JPH0317663A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To provide a liq. developer enabling the production of an original plate for offset printing having superior sensitivity to printing ink and superior printing resistance by an electrophotographic process by copolymerizing a monofunctional monomer which is soluble in a monaq. solvent but is insolubilized by polymn. in the nonaq. solvent in the presence of a dispersion stabilizing resin with specified monofunctional macromonomer. CONSTITUTION:Nonaq. dispersible resin particles as the most important constituent of a liq. developer are produced by copolymerizing a monofunctional monomer (A) with a monofunctional macromonomer (B) in a nonaq. solvent in the presence of a dispersion stabilizing resin soluble in the nonaq. solvent and obtd. by cross-linking part of the chain of a polymer contg. repeating units represented by general formula I. The monomer A may be any monofunctional monomer which is soluble in the nonaq. solvent but is insolubilized by polymn. The macromonomer B is a macromonomer having <=10<4> number average mol. wt. obtd. by bonding a group having a polymerizable double bond represented by general formula III to only one terminal of the principal chain of a polymer consisting of repeating units represented by general formula II.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a #% electrophotographic liquid developer comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 109 Ω or more and a dielectric constant of 3.5 or less. Yes, especially redispersibility, storage stability,
Concerning liquid developers with excellent stability, image reproducibility, and fixing properties. (Prior art) General liquid developers for electrophotography use 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 Hekai rubber. Dispersed in a liquid with high insulating properties and low dielectric constant, such as aliphatic hydrocarbons, and added with a polarity control agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acids, and vinylpyrrolidone. It is. In such developers, the resin is dispersed as insoluble latex particles in the form of particles with a diameter of several nanoseconds to several hundred diameters, but in conventional liquid developers, the resin is dispersed in the form of insoluble latex particles with a diameter of several nanoseconds to several hundred diameters. Due to insufficient bonding with the latex particles, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, 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. Also, once agglomerated,
Since the accumulated particles are difficult to redisperse, they remain attached to various parts of the developing machine, leading to developing machine malfunctions such as staining of the image area and clogging of the liquid supply cylinder. In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles was devised, as disclosed in US Patent No. 3. 990. No. 980, etc. 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. solidified into
In addition to being difficult to redisperse, it also causes equipment failure, stains on copied images, etc., and the redispersion stability is insufficient for practical use. 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; 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 formed. 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 11 or more or 0.1p are difficult to obtain.
The following very @fine particles were marked. 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, the monomer to be insolubilized is polymerized to form insoluble dispersed resin particles in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction. A method for improving dispersion, redispersibility, and storage stability is disclosed in JP-A-60-185962,
It is disclosed in No. 61-43757, etc. (Intelligence to be Solved by the Invention) On the other hand, in recent years, the operation time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixation process. In addition, the demand for rationalization of electrophotographic engraving systems has increased,
Specifically, efforts are being made to extend the maintenance period for plate-making machines. This creates a need for a liquid imitation agent that can be used for long periods of time without being replaced. JP-A-60-185962 and JP-A-61-43757
The dispersed resin particles produced according to the method disclosed in the above issue are still not necessarily satisfactory in terms of particle dispersibility and redispersibility when the development speed is increased or the maintenance period is extended. It wasn't about performance. 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 has excellent dispersion stability, redispersibility, and fixing properties even in an electrophotographic printing system that speeds up the development and fixed fixation processes and uses long maintenance intervals. The goal is to provide the following. Another object of the present invention is to provide a liquid developer that enables the production of offset printing plates having excellent printing ink oil sensitivity and printing durability by electrophotography. Another object of the present invention is to provide a liquid developer suitable for various 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 static changes. It is to be. (Means for Solving the Problems) An object of the present invention is to prepare a liquid developer for electrostatic photography by dispersing at least a resin in a non-aqueous solvent having an electrical resistance of 104 ΩCl1 or more and a dielectric constant of 3.5 or less. , the dispersed resin particles are a polymer containing a repeating unit represented by the following general formula (1), a portion of the polymer main chain is crosslinked, and the dispersion stabilizing resin is soluble in the well water solvent. A monofunctional monomer (A) which is soluble in a non-aqueous solvent but becomes insolubilized by polymerization in the presence of the monomer (A), and the following general formula (ff)
A polymerizable double bond group represented by [[[] is bonded to only one end of the main chain of a certain polymer from the repeating unit represented by This achievement was achieved by a liquid developer for electrostatic photography characterized by copolymer resin particles obtained by polymerizing a solution containing at least one monofunctional macromonomer (B). It represents -〇〇〇-Z' (here, Zl represents a hydrocarbon group having 1 to 2z carbon atoms) via a hydrocarbon group of general formula (1).

General formula (II) General formula (III) T'- In general formula (II), T is -C00-, -OCO-, -C
H. OCO-, in general formula (1), X- is -COO-, -
Represents OCO-, -CIIfOCO-, CH-rich COO-, 101 or -tot-. Y' represents an aliphatic group having 6 to 32 carbon atoms. a1 and 1 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 carbon atom.
~8 hydrogen groups). R- has 1 to 22 carbon atoms
represents a hydrocarbon group. b1 and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom,
Cyano group, hydrocarbon group having 1 to 8 carbon atoms, -Coo-R"
Or COO-1 via a hydrocarbon group having 1 to 8 carbon atoms? '
(R' represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). In general formula (III), T° has the same meaning as T in general formula (II). d' and may be the same or different, and each represents b- or b! in general formula (n). It is synonymous with The liquid developer of the present invention will be explained in detail below. The carrier liquid having an electrical resistance of 10 ΩC or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon; These halogen-substituted products can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isovar E1 Isopar G, Isovar H1 Isopar L (Isovar; Exxon product name) , Ciel Sol 70, Ciel Sol 71 (Ciel Sol; trade name of Ciel Oil Co., Ltd.)
, Amsco MS, Amsco 460 solvent (Amsco; trade name of Spirits Co.), etc. are used alone or in combination.

