JPH0318863A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve dispersion stability, redispersibility and fixability by polymerizing a specified monofunctional monomer and a specified oligomer in the presence of a specified dispersion stabilizing resin and dispersing the resulting resin particles in a nonaq. solvent. CONSTITUTION:A monofunctional monomer which is soluble in a nonaq. solvent and is insolubilized by polymn. and an oligomer having <=10<4> number average mol. wt. obtd. by bonding a polar group such as a carboxyl or sulfo group to only one terminal of the principal chain of a polymer consisting of repeating units represented by formula II are polymerized in the presence of a dispersion stabilizing resin made of a polymer contg. repeating units represented by formula I, having a cross-linked part in the principal chain and soluble in the nonaq. solvent and the resulting resin particles are dispersed in the nonaq. solvent. In the formula I, X<1> is -COO-, -OCO-, etc., Y<1> is an aliphatic group and each of a<1> and a<2> is H, halogen, etc. In the formula II, T<1> is -COO-, -CH2OCO-, etc., R<2> is hydrocarbon and each of b<1> and b<2> is H, cyano, etc. Dispersion stability, redispersibility and fixability can be improved.

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 aliphatic hydrocarbon, and further contains a polarity control agent such as a metal soap, lecithin, linseed oil, higher fatty acid, or a polymer containing vinyl pyrrolidone. be.

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

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner adhering to various parts of the device is It solidifies into a film, making redispersion difficult, and furthermore, it 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; The particles had a wide particle size distribution containing a large amount of coarse particles, or the particles had a polydisperse particle size with two or more average particle sizes.

Furthermore, it was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 14 or more or very fine particles of 0.1 or less were formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersion resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety are used to improve particle dispersion and redispersibility. , a method for improving storage stability is disclosed in JP-A-60-179.
No. 751.

Furthermore, in JP-A No. 61-43757, in the presence of a polymer using a polymer reaction, a monomer to be insolubilized is polymerized to form insoluble dispersed resin particles, thereby improving the dispersion, redispersibility, and storage of the particles. A method of improving stability is disclosed.

(Problems to be Solved by the Invention) On the other hand, in recent years, the operating time of electrophotolithographic 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 developer that can be used for a long period of time without being replaced.

JP-A-60-179751 and JP-A No. 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 constant development process and uses long maintenance intervals. It is to provide.

Another object of the present invention is to provide a liquid developer that enables the production of offset printing original 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 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 10'Ωcm 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 (I), a part of the polymer main chain is crosslinked, and a dispersion stabilizing resin soluble in the non-aqueous solvent is used. A monofunctional monomer (A) which is soluble in the nonaqueous solvent but becomes insolubilized by polymerization in the presence of the monomer (A) and the following general formula (II)
A carboxyl group, a sulfo group, a hydroxyl group,
Formyl group, amino group, H 01? ' group and R+ represents a hydrocarbon group], each containing at least one kind of oligomer (B) having a number average molecular weight of 10' or less, which is formed by bonding at least one kind of polar group selected from This was achieved by an electrostatic photographic liquid developer characterized by copolymer resin particles obtained by polymerization reaction.

General formula (I) %Formula% In general formula (I), Xl is -COO-1-OCO-1-c
o, oco-1-CI (, COO-1-〇, or -5O
Represents x-.

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

al and a'' Lt may be the same or different, and each has a hydrogen atom, a halogen atom, a cyano group, and a carbon number of 1
-8 hydrocarbon group, -coo-z' or 1000-Z' (herein, 21 represents a hydrocarbon group having 1 to 22 carbon atoms) via a hydrocarbon group having 1 to 8 carbon atoms represent.

General formula (■) In the HT'-R mushroom general formula (It), T1 is -COO-1-OCO-1-
CH, represents a hydrocarbon group of 0CO-1 to 18.

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

b+ and b2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-R', or a hydrocarbon group having 1 to 8 carbon atoms. I? represents one Coo-R'. 4 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

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

The carrier liquid having an electrical resistance of 10"ΩCa1 or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon; 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 Corporation), Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Corporation), Amsco OMS, Amsco 460 Dissection (Amsco; trade name of Spirits Corporation), etc. Use alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are made of a polymer containing repeating units represented by the general formula (I) in a non-aqueous solvent. Polymerizing the above-mentioned functional monomer (A) and oligomer (B) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, in which a portion of the polymer chain is cross-linked (so-called polymerization granulation). It is manufactured by the law).

