

Production Example 5 of Dispersion Stabilizing Resin A mixed solution of 98.5 g of tridecyl methacrylate, 1.5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 65°C. 2. Add 1.0 g of 2'-azobis(isobutyronitrile) (abbreviation A, 1.B, N,) and stir for 5 hours, then add 0.3 g of A, [, B, N, and further 4 Stir for hours.

The h of the obtained polymer was 24,000.

Production example 6 of resin for dispersion stabilization 98.0g of octadecyl methacrylate, 2.0g of 2-mercaptoethanesulfonic acid, 200t of toluene
A mixed solution of methanol and LOOG was heated at a temperature of 6°C under a nitrogen stream.
Warmed to 5°C. ^, 1. After adding 0.8 g of B and N and reacting for 5 hours, A, 1. 0.3 g of B and N were added and reacted for 2.5 hours. This reaction solution was reprecipitated into acetonitrile 2P to obtain 88 g of white powder. W- is 25
,000.

Production Example 7 of Dispersion Stabilizing Resin A mixed solution of 90 g of hexadecyl methacrylate, 8 g of 2-chloroethyl methacrylate, 2.0 g of thiomalic acid, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 75°C. 1.0 g of 1°-azobis(cyclohexane-1-carbonitrile) was added and reacted for 6 hours, and further 0.4 g of the above initiator was added and reacted for 6 hours. After cooling, it was reprecipitated into methanol 21 to obtain 86 g of a colorless and transparent viscous substance. Mw was 23.000.

Production Example 8 of Dispersion Stabilizing Resin A mixed solution of tetradecyl methacrylate loog, 100 g of tetrahydrofuran, and 100 g of methanol was heated to 70° C. with stirring under a nitrogen stream. 2.2゛Azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propioamide 1
5 g was added and reacted for 8 hours. After cooling, methanol/water (
The mixture was reprecipitated in a mixed solution 22 (volume ratio: 7/3) to obtain 80 g of a colorless viscous substance. h was 28,000.

Production Example 9 of Dispersion Stabilizing Resin A mixed solution of 95 g of dodecyl methacrylate and 200 g of toluene was heated to a temperature under a nitrogen stream. 5 g of 4,4'-azobis(4-cyanopentanol) was processed and reacted for 8 hours.Next, 1 N,N-dimethylaniline was added to the reaction solution.
．． Add 0g and Log glutaconic anhydride and temperature 90°C.
The mixture was stirred for 12 hours. After cooling, it was reprecipitated into 2N methanol to obtain 88 g of a pale yellow viscous substance. ffw is 28.000
Met.

Production Examples 10 to 17 of Dispersion Stabilizing Resin In Production Example 1, in place of octadecyl methacrylate and the initiators A, C, and V, each of the compounds in Table A below was used to produce a dispersion stabilizing resin. did.

〃5　: C.I.

HOOC-CL S-+-CIb-C→-COOC+
zH□〃6: CH.

It(hS-CHtCHz-5-+-CHt-C→-C
OOC+aHsq Cap 1 ratio) N C00C+Jis The terminal portion containing the polar group and the repeating unit of the main chain of the resins obtained in Production Examples 1 to 17 of the above-mentioned dispersion stabilizing resins are shown below.

Production example 1 of resin for dispersion stabilization: N JOOC+5Hsv N C00C+al13t (weight ratio) 110: Hs CH3 N cooc,. ■.

〃12: CH3 〃13: Hi CHl 〃14: CH3 H3 Production example 1 of latex particles Compound example II of 20 g of resin obtained in production example 1 of dispersion stabilizing resin, 100 g of vinyl acetate, and macromonomer (M) -
(8) 1. A mixed solution of 380 g of OG and Isopar H was heated to a temperature of 75°C while stirring under a nitrogen stream. A
.

0.8 g of 1, B, and N were added and reacted for 6 hours. 20 minutes after the addition of the initiator, clouding occurred and the reaction temperature rose to 88°C. The temperature was raised to 100°C, and the mixture was stirred for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, the resulting white dispersion was passed through a 200-molecular weight nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 90% and an average particle size of 0.241M.

Production Example 2 of Latex Particles Compound Example 11-(
3) 1.2 g and 380 g of Isopar H 17> The mixed solution was heated to 70°C while stirring under a nitrogen stream. 0.9 g of benzoyl peroxide was added and reacted for 6 hours. 40 minutes after the addition of the initiator, the solution began to become cloudy and the reaction temperature rose to 85°C. After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was a latex with a polymerization rate of 88% and an average particle size of 0.27M.

Production Example 3 of Latex Particles 12g of the resin obtained in Production Example 1 of the resin for dispersion stabilization, 38g of poly[octadecyl methacrylate, 100g of vinyl acetate
, Compound example n-(9) of macromonomer (M) 1.5
A mixed solution of 450 g of Isopar H and Isopar H was heated to 75° C. with stirring under a nitrogen stream. A.1. B.

Added 0.7 g of N, reacted for 4 hours, and then added A, 1. B,
N.