The most important precept in the present invention is that non-ice-based dispersed resin particles (hereinafter sometimes referred to as latex particles) contain repeating units represented by the above general formula (1) in a non-aqueous solvent. Copolymerizing the monofunctional monomer (A) and the monofunctional macromonomer (B) in the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent, in which a portion of the polymer chain of the polymer is crosslinked. (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. For example, hexane, octane, isooctane,
Decane, Isodecane, Decalin, Nonane, Dodecane, Isododecane, Isobar E, Isopar G1 Isopar H1 Isobar L1 Cielsol 70, Cielsol 7
1. Use Amsco OMS, Amsco 460 solvent, etc. alone or in combination. Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, probyl alcohol, phthyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.) ), carboxylic acid esters (e.g. methyl acetate, ethyl acetate, probyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogens Hydrocarbons (for example, 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 satisfies the condition of 104ΩcII1 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 of the present invention is used to make a stable resin dispersion of a solvent-insoluble copolymer obtained by copolymerizing a monomer (A) and a macromonomer (B) in a non-aqueous solvent. The stabilizing resin is a polymer soluble in the non-aqueous solvent, in which a portion of the polymer chain is crosslinked with a polymer containing a repeating unit represented by the general formula (1). The repeating unit represented by general formula (1) will be explained in more detail below. In the repeating unit represented by general formula (1), aliphatic groups and hydrocarbon groups may be substituted.

In general formula (1), x1 is preferably -COO-,
OCO- -CLOCO-, -CII. Represents COO1 or 101, more preferably -C00-, -Clt
Coo represents one or -0-. v1 may preferably be substituted with W having 8 to 22 carbon atoms,
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'' -OCO- (CO.::TEZ'' 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, etc.) Examples include substituents such as More preferably, 1 and I1 represent an alkyl group or an alkenyl group having 8 to 22 carbon atoms. For example, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group,
Examples include octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, and the like. 1 and a! may be the same or different, 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 l to
3 alkyl group, -COO-Z3 or 10 old coo-Z
(Here, Z3 represents an aliphatic group having 1 to 22 carbon atoms, such as methyl group, ethyl group, proyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include hexadecyl group, octadecyl group, docosanyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, and these aliphatic groups are represented by yl above. may have similar substituents).
More preferably, al and a2 each represent a hydrogen atom,
Alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, probyl group, etc.), -Coo-Z4 or -CH*C
OO-Z' (here, 24 represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, proyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, pentenyl group) group, hexenyl group, heptenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups may have the same substituents as those represented by Y' above.
The dispersion stability of the present invention is used to make a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing monomer (A) and macromonomer (B) in a nonaqueous solvent. The resin for use is a resin that does not contain a graft group that polymerizes with the monomer (A) and the macromonomer (B), and has the general formula (
1) A polymer containing at least one type of repeating unit shown in 1), in which a portion of the polymer main chain is crosslinked, and is soluble in the non-aqueous solvent. The polymer of the dispersion stabilizing resin of the present invention has the general formula (1)
Homopolymer fraction or copolymer fraction selected from the repeating units represented by or other monomers that can be copolymerized with the monomer corresponding to the repeating unit represented by general formula (1) It is a polymer containing a copolymer component obtained by polymerizing , and a part of the main chain of the polymer is crosslinked.

Other copolymerizable monomers may be any as long as they contain a polymerizable double bond group, such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; carbon atoms of 6 or less; Examples include ester derivatives or amide derivatives of unsaturated carboxylic acids; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile: heterocyclic compounds containing a polymerizable double bond group; More specifically, examples include compounds having the same content as the monomer (A) to be insolubilized, which will be described later. In the polymer in the dispersion stabilizing resin, the proportion of repeating units represented by general formula (1) is at least 3% or more, preferably 5% or more, based on the total proportion of the polymer. More preferably, it is 70% by weight or more. Generally known methods can be used to introduce a crosslinked structure into a polymer. Namely, (1) a method in which a polyfunctional monomer is coexisting in the polymerization reaction of a monomer, and (2) a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction. ．． The dispersion stabilizing resin of the present invention has a simple manufacturing method (for example, a long reaction time is required, the reaction is not quantitative, impurities are mixed in due to the use of a reaction accelerator, etc.).
Functional group with self-crosslinking reaction: CONIICHz
OZ' (here, zS represents a hydrogen atom or an alkyl group) or the orange reaction by polymerization is effective. In the polymerization reaction, preferably, a method of cross-linking between polymer chains by polymerizing a monomer having two or more polymerizable functional groups together with a monomer corresponding to the repeating unit represented by the above formula (1). It is. Specifically, the polymerizable functional group is CH.・CHCHx=l;HL;Ht-%
1. ;tlt-LJ-Lr-u-, shinxs
b-shi-u-, 11 0 C}13 CHff11 CHx=IC-CONHCOO-, CHIC-CONI
ICONH0 1j CTo-CH-C[lt-0-C-, CHz=CH
-NHCO-, CHt-(Jl-CHg-N}ICO-
, CHz=CII-SOtCH! ．． CI-CO-, CH
．． =CH-0-, C}It=CH-S-, etc. However, monomers having two or more of the above polymerizable functional groups may have these polymerizable functional groups as the same or Any monomer containing two or more different molecules is sufficient. Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylbenzene and trivinylbenzene; polyhydric alcohols (e.g. ethylene Glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #400, #600, 1.3
- butylene glycol, neobentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxydiphenol (
esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid (e.g. hydroquinone, resorcinol, catechol and their derivatives); dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adivic acid, pimelic acid) , maleic acid, phthalic acid,
Itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or allylamides; polyamines (e.g. ethylenediamine, I,3-propylene diamine,
14-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.). In addition, examples of monomers having different polymerizable functional groups include carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylbrobionic acid, Itaconyl acetic acid, itaconyl brobionic acid, reactants of carboxylic acid anhydrides and alcohols or amines (e.g. allyloxycarbonylpropionic acid, allyloxycarbonyl acetic acid, 2-allyloxycarbonylbenzoic acid, allylaminoproponylprobionic acid, etc.)
Ester derivatives or amide derivatives containing vinyl groups (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylbrobionate, etc.) Allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl methyloxycarbonyl ethylene acrylate, N-allyl acrylamide, N-allyl methacrylamide, N-
allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.); and amino alcohols (e.g. aminoethanol, 1-aminobubutanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group-containing Examples include condensates with carboxyl acids.