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, such as hexane, octane, isooctane,
Decane, isodecane, decalin, nonane, dodecane, isododecane, isoparaffin-based petroleum solvents Isopar E, Isopar G1 Isopar H1 Isopar L,
Scherzol 70, Scherzol 71, Amsco OMS
, Amsco 460 TL agent, 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, methyl alcohol, fluorinated alcohol, etc.), ketones III (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, 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 satisfies the condition of 10 drops ΩC- 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.

Dispersion stability according to the present invention, which is used to make a stable resin dispersion of a solvent-insoluble copolymer produced by copolymerizing monomer (A) and oligomer (B) in a nonaqueous solvent. The resin for use is a polymer soluble in the non-aqueous solvent, in which a portion of the polymer chain is crosslinked with a polymer containing repeating units represented by the general formula (I).

Below, the repeating unit represented by general formula (I) will be explained in more detail.

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

In general formula (I), x' is preferably -COO-1
-OCO--CHiOCO-1-CHgCOO- or-
Represents 〇-, more preferably -COO-1-co, c
Represents oo- or -0-.

Yl preferably has 8 to 22 carbon atoms and may be substituted,
represents an alkyl group, alkenyl group or aralkyl group,
Examples of the substituent include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-Z''-
CoO-Z"-0CO-2"(: ,:: Te2'
represents an alkyl group having 6 to 22 carbon atoms, and includes substituents such as hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc. More preferably, Yl represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms, such as an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a docosanyl group, an octenyl group, Examples include decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, and octadecenyl group.

al and al may be the same or different, preferably a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a carbon number 1
~3 alkyl group, -COO-Z'' or -CHxCO
O-Z" (nee Z' represents an aliphatic group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group) , tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc., and these aliphatic groups include the above-mentioned may have the same substituent as represented by Y-)
More preferably, al and al each represent
Hydrogen atom, alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), -Coo-Z4 or -CHICoo-Z' (where 24 is 1 to 12 carbon atoms)
represents an alkyl group or alkenyl group, such as methyl group, ethyl group, propyl group, butyl group, hexyl group,
Examples include octyl group, decyl group, dodecyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups have the same substituents as those represented by yl above. good)
represents.

The dispersion stabilizing resin of the present invention used to make a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing monomer (A) and oligomer (B) in a non-aqueous solvent contains at least one repeating unit represented by general formula (I)
The resin is a polymer containing seeds, in which a portion of the main chain of the polymer is crosslinked, and is soluble in the non-aqueous solvent.

The polymer component of the dispersion stabilizing resin of the present invention is expressed by -S formula (I)
Polymerization of a homopolymer component or copolymer component selected from the repeating units represented by or other monomers that can be copolymerized with a monomer corresponding to the repeating unit represented by general formula (I) This is a polymer that contains a copolymer component obtained by doing this, and a portion 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 conductors of unsaturated carboxylic acids; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; and 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 component of the dispersion stabilizing resin, the component of the repeating unit represented by general formula (I) is at least 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight based on the total polymer components. % or more.

As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used.

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, it requires a long reaction time, the reaction is not stationary, and impurities are mixed in due to the use of reaction accelerators, etc.).
Functional group having self-flaring reaction: C0NIICHt
OZ'(;-CO'?'Zs represents a hydrogen atom or an alkyl group) or a cross-linking 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 (I). It is.

Specifically, the polymerizable functional group includes CO, ・CI+o
CL l CHg1=CH-CHx-, CHx=CH-C-0-,
CIIz=C-C-0-1■ C)+3 0 CI
+31 CH=CH-C-0-1ljltoC)1-CONII-
1CI11C-CONIIC)Ii-CH-C41*-
0-C-, C) Ii-CH-NHCO-1CHi=CH
-CHx-NHCO-1CH1C)I-5Oz-CHx
・CH-CO-1CHwCustomer CH-0-, CI!・CH-
3-, etc., but the monomers having two or more of the above polymerizable functional groups are monomers having two or more of the same or different polymerizable functional groups. That's fine.

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 gelicol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhydroxyphenol (
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, adipic acid, pimelic acid) , maleic acid, phthalic acid,
Itaconic acid, etc.) vinyl esters, allyl esters, vinylamides or allylamides; polyamines (e.g. ethylenediamine, 1,3-propylenediamine,
1,4-butylene diamine, etc.) and a vinyl group-containing carboxylic acid (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

Further, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconylyl acetic acid, Itaconiloylpropionic acid, reactants of carboxylic anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylacetic acid, allylaminocarbonylpropionic 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 methacryloylpropionate, methacryloyl Allyl propionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl methyloxycarbonyl ethylene ester acrylate, N-allylacrylamide, N-allylmethacrylamide, N-
allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.); and amino alcohols (e.g. aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.); Examples include condensates with carboxylic 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. form a certain resin.