0.5 g 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 0.20.

Production example 4 of latex particles Compound example U-(1
0) A mixed solution of 1.5 g and 380 g of isodecane was heated to 75°C while stirring under a nitrogen stream. A.

Add 1.0 g of r, B, and N, react for 4 hours, and then add A
, 1. B.

0.5 g of N was added and reacted for 2 hours. 200 after cooling
The resulting white dispersion was passed through a mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.23-.

Production Example 5 of Latex Particles 18 g of the resin obtained in Production Example IO of Dispersion Stabilizing Resin (as solid content), 100 g of vinyl acetate, macromonomer (M
) A mixed solution of 1.2 g of compound n-(15) and 380 g of n-decane was heated to a temperature of 75% while stirring under a nitrogen stream.
Warmed to °C. A, [, B, N, 1. Add og 4
time reaction, and further A, 1. 0.5 g of B and N were added and reacted for 2 hours. The temperature was raised to 110°C and the mixture was stirred for 2 hours to distill off the low boiling point solvent and residual vinyl acetate. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with an average particle size of 0.23I! It was latex of m.

Production Example 6 of Latex Particles 20 g of the resin obtained in Production Example 12 of Dispersion Stabilizing Resin (as solid content), 100 g of vinyl acetate, macromonomer (M
) A mixed solution of 1.5 g of Compound Example II-(18) and 380 g of Shell Silua 1 was heated to 75° C. with stirring under a nitrogen stream. 1.5 g of benzoyl peroxide was added and reacted for 6 hours. Ten minutes after the initiator was added, cloudiness occurred and the reaction temperature was raised to 90°C. 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 mm nylon cloth, with a weight percentage of 90% and an average particle size of 0.25%.
- latex.

Production Example 7 of Latex Particles A mixed solution of 18 g of the resin obtained in Production Example 6 of dispersion stabilizing resin and 1200 g of shell silua was heated to a temperature of 70° C. while stirring under a nitrogen stream. Vinyl acetate loog, macromonomer (M) compound example II-(11) 2.0g,
180 g of Shell Silua 1 and 2,2゛-azobis(isovaleronitrile) (abbreviations A, 1.V, 11.) 1.0
A mixed solution of g was added dropwise over 2 hours, and the mixture was further stirred for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth, with a weight percentage of 85% and an average particle size of 0.
It was 20μ latex.

Production Example 8 of Latex Particles Mixing of 20 g of the resin obtained in Production Example 7 of Dispersion Stabilizing Resin, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 2.0 g of Macromonomer (M) Compound Example It-(32), and 400 g of isododecane. The solution was heated to a temperature of 65°C with stirring under nitrogen flow. A.1. B, N, 1.
5 g was added and reacted for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with an average particle size of 0.2.
It was 8- latex.

Production Example 9 of Latex Particles 20 g of the resin obtained in Production Example 1 of the resin for dispersion stabilization, 100 g of vinyl acetate, 5 g of 4-pentene M, macromonomer (
M) Compound Example II-(21) A mixed solution of 1.5 g and Isopar G was heated at a temperature of 60° while stirring under a nitrogen stream.
It was heated to C. A.1. V, N, 1. Add Og 2
Time reacted. Furthermore ^, 1. 1.0.5 g of V and I were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.28.

Production Example 10 of Latex Particles 25 g of the resin obtained in Production Example 2 of Dispersion Stabilizing Resin, 100 g of isopropyl methacrylate, a mixed solution of 1.2 g of macromonomer (M) [-(1)] and Isopar H were mixed in a nitrogen stream. The mixture was heated to 70°C while stirring. A.1. 1.2 g of V and N were added and reacted for 4 hours.

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 0.45.

Production example 11 of latex particles Compound example (23) of 25 g of resin obtained in production example 1 of resin for dispersion stabilization, 100 g of styrene, and macromonomer (M)
A mixed solution of 1.0 g and 380 g of Isopar H was heated to 50° C. with stirring under a nitrogen stream. An amount of n-butyllithium hexane solution having a solid content of 1.0 g was added, and the mixture was reacted for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mm x 7 mm nylon cloth, and the average particle size was 0.3.
It was 6- latex.

Production Examples 12 to 17 of Latex Particles In Production Example 1 of Latex Particles, latex was produced in the same manner as in Production Example 1, except that the resin shown in Table B was used instead of the polymer of Production Example 1 as the dispersion stabilizing resin. Particles were produced.

Table B Production Example 18 of Latex Particles (Comparative Example A) Polymerization rate A white dispersion of latex particles with an average particle size of 0.23μ was obtained at 88%.

Production example 19 of latex particles (comparative example B) [octadecyl nucleate/acrylic acid (copolymerization ratio (9515)
[Weight ratio] Using a mixed solution of 20 g of copolymer, 100 g of vinyl acetate, and 380 g of Isopar H, the following process was carried out in the same manner as in Production Example 1 of latex particles to obtain latex particles with a polymerization rate of 90% and an average particle size of 0.25-. A white dispersion was obtained.