The monomer having two or more polymerizable functional groups used in the present invention is polymerized in an amount of 10% by weight or less, preferably 5% by weight or less of the total monomers, and is soluble in the nonaqueous solvent of the present invention. Forms a certain resin. The weight average molecular weight of the dispersion stabilizing resin of the present invention is IXIO
'~2X104 is preferred, more preferably 2. 5
XIO'~IXIOS. Weight average molecular weight is IXI
If it is less than O', the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5) and the particle size distribution becomes wide. In addition, if it exceeds 2 x 104, the average particle size of the resin particles obtained by polymerization granulation becomes too small, making it difficult to align the average particle size within the preferred range of 0.15 to 0.4. Sometimes. Specifically, the dispersion stabilizing resin polymer used in the present invention is prepared by using a monomer corresponding to the repeating unit represented by general formula (1), which is a known method, and the above-mentioned polyfunctional monomer. A method of polymerizing with a polymerization initiator (for example, an azobis compound, peroxide, etc.) while at least coexisting is simple and preferred.

The polymerization initiators used here each have a total monomer content of 100%
The amount is 0.5 to 15% by weight, preferably 1 to 10% by weight. The dispersion stabilizing resin of the present invention produced as described above is
It interacts with and adsorbs to insoluble resin particles. The particles on which the dispersion stabilizing resin has been adsorbed have significantly improved affinity for nonaqueous solvents because the dispersion stabilizing resin is crosslinked to make them soluble in nonaqueous solvents. In addition to improving the affinity of the insoluble resin particle interface in this way, the dispersion stabilizing resin that exists in the nonaqueous solvent without being adsorbed to the particles can cause the dispersion stabilizing resin to bond between the adsorbed particles. It is presumed that the approach is three-dimensionally suppressed. It is thought that these things suppress agglomeration and precipitation of insoluble particles and significantly improve redispersibility. The monomers used in producing the non-aqueous dispersion resin are a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a monomer that is copolymerized with the monomer (A). It can be distinguished into monofunctional macroheptanomers (B) that give rise to The monofunctional 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, a monomer represented by the general formula (TV) may be mentioned. General formula (IV) e1et CH-C U-R' In general formula (VI), U is -C00-, -OCO-, -C
II. Represents OCO-. Here, RS is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, proyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromoethyl group, -cyanoethyl group, 2-hydroxyethyl group, henzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylpencil group, fluorobenzyl group, 2-methoxyethyl group, 3- methoxypyl group, etc.). R4 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, probyl group, butyl group, 2-chloroethyl group, 2.2-dichloroethyl L 2.2. 2-trifluoroethyl group, 2-promoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxybrobyl group, 2-3-dihydroxybuchivyl group, 2-hydroxy-3-chlorobuchivyl group group, 2-cyanoethyl group, 3-cyanopropyl L2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethyl 1 noethyl group,
trimethoxysilylbropyl group, 3-bromobrobyl group, 4-hydroxybutyl group, 2-furfurylethyl group,
2-chenylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carpoxybrobyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfobrobyl group, 4-sulfobutyl group group, 2-carboxyamidoethyl group, 3-sulfoamidebutyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.). e1 and eX may be the same or different, and each has the same meaning as b1 or bt in the general formula (n). Specific monofunctional monomers (A) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, brohyonic acid, butyric acid, monochloroacetic acid, trifluoroprobionic acid, etc.); Or allyl esters; optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (for example, a methyl group as an alkyl group). , ethyl group, proyl group, butyl group, 2
-chloroethyl group, 2-promoethyl group, 2-fluoroethyl group, trifluoroethyl L2-hydroxyethyl group,
2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylano)ethyl group, 2-(N,N -diethylaξno)ethyl group, 2-carboxyethyl group, 2-phosphoethyl group,
4-carboxybutyl group, 3-sulfobrobi/L4,4
-Sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-furfuryl ethyl group, 2-pyridinylethyl group, 2-chenylethyl group, trimethoxysilylbucutyl group, 2-carboxamide ethyl group, etc.); styrene derivatives (e.g., t-bar, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dicarostyrene, promostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethylstyrene, vinylbenzene lupoxyamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; Cyclic anhydride of maleic acid and itaconic acid; acrylonitrile; methacrylic nitrile: heterocyclic compound containing a polymerizable double bond group (specifically, for example, , ,p
175-184, compounds described in Baifu Gii (published in 1986), such as N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene,
vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.). Two or more monomers (A) may be used in combination. The monofunctional macromonomer (B) can be copolymerized with the monomer (A) only at one end of the main chain of the polymer consisting of repeating units represented by the general formula (II). [The number average molecular weight formed by bonding the polymerizable double bond group shown in [] is 104
The macromonomer is as follows. General formula ([[) and (III) 7b', b'',
The hydrocarbon groups contained in T, R1, d1, d1 and T° each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group).
However, these hydrocarbon groups may be substituted. In formula (II), in addition to a hydrogen atom, R2 in the substituent represented by T is preferably a hydrocarbon group having 1 carbon number.
~18 optionally substituted alkyl groups (e.g., methyl group, ethyl group, probyl group, butyl group, hebutyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group) , 2-
(promoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-promopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl-1 -probenyl group,
2-butenyl group, 2-pentenyl group, 3methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2
-hexenyl group, 4-methyl-2-hexenyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, phenethyl group, 3-ph5nylbrobyl group, naphthylmethyl group, 2-naphthylethyl group, chlorohenzyl group, promobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl 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, probylphenyl group, butyl group) Phenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, ptoxyphenyl group, decyloxyphenyl group, chlorophenyl group, cyclophenyl group, promophenyl group, cyanophenyl group, acetylphenyl group, methoxy carbonylphenyl group, ethoxycarponylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecoylamidophenyl group, etc.). It may have a substituent. As a substituent, a halogen atom (
Examples include chlorine atom, bromine atom, etc.), alkyl groups (eg, methyl group, ethyl group, probyl group, petit/L4, chloromethyl group, methoxymethyl group, etc.).