The weight average molecular weight of the dispersion stabilizing resin of the present invention is lXl0
'~2X10' is preferred, more preferably 2.5X
The zero weight average molecular weight is lXl0, which is IO'~lXl0'
If it is less than ', 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 10', 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 preferable range of 0.15 to 0.4. It may happen.

Specifically, the dispersion stabilizing resin polymer used in the present invention is prepared by using a known method to obtain a monomer corresponding to the repeating unit represented by the general formula (+) 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 total number of polymerization initiators used here was 111 and 100, respectively.
The amount is 0.5 to 15% by weight, preferably 1 to 141% based on the weight part.

The dispersion stabilizing resin of the present invention produced as described above is
The adsorbed particles of the zero-dispersion stabilizing resin that interact with and adsorb to the insoluble resin particles are soluble in non-aqueous solvents because the dispersion-stabilizing resin is cross-linked and becomes soluble in non-aqueous solvents. Affinity is significantly improved. 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). can be distinguished into oligomers (B).

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

General formula (In) 7m-R5 In general formula (III), T1 is -000-1OCO-1-
CH,0CO-1, where R6 is a hydrogen atom or a carbon number of 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, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxy ethyl group, 3-methoxypropyl group, etc.).

Rs is a hydrogen atom or an optionally substituted aliphatic group having 1 to G carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2°2-dichloroethyl L 2,2. 2-) lyfluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group,
2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group , trimethoxysilylpropyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group , 2-carboxamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group,
cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

d' and d3 may be the same or different, and each represents the same content as bl or b in the general formula (II).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, acetic acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. C1-C4 optionally substituted alkyl esters or amides of acids (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group) ,
Trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-cotroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylamino ) ethyl group, 2-(N,N-diethylamino)ethyl group, 2
-Carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.)
; Styrene derivatives (91t) styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene , N,N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid;
Cyclic anhydrides of maleic acid and itaconic acid; acrylonitrile; methacriconitrile; heterocyclic compounds containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook - Basic Edition" edited by The Polymer Society of Japan) , p175-184
, Baifukan (published in 1986), for example, N
-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-
vinylmorpholine, etc.).

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

Oligomer (B) is an oligomer with a number average molecular weight of 10' or less, which is formed by bonding the above-mentioned specific polar group only to one end of the main chain of a polymer consisting of repeating units represented by the general formula. be.

In general formula (II), the hydrocarbon groups contained in blSbM, T1 and 11 each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted.

In general formula (II), e in the substituent represented by T1
In addition to hydrogen atoms, preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group). , decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group,
2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl -1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-
2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl 1,4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. (benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethy7L4,2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) , carbon number 5~
8 optionally substituted alicyclic groups (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), or optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chloroethyl group, dichlorophenyl group, Bromophenyl group, cyanophenyl group,
acetylphenyl group, methoxycarbonylphenyl group,
(ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

Examples of the substituent which may have a substituent include a nitrogen 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, methoxymethyl group, etc.).

R8 preferably represents a hydrocarbon group having 1 to 18 carbon atoms, and specifically represents the same content as described for R3 above.

bl and b wealth may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -
Coo-R4 or -CIICOOR'(R' preferably represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted. , specifically, represents the same content as that described for R1 above).

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

11 represents a polarity Δ□ that is bonded only to one end of the main chain of a polymer having a number average molecular weight of 1 The hydrocarbon group represented by R1 is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group). , hexenyl 1.2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), or an optionally substituted aromatic group (e.g., phenyl group) , tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Moreover, among the polar groups of the present invention, the amino group is -MHI.

Represents a hydrocarbon group having a prime number of 1 to 18, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically represents the above-mentioned R
Represents the same content as the hydrocarbon group in I.

Even more preferably, the hydrocarbon group of R1, R1, R1 and R9 is an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, or an optionally substituted phenyl group. It will be done.

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

Among the oligomers (B) of the present invention, preferred are those represented by the general formula (■a) or the general formula (IVb).

General formula (IVa) b' bfu〇-ga-(C1l-C)-l pt General formula (rVb) bl bffi-(CH-C)-ga-Q Book Tly* General formula (IVa) and (IVb) Medium, bl, b! , T1
and Hl represent the same contents as the symbols in general formula (II).