Example 1 [Dodecyl methacrylate-acrylic acid (copolymerization ratio (9
5/5) Weight ratio)) Copolymer Log, Nigrosine L
30 g of Og and Shell Silua 1 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

By diluting 30 g of the resin dispersion of Latex Particle Production Example 1, 2.5 g of the above nigrosine dispersion, and 10.08 g of [occudecene-half-maleic acid octadecylamide copolymer] to 11 of Shell Sila 1, a liquid developer for electrophotography was prepared. was created.

(Comparative Example Developer A-B) Two types of comparative liquid developers A and B were prepared by replacing the resin dispersion in the above production example with the following resin particles.

Comparative liquid developer A Resin dispersion of Nilatex particle production example 18 Comparative liquid developer B Resin dispersion of Nilatex particle production example 19 These liquid developers were processed using a fully automatic plate making machine ELP404ν (Fuji Photo Film ■ ELP Master ■ type (manufactured by Fuji Photo Film ■), which is an electrophotographic light-sensitive material, 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 1.

Table 1 When plate making was performed using each developer under the plate making conditions described above, as is clear from the results in Table 1, the developing device was not contaminated and the image on the 2000th plate making plate was clear. The developer used was only the developer of the present invention.

On the other hand, offset printing master plates (ELP-masters) obtained by plate making using each developer were printed in a conventional manner, and the number of prints was compared until the printed image showed missing characters, fading in solid areas, etc. However, the present invention and comparative example A
In the master plate obtained using the developer of Comparative Example B, no problem occurred even after 10,000 sheets or more were produced.

As shown in the above results, only the developer made using the resin particles of the present invention does not cause any staining of the developing device, and
The number of printed master plates was also good.

That is, in the case of Comparative Examples A and B, there was no problem with the number of prints, but the developing device was so dirty that it could not withstand continuous use.

In particular, the dispersion stabilizing resin used in Comparative Example B uses acrylic acid as a copolymerization component and contains a carboxy group in the middle of the polymer main chain, which is different from the polymer main chain according to the present invention. The redispersibility was significantly poorer than that of a polymer containing a carboxy group only at one end.

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

Example 2 White background dispersion obtained in latex particle production example 2>110
A mixture of 0g and 1.5g of Sumikalon blank was heated to temperature 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 0.201M.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． 05 g to Shell Silua 1 of 11! A liquid developer was prepared by diluting it to .

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 printing 10,000 sheets was also very clear.

Example 3 White dispersion 100 obtained in latex particle production example 9
g and 83 g of Victoria Blue at a temperature of 70”
The mixture was heated to ~80°C and stirred for 6 hours. After cooling to room temperature 20
The remaining dye was removed by passing it through a 0 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.16μ.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05 g of Isopar H1ffi.

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, 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 2
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 into Isopar G11.

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. Also, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were clear.

Furthermore, after leaving this developer for 3 months, the same treatment as above was carried out, but there was no difference at all from before the aging.

Example 5 Poly (decyl methacrylate) 10g, Isopar H
30 g 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.

White resin dispersion 3 obtained in latex particle production example 3
A liquid developer was prepared by diluting 0 g of the above-mentioned alkali blue dispersion, and 0.06 g of a semi-docosanylamidated product of a copolymer of diisobutylene and maleic anhydride to Isopar G11.

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. In addition, 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 9 In Example 5, instead of the white resin dispersion of latex particle production example 3, the latex particles shown in Table 2 were used in an amount that gave a solid content of 6.0 g. A liquid developer was prepared in the same manner as above.

Table 2 When this was developed using the same device as in Example 1, 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.

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: At least one polar group selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group, and a phospho group is bonded to only one end of the main chain of the polymer containing the repeating unit represented by the general formula (I). The weight average molecular weight is 1×1
A monofunctional monomer (A) which is soluble in a non-aqueous solvent but becomes insolubilized by polymerization in the presence of a dispersing resin having a molecular weight of 0^4 or more and a monofunctional monomer represented by the following general formula (II). A monofunctional polymer with a number average molecular weight of 1 x 10^4 or less, which is formed by bonding a polymerizable double bond group represented by the following general formula (III) only to one end of the main chain of a polymer consisting of repeating units. A liquid developer for electrostatic photography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing at least one macromonomer (B). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), X is -COO-, -OCO-, -CH_
2OCO-, -CH_2COO-, -O- or -SO_
Represents 2-. Y 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, or -COO-Z via a hydrocarbon group having 1 to 8 carbon atoms (Z represents a hydrocarbon group having 1 to 22 carbon atoms). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (II), V is -COO-, -OCO-, -CH_2
OCO-, -CH_2COO-, -O-, -SO_2-
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1_1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). W 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-Q, or -COO-Q via a hydrocarbon group having 1 to 8 carbon atoms (Q represents a hydrocarbon group having 1 to 18 carbon atoms). General formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In formula (III), V' has the same meaning as V in formula (II). c_1 and c_2 may be the same or different from each other,
Each is synonymous with b_1 or b_2.