R1 preferably represents a hydrocarbon group having 1 to 1 carbon atoms, and specifically represents the same content as described for R2 above.

bl and b8 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 probyl group, etc.)
, -Coo-R' or -CI! COOR' (R3 is a hydrogen atom or an alkyl group or alkenyl group having 1 to 1 carbon atoms,
represents an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, and specifically represents the same content as described for R2 above.

In formula (II), T' has the same meaning as T in formula (II), and d1 and d! may be the same or different, and b1 or b! in the above formula (It) may be the same or different from each other. is synonymous with

Preferred ranges of T'', d1 and d2 are T, b' and b! described above, respectively. The content is similar to that explained in . bl and bl of formula (n) or d' and d of formula (I[l)! It is more preferable that either one of them is a hydrogen atom. The macromonomer provided in the present invention has a polymerizable double bond represented by general formula (III) only at one end of the polymer main chain consisting of repeating units represented by general formula (II) as described above. It has a chemical structure in which the groups are directly bonded or bonded by an arbitrary linking group. 2 (I) The group connecting the precept and the formula (I [I) component includes a carbon-carbon bond (single bond or double bond), a carbon-carbon heteroatom bond (heteroatoms include, for example, an oxygen atom) , sulfur atom, nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

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

Formula (V) dl dZ CH-C b'b" In formula (V), bl, b-value, d1, d", T, R'
, TJf, respectively, represent the same contents as explained in formula (■) and formula (III). R6 Q is a simple bond or →C)-(R", R' is each R7 hydrogen atom, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), soano group, hydroxyl group, alkyl group (e.g. , methyl group, ethyl group, proyl group, etc.), -fcn=cH)-, 0 R@COO- -SOt- -CON- -S
O. selected from atomic groups such as N-, -NHCOORI Rl RI NICONlt-, -Si- (i?', R9 each represents a hydrogen atom or a hydrocarbon group having the same content as Rt above) Represents a single linking group or a linking group composed of any combination.

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

In the general formula (II), (III) or (V), TSR', T, b', b! , al, and d2, particularly preferred examples are shown below.

T is -COO- -OCO- -0- -
CI{zcOo- or -Cll, OCO-, R+ is an alkyl group or alkenyl group having 18 or less carbon atoms, T° is all of the above (however, R2 is a hydrogen atom), bl, b! , d1 and d2 include a hydrogen atom or a methyl group.

The macromonomer (B) of the present invention can be produced by a conventionally known method. For example, ■methods using ionic polymerization, in which the ends of living polymers obtained by anionic polymerization or cationic polymerization are reacted with various reagents to form macromers; ■methods using reactivity such as carboxyl groups, hydroxyl groups, and amino groups in molecules; A radical polymerization method in which various reagents are reacted with oligomers with terminal reactive group bonds obtained by radical polymerization using a polymerization initiator and/or a chain transfer agent containing a group to form a macromer; Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer obtained by an addition or polycondensation reaction in the same manner as the radical polymerization method described above. Specifically, P. Dreyfuss & R. P.
QuirkEncycle. Polym. Sci.
Eng. ．． 7, 551 (1987), P. F.
Rempp & E. Franta + Adu.
Polys. Sci. ,58. 1 (1984), V.
．． Percec, Appl. Polym. Sc
i. +28595 (1984), R. Asam
i. M. TakaRi, Makvamol. Ch
ew. Suppl. + Top 2, 163 (
1985), P. Rempp, et. al.
+ Makvamol. Chew. Suppl. ．．
8. 3 (1984), Yuji Kawakami, “Chemical Industry”
, Tsuchi, 56 (1987), Yuya Yamashita, “Polymer J
, 31, 988 (1982), Shiro Kobayashi, "Polymer", Betsu, 625 (1981), Toshinobu Higashimura, "Japanese Society Journal", Dan. 536 (1982), Koichi Ito, "Polymer Processing", Kawa, 262 (1986), Kishiro Higashi. Takashi Tsuda, “Functional Materials J, lfp. N [LI
0, 5, etc. and the literature/patents cited therein. More specifically, the macromonomer (B) of the present invention can be exemplified by the following compounds. However, the scope of the present invention is not limited to these.