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

16 W is a single bond or -((:)-(R'', R' is water R1 straight atom, halogen atom (e.g., ], chlorine atom, bromine atom, etc.), cyano group, Hydroxy group, alkyl group (e.g., methyl group, ethyl group, proR1!-3i-(R"-, R" each independently represents a hydrogen atom, a hydrocarbon group having the same content as R1!R3 above, etc.) Represents a single linking group or a linking group composed of any combination selected from atomic groups such as [shown].

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

The oligomer (B) of the present invention is a homopolymer component or a copolymer component selected from repeating units represented by general formula (II) or monomers corresponding to repeating units represented by general formula (II). It is composed of a copolymer component obtained by polymerizing the monomer and other monomers that can be copolymerized with the monomer.

Examples of other monomers that can be used as a copolymer component together with the polymer component of general formula (It) include acrylonitrile, methacrylonitrile, and a heterocyclic compound containing a polymerizable double bond group (specifically, Compounds similar to the beterocyclic compounds described for monomer (A)), compounds containing a carboxamide group or sulfamide group and a polymerizable double bond group (for example, acrylamide, methacrylamide, diacetone acrylamide, 2 -carboxamidoethyl methacrylate, vinylbenzenecarboxamide, vinylbenzenesulfamide, 3-sulfamidopropyl methacrylate, etc.).

The repeating unit represented by the general formula (II) described above accounts for 30% by weight to 1% by weight in the oligomer (B) used in the present invention.
00% by weight is appropriate, preferably 50% by weight to lO
It is 1%.

In addition, those containing no co-electronically synthesized H component containing polar groups such as phosphono group, carboxyl group, sulfo group, hydroxyl group, formyl group, 1-amino group, and -P-R'' group in the polymer main chain. preferable.

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

Specifically, P, Dreyfuss & R,P,
QuirkEncycle, Polym, Sci,
Eng,, 1.551 (I987), Yoshiki Nakajo, Yuya Yamashita [Dye and Medicine J, 30.232 (I985)
, Akira Ueda, Susumu Nagai, Science and Industry J, 60.57 (I
986) and the literature cited therein.

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

(Margin below) (I) CH.

n = integer of 1-10, (2) C11゜αphantom R p: integer of 1 to 4 (5) (8) (9) l15 CH3 CH3 CH3 804Hz'h-NlIC匡11□C1+2CTo
CH2C(CH2-C)-CN C0OR +1O-C1lt C1(.

C11゜)10C)IrC-NHCOCHzCIh C(Cl
hC)-110-CI(.

C.N. 0OR CH.

HOiS-CHxC)It-3-(CHxC)-α
The dispersion resin of the present invention comprises at least one of each of a -functional monomer (A) and an oligomer (B), and the important thing is that the resin synthesized from these If it is insoluble in the solvent, a desired dispersed resin can be obtained.

More specifically, the oligomer (B) represented by the general formula (II) is added in an amount of 0.05 to 0.05 to the monomer (A) to be insolubilized.
It is preferable to use 10% by weight, more preferably 0
．． It is 1 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~
10", preferably 104 to 5 x 105.

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 oligomer (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 benzoyl oxide, azobisisobutyronitrile, butyl lithium, etc. Specifically, (1) dispersion stabilizing resin, monomer (A)
and a method of adding a polymerization initiator to a mixed solution of oligomer (B); (2) a method of dropping monomer (A) and oligomer (B) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved; or (2) a method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing the entire amount of the dispersion stabilizing resin and a portion of the mixture of monomer (A) and oligomer (B); Furthermore, there is a method in which a mixed solution of a dispersion stabilizing resin, monomer (A), and oligomer (B) is optionally added together with a polymerization initiator into a nonaqueous solvent. can also be manufactured.

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

The soluble resin which is the dispersion stabilizing resin is 1 to 100 parts by weight based on 100 parts by weight of the total monomers used above,
Preferably it is 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 zero reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers, and esters is used in combination with the nonaqueous solvent used in the reaction, or when unreacted monomers (A) to be polymerized and granulated are If it remains, it is preferable to remove it by heating it to a temperature above the boiling point of the solvent or monomer or 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 redisperse even when the development speed is increased, and no stains are observed at all 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.

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

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

In the liquid developer of the present invention, a colorant may be used if desired, but the colorant is not particularly limited.
Various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. Examples of such materials include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa yellow, 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 (see, for example, Yuji Harasaki "Electronic Photography" Vol. 16, Vol. 2).
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), and copolymers containing half-maleic acid amide components.