(B)-1 (B)-2 (B)-3 Cll3 (B)-4 CH, 1 COOCJs (B) 5 (B) 6 (B)-7 (B) 8 (B) l3 CH3 coz-c CH, ? OONH(CHz)zs-{CI■ C}- COOCJs (B) 14 CH, (B)-15 Clh (B)-16 COOCI1, (B) 9 (B) 10 (B) 1l (B)-12 ( B)-17 (B) 18 (B) 20 CH. CH3 Clb COOC. l1, (B)-23 (B)-33 (B) 25 (B) 26 ZaC. }I, (B)-27 CHi (B)-28 Shi~ UUUI. ：+zHzs し Uυ し+olf+ (B) 34 l COOCJ+, The dispersion resin of the present invention has an important property that it contains at least one kind of each of the monofunctional monomer (A) and the monofunctional macroheptanomer (B). What is important is that if the resin synthesized from these is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, for the monomer (A) to be insolubilized,
It is preferable to use the macromonomer (B) in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. Particularly preferred is 0.3 to 3% by weight. Further, the molecular weight of the dispersion resin of the present invention is preferably 101 to 106,
More preferably, it is 104 to 5X104.

In order to produce the dispersion resin (latex particles) 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 through a process. The polymerization may be carried out by heating in the presence of a polymerization initiator such as henzoyl oxide, COOC1sHst zobisisobutyronitrile, butyllithium, or the like.

Specifically, 1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (A), and a macromonomer (B); 2) a method of adding a polymerization initiator to a solution in which a dispersion stabilizing resin is dissolved; (A
) and macromonomer (B) together with a polymerization initiator, or (2) into a mixed solution containing the entire amount of the dispersion stabilizing resin and a portion of the mixture of monomer (A) and macromonomer (B). , a method of optionally adding the remaining monomer mixture together with a polymerization initiator;
There is a method of optionally adding a mixed solution of ) together with a polymerization initiator, and it can be produced using any of the methods.

The total amount of the monomer (A) and the macromonomer (I3) 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 10 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 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 preferable to remove it by heating it to a temperature above the boiling point of the solvent or monomer or by distilling it off under reduced pressure. The non-aqueous latex particles produced as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, especially after repeated use over a long period of time in a developing device. It has good dispersibility and is easy to re-disperse even when the development speed is increased, 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 has excellent dispersion stability, redispersibility, and fixing properties even when the development and fixation process is accelerated and the maintenance interval is extended for a long time. In the liquid developer of the present invention, a coloring agent may be used if desired. The coloring agent is not particularly limited, and 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 blank, 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. As described above, there is a method of producing a copolymer containing a dye 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. Examples include di-2-ethylhexylsulfosuccinic acid metal salts, naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), copolymers containing half maleic acid amide, and the like.

The amounts of each of the main components of the liquid developer of the present invention are explained below. The amount of toner particles containing a resin (and optionally used colorant) as a main component is preferably 0.5 parts by weight to 50 parts by weight based on 1000 parts by weight of the carrier liquid.

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 above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and may be added in an amount of 1 to 2 parts by weight per 1000 parts by weight of the carrier liquid.
．． About 5 parts by weight to 100 parts by weight can be added.

The charge control agent as described above is added in an amount of o. ooi parts by weight ~l. 0 parts by weight is preferred. Furthermore, various additives may be added as desired, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, when the electrical resistance of the liquid developer with toner particles removed is lower than 109ΩC, it is considered to be a good quality continuum III.
Since it becomes difficult to obtain toned images, it is necessary to control the amount of each additive added within this limit.

(Examples) Examples of manufacturing the resin for dispersion stabilization of the present invention, examples of manufacturing the Lajx particles, and examples are illustrated below, but the present invention is not limited thereto.

A mixed solution of 100 g of P octadecyl methacrylate, 2 g of divinylbenzene and 200 g of toluene was heated to a temperature of 85°C while stirring under a nitrogen stream. B.N) 3
．． 0g was added and reacted for 4 hours, and further A. I. B. N to l. h
In addition, the reaction was continued for 2 hours, and further ^. I. B. N to 0.51B
In addition, the reaction was continued for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5N methanol, and the white powder was collected and dried to obtain 88 g of powder. The weight average molecular weight of the obtained polymer was 3.3×104. 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 in place of octadecyl methacrylate-1.

The weight average molecular weight of each resin is 3. oxto'~5X104
Met. Table 1: Manufactured by one man, Germany, for 2 minutes, 15 to 27:
'-'Production Example 1 except that the polyfunctional monomer or oligomer shown in Table 2 below was used instead of 2 g of divinylbenzene, which is a crosslinking polyfunctional monomer.
Each dispersion stabilizing resin was manufactured in the same manner as above. The weight average molecular weight of each resin was 3XIQ' to 6X104. Table 2: A mixture of 95 g of 28:P octadecyl methacrylate, 5 g of N-methoxymethylacrylamide, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75° C. under a nitrogen stream. lB. ! 1, to 3. Og was added and the mixture was reacted for 8 hours. Next, using Dean-Stark,
The mixture was heated to 10°C and stirred for 6 hours. The solvent used, isoprobanol, and methanol produced as a by-product in the reaction were removed. After cooling, it was reprecipitated into 1.5N methanol, and a white powder was collected by filtration and dried. The yield is 82g and the weight average molecular weight is 5.
It was 6 x 104.

7ku0-T:/mer's ``1: Macromonomer M-1
A mixed solution of 92 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was heated to a temperature of 75°C while stirring under a nitrogen stream to prepare 2.2' azobis(cyanovaleric acid) (abbreviated as A.C.). V.) 31 g was added and reacted for 8 hours. Next, 8 g of Grindyl methacrylate and 1.
Add Og and 0.5 g of t,-butylhydroquinone,
The temperature was brought to +00'C and stirred for 12 hours.

After cooling, the reaction solution was mixed with 2 p.m. of methanol. The mixture was reprecipitated into a white powder to obtain 82 g of a white homogenized powder. The number average molecular weight of the polymer is 6,50
It was 0.

A mixed solution of 95 g of methyl methacrylate, 5 g of thioglycolic acid, and 200 g of 1-toluene was heated to a temperature of 70° C. while stirring under a nitrogen stream. 2.2'-azobis(isobutyronitrile) (abbreviation A.I.B.N.)1.
5g was added and reacted for 8 hours. Next, 7.5 g of glycidyl methacrylate, N. N~dimethyldodecylaneξ1. 0.8 g of Og and L-butylhydroquinone were added, and the mixture was stirred at a temperature of 100°C for 12 hours. After cooling, the reaction solution was reprecipitated into 2 liters of methanol to obtain 85 g of a colorless and transparent viscous substance. The number average molecular weight of the polymer was 2,400.ヱ7 t2F-/-jin: Δ
Jukuzo - Kono 3 - Production of macromonomer M-3 A mixed solution of 1.94 g of methylnotacrylate, 6 g of 2-mercap 1.ethanol and 200 g of toluene was heated to a temperature of 70°C under a nitrogen stream. A, I. B. N. 1
．． 2g was added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 20°C and treated with triethylamine lo. 2 g of methacrylic acid chloride was added thereto, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature below 25°C. After the dropwise addition, the mixture was further stirred for 1 hour.

Thereafter, 0.5 g of t-butylhydroquinone was added and the mixture was heated to 60°C and stirred for 4 hours. After cooling, it was reprecipitated in methanol 21 to obtain 79 g of a colorless and transparent viscous substance. @
The average molecular weight was 4,500.

Macromo and Enishoku Co., Ltd., Son I: Production of Macromonomer M-4 A mixed solution of 95 g of hexyl methacrylate and 200 g of toluene was heated to 70° C. under a nitrogen stream.

5 g of 2.2'-azopis (cyanoheptanol) was added and reacted for 8 hours.

After cooling, the reaction solution was brought to a temperature of 20°C in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour, and then stirred for 6 hours at a temperature of 60°C. After cooling the resulting reaction product, it was reprecipitated in 2 liters of methanol to obtain 75 g of a colorless and transparent viscous material. The number average molecular weight is 6.
It was 200. Macromonomer 1゛5: Production of macromonomer M-5 Dodecyl methacrylate} 93g, 3-mercaptopropionic acid 7g 1 A mixture of 170g of toluene and 30g of isopropanol was heated to a temperature of 70°C under a nitrogen stream,
A. I. B. N. 2.0g was added and reacted for 8 hours. After cooling, the mixture was reprecipitated into 2 liters of methanol, heated under reduced pressure to a temperature of 50°C, and the solvent was distilled off.
The obtained viscous substance was dissolved in 200 g of toluene, and 16 g of glycidyl methacrylate, 1.0 g of NN-dimethyldodecyl methacrylate, and 1.0 g of t-butylhydroquinone were added to this mixed solution. og was added and stirred at a temperature of 110°C for 10 hours. This reaction solution was reprecipitated again into 2 liters of methanol. The number average molecular weight of the pale yellow viscous substance obtained was 3.40.
It was 0.

Macro-7nomano-1 Report 6; Preparation of Macromonomer M-6 A mixed solution of 95 g of octadecyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 75° C. with stirring under a nitrogen stream. A. T. B. N. 1
．． 5g was added and reacted for 8 hours. Next, 13 g of glycidyl methacrylate, 1. 1.0 g of Og and L-butylhydroquinone were added, and the mixture was stirred at a temperature of 110°C for 10 hours. After cooling,
This reaction solution was reprecipitated into methanol 2i to obtain 86 g of white powder. The number average molecular weight was 2,300.

Z Lomomer's LjLfLL: Macromonomer M-7
Production of methyl methacrylate 40 g 1 ethyl methacrylate 5
4g,2-mercabutethylamine 6g2 Toluene 1
A mixture of 50 g of tetrahydrofuran and 50 g of tetrahydrofuran was heated to 75° C. with stirring under a nitrogen stream.

A. I. B. N. 2.0g was added and reacted for 8 hours.
Next, this reaction solution was brought to a temperature of 20° C. in a water bath, and 23 g of methacrylic anhydride was added dropwise thereto without the temperature exceeding 25° C., followed by further stirring for 1 hour.

0.5 g of 2.2'-methylenebis(6-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 40°C for 3 hours. After cooling, this solution was reprecipitated into 2N methanol to obtain 83 g of a viscous substance. The number average molecular weight was 2,200. 1' Report of Macromonomer 8: Preparation of Macromonomer M-8 A mixed solution of 95g of methyl methacrylate and 200g of toluene was heated to 75°C under a nitrogen stream.

A, C. V. 5g of was added and reacted for 8 hours. Next, 5 g of glycidyl acrylate and 71 g of N,N-dimethyldodecyl acrylate. Add Og and 1.0 g of 2.2'-methylenebis(6-L-butyl-p-cresol) and raise the temperature to 100.
'C and stirred for 15 hours. After cooling, this reaction solution was reprecipitated into 2 liters of methanol to obtain 83 g of a transparent viscous substance. The number average molecular weight was 3,600.

11・'St゛:Latenox particle D-
12g of resin P-1 obtained in Production Example 1 of dispersion stabilizing resin,
100 g of vinyl acetate, 1.0 g of the M-1 macromonomer obtained in Macromonomer Production Example 1, and Isopar H 3
A. 80 g of mixed solution was heated to a temperature of 75°C while stirring under nitrogen flow. I. B. N. Add 1.7g of
Time reacted. 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 to distill off unreacted vinyl acetate. After cooling, it was passed through a 200 mesh nylon cloth, and the obtained white dispersion was a latex with a polymerization rate of 90% and an average particle size of 0.20/II1. 1-1: Production of latex particles D-2 to D-11 In production example 1 of latex particles, dispersion stabilizing resin P
-1 and macromonomer M-1, the table below -3
The procedure was repeated in the same manner as in Production Example 1, except that each compound was used.
A white dispersion with a polymerization rate of 85-90% was obtained. Part 1: Latinx particle D-12
Production of resin for dispersion stabilization 13 g of l'-2 resin obtained in Production Example 2
A mixed solution of 100 g of vinegar [hinyl, 5 g of crotonic acid, 1.0 g of M-1 obtained in Macromonomer Production Example 1, and 468 g of Isopar was stirred under a nitrogen stream at a temperature of 7.
2. 1.3 g of 2'-azobis(isovaleronitrile) (abbreviated as A.I.ν.N.) was added, and after reacting for 6 hours, the temperature was raised to 100°C and the mixture was heated to 100°C. After stirring for an hour, the remaining vinyl acetate was distilled off. After cooling, the
The white dispersion obtained by passing through a 0 mesh nylon cloth had a polymerization rate of 85% and an average particle size of o. It was 21-inch latex. -Shiba j-zji LZ'LlPukomikobko7D1: Production of Latinx particles D-13 14g of I"l resin obtained in Production Example 1 of resin for dispersion stabilization,
A mixed solution of 100 g of vinyl acetate, 6.0 g of 4-bentenoic acid, 1.5 g of M-7 obtained in Macroheptanomer Production Example 7, and 380 g of Isovar G was heated to a temperature of 75°C while stirring under a nitrogen stream. Warmed. A. lB. N. 0.7
g was added and reacted for 4 hours, and further A.g. I,B. N. 0.
5g was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth and had an average particle size of 0.
It was a 24-Latinx.

Danjw-25 (T to L) ↓Relatex particles D-
14 g of P-2 resin obtained in Production Example 2 of dispersion stabilizing resin,
85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of M-1 obtained in Macroheptanomer Production Example 1 and n-
A mixed solution of 380 g of decane was heated to a temperature of 75°C while stirring under a nitrogen stream.A. I. B. N. 1.7
g was added and reacted for 4 hours, and further A.g. I. B. N. O. S
g was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with an average particle size of 0.25.
It was μ latex.

11 Kus' lhl5: Latex particles D-1
18 g of resin P-1 obtained in Example 1 of manufacturing dispersion stabilizing resin,
100 g of methyl methacrylate, 1.5 g of M-2 obtained in Macromonomer Production Example 2, and 470 g of n-octacrylate
The mixed solution was heated to 70°C with stirring under a nitrogen stream. A. I. V. N. 1,0g of was added and reacted for 2 hours. A few minutes after adding the initiator, 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 a particle size of approximately 0.354. 11. +1 16 (Comparative Example A) In production example 1 of latex particles, except for macromonomer M-1,
The others were tested in the same way. The white dispersion obtained was a latex with a polymerization rate of 85% and an average particle size of 0.20. 11.S.'s Relic U (Comparative Example B) In Production Example 1 of Latex Particles, the same procedure as Production Example 1 was used except that 1.0 g of octadecyl methacrylate was used instead of the macromonomer M-1. I operated it. The obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.22-. 11. "(Comparative Example C) In Production Example 1 of Latex Particles, except that monomer (1) having the following structure was used instead of macromonomer M-1, Production Example I
It was operated in the same way. The obtained white dispersion had a polymerization rate of 86%.
and the average particle size o. It was 221 latex. Monomer (1) CI. CHz-C OCOCJ+s COOCH*C CHxOCOCJ+3 Example 1 Dodecyl methacrylate/acrylic acid copolymer [copolymerization ratio. (95/5) weight ratio] 10g, nigrosine 10g
and 30 g of 7 liters of Cielsol were placed in a paint shaker (Tokyo Seiki@) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine. 30 g of resin dispersion D-1 of latex particle production example 1, 2.5 g of the above nigrosine dispersion, higher alcohol F O C -1400
(manufactured by Nissan Chemical ■) 15g, and octadecyl vinyl ether/half maleic acid octadecylamide copolymer 0.0
A liquid developer for electrostatic photography was prepared by diluting 8 g of Cielsol to 1 liter of 7 liters of Schielsol. (Comparative developer A-C) Comparative liquid developers A, B, and C were prepared by replacing resin dispersion D-1 with the following resin dispersion in the production example of the liquid developer described above.
Three types were created.

Comparative liquid developer A: Resin dispersion of latex particle production example 16 Comparative liquid developer B: Resin dispersion of latex particle production example 17 Comparative liquid developer C: Resin dispersion of latex particle production example 18 These liquid developers were used as a developer in a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Ltd.) to expose and develop an electrophotographic light-sensitive material, EPL Master type (manufactured by Fuji Photo Film Ltd.).

The plate making speed was 7 plates/min. Furthermore, E.L.P.
After processing 3,000 sheets of the master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (Ii image area) of the copied image was determined using a 30% original. The results are shown in Table 4. Table 4 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 stain the developing device and provided a clear image on the 3000th plate-making plate. On the other hand, is the offset obtained by plate making from each current copying agent? Printing Master Plate (ELP-Master) Comparing the number of prints until the printed image shows missing characters, fading in solid areas, etc. when printed using a conventional method, the present invention, Comparative Example A, and Comparative Example In the master plate obtained using developer C, the problem did not occur even after 10,000 sheets or more, and in the master 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 copies printed, but the current copying device was so dirty that it could not withstand continuous use. In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 7.
When used at high plate-making speeds such as sheets per minute (conventionally, the plate-making speed was 2 to 3 sheets per minute), the developing device (especially on the back electrode plate) becomes dirty, and after 3,000 sheets, The image quality of the copied image on the plate began to be affected (decreased D.■, fading of fine lines, etc.). master play 1
There was no problem with the number of printed sheets in Comparative Example C, but it decreased in Comparative Example B. These results demonstrate that the resin particles of the present invention are clearly superior.

Example 2 White turtle rot product D-1 obtained in latex particle production example 1
A mixture of 100 g of Sumikalon Black and 1.5 g of Sumikaron Black was heated to 100'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 0.21. 32g of the above black resin dispersion, 0 zirconium naphthenate
．． 05g of Ciel Sol 7l II! A liquid developer was prepared by diluting it to .

When this was developed using the same device as in Example 1, the result was 3.0
Even after developing 00 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 D- obtained in latex particle production example 12
A mixture of 100g of No. 12 and 3g of Victoria Blue B was heated to 70-80°C and stirred for 6 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain an average grain aO. A blue resin dispersion of No. 21- was obtained. 32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05g of Isobar H to 1N.

This was developed using the same apparatus as in Example 1. 3.
Even after developing 1,000 sheets, no toner stains were observed on the device. Furthermore, 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 copies was also very clear.

Example 4 White resin dispersion D-2 obtained in latex particle production example 2
32g, 2.5g of the nigrosine fraction obtained in Example 1,
0.02 g of semi-docosanylamidated copolymer of diisobutylene and maleic anhydride and higher alcohol F O
A liquid developer was prepared by diluting 15 g of C-1400 (manufactured by Nissan Chemical Industries, Ltd.) to Isopar G if.

This was developed using the same apparatus as in Example 1, and 3.
Even after developing 1,000 sheets, no toner adhesion stains were observed on the device. The image quality of the obtained master plate for offset printing and the image quality of printed matter after printing 10,000 sheets were also 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. Example 5 Poly (decyl methacrylate) 10g, Isopar H3
0g and 8g of alkali blue with glass beads,
The mixture was placed in a paint shaker and dispersed for 2 hours to obtain a fine alkali blue dispersion. 30 g of white resin dispersion D-11 obtained in latex particle production example 11,
A liquid developer was prepared by diluting 4.2 g of the above alkaline blue decomposition product and 0.06 g of a semi-docosanylamidated product of a copolymer of diisobutylene and maleic anhydride to 11 of Isovar G.

When this was developed using the same device as in Example 1, the result was 3.0
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Furthermore, both the image quality of the obtained master plate for offset printing and the Nt of the printed matter after printing 10,000 sheets were very clear. Examples 6 to 15 In production example 1 of latex particles, dispersion stabilizing resin P
Latex particles D-19 to D-28 were produced in the same manner as in Production Example 1 of Latex particles, using the compounds shown in Table 5 below in place of Macromonomer M-1 and Macromonomer M-1. In Example 1, each of the latex particles D-19 to D-28 was used instead of latex particle D-1.
A liquid developer of the present invention was prepared in the same manner as in Example 1. 3. These were developed using the same apparatus as in Example 1.
Even after developing 1,000 sheets, no toner stains were observed on the device. In addition, the image quality of the obtained offset printing master plate and the image quality of the printed matter after printing 10,000 sheets were both very clear. (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 very high plate-making speeds, the developing device does not become dirty, and maintenance intervals can be extended for a long period of time. After printing 10,000 copies, the image quality of the printed matter was extremely clear. (3 others)

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: In the presence of a dispersion stabilizing resin which is a polymer containing a repeating unit represented by the general formula (I) and in which a portion of the main chain of the polymer is crosslinked and is soluble in the non-aqueous solvent, the non-aqueous solvent is The following general formula is present only at one end of the main chain of a polymer consisting of a monofunctional monomer (A) that is soluble but becomes insolubilized by polymerization, and a repeating unit represented by the following general formula (II). By polymerizing a solution containing at least one monofunctional macromonomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding a polymerizable double bond group represented by (III). A liquid developer for electrostatic photography characterized by comprising copolymer resin particles obtained. 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
hydrocarbon group, -COO-Z^1 or -COO-Z^1 via a hydrocarbon group having 1 to 8 carbon atoms (here, Z^1 represents a hydrocarbon group having 1 to 22 carbon atoms) represent. General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In general formula (II), T is -COO-, -OCO-, -CH
_2OCO-, -CH_2COO-, -O-, -SO_
2-, -CON-, -SO_2N or ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (R^2 is a hydrogen atom or a carbon number of 1 to 1
8 hydrocarbon group), R^1 has 1 carbon number
~22 hydrocarbon groups, b^1 and b^2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -C
- via OO-R^3 or a hydrocarbon group having 1 to 8 carbon atoms
COO-R^3 (R^3 is a hydrogen atom or a carbon number of 1 to 18
represents a hydrocarbon group). In general formula (III), T^1 is T in general formula (II)
d^1 and d^2 may be the same or different, and each has the same meaning as b^1 or b^2 in general formula (II).