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

The toner particles mainly composed of resin (and optionally used colorant) are preferably 0.5 parts by weight to 50 parts by weight based on 1,000 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, capri will likely occur in non-image areas.

Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and the amount is 0.5 parts by weight per 1000 parts by weight of the carrier liquid.
Approximately 100 parts by weight can be added.

The charge control agent as described above is used in an amount of 0.001 to 1.0 parts by weight per 1000 parts by weight of the carrier liquid. 1 part is preferable, and 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, if the electrical resistance of the liquid developer with toner particles removed becomes lower than 10' CII, it will be 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 manufacturing the dispersion stabilizing resin, manufacturing examples of latex particles, and examples of the present invention are illustrated below, but the present invention is not limited to these.

A mixed solution of 100 g of 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. 2.2゜3.0g of azobis(isobutyronitrile) (abbreviated as A, r, B, N) was added and reacted for 4 hours, and further ^, 1. B, N 1.
0g was added and reacted for 2 hours, and further A, 1. B, N 0.5
g and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5 ml of methanol, and the white powder was collected by filtration and dried to obtain 88 g of powder. The weight average molecular weight of the obtained polymer was 3.3 x 10'.

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

The weight average molecular weight of each resin is 3. OX 10'~5XlO
'Met.

Table 1 to 7: In Production Example 1, the same procedure as Production Example 1 was used 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 produced in the same manner.

The weight average molecular weight of each resin was 3X10' to 6X10'.

Table 2 A mixture of 95 g of Ni-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. A.1. B, N, 3. After adding Og and reacting for 8 hours, the mixture was heated to 110° C. using a Dean-3 tark and stirred for 6 hours. The solvent used, isopropanol, and methanol produced as a by-product in the reaction were removed. After cooling, it was reprecipitated into 1.5 liters of methanol, and a white powder was collected by filtration and dried. Yield: 82g, weight average molecular weight: 5.6
It was X 10'.

O sesame's Nio sesame B Methyl methacrylate 100g, thioglycolic acid 5g
A mixed solution of 150 g of toluene and 50 g of methanol was heated to 70° C. while stirring under a nitrogen stream.
A.1. 1.5g of B and N were added and reacted for 4 hours.

Furthermore, A.1. 0.4g of B and N were added and reacted for 4 hours. After cooling, the reaction solution was mixed with methanol/water ((4/1)
Volume ratio] After reprecipitation in a 2N mixed solution, separating the methanol solution by decantation, and drying the viscous substance, 75 g of a colorless viscous substance was obtained. The number average molecular weight of the 0 polymer was 2.800.
Met.

2 to 12% of oligomer I3-2
Each oligomer B-2 to
B-12 was manufactured. The number average molecular weight of the obtained oligomer was 2,500 to 3.500.

Table 3 In Production Example 1 of Sesame - Nio Sesame Logomer, each oligomer B- 13 to B-23 were manufactured. The number average molecular weight of the obtained oligomer was 2.500 to 3,500.

Table 4: 100g of black sesame methyl methacrylate, 150g of toluene and 5g of ethanol
While stirring 0g of the mixed solution under a nitrogen stream, the temperature was 75°C.
It was heated to 2.2'-azobis(cyanovaleric acid) (
8g of A, C, V) was added and reacted for 5 hours, and then A
, C, V, were added and reacted for 4 hours. After cooling the obtained reaction solution, it was reprecipitated into a mixed aqueous solution of methanol/water ((4/1) volume ratio), and after separating the aqueous methanol solution with decane silane, the viscous material was dried. The yield was 70 g, and the number average molecular weight of the polymer was 2.600.

In Oligomer Production Example 24, the polymerization initiation side A, C,
Each oligomer B-25 to
B-33 was manufactured. The number average molecular weight of the obtained oligomer was 2.000 to 4,000.

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

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 88% and an average particle size of 0.24.

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

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

Table 7 --S: --S D-20g of dispersion stabilizing resin P-10, 100g of vinyl acetate, 5g of crotonic acid, 1.0g of oligomer B-3 and Isopar E
A mixed solution of 468 g was heated to 70°C while stirring under a nitrogen stream. A, B, V, N.

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

-3 Nix D-A mixed solution of 20g of dispersion stabilizing resin P-7, 100g of vinyl acetate, 6.0g of 4-pentenoic acid, 0.8g of oligomer B-15 and 380g of Isoppar G, The mixture was heated to a temperature of 70'C while stirring under a nitrogen stream.

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

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.24.

--S 38: --A mixed solution of 18 g of Cus D-38 dispersion stabilizing resin P-6, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of oligomer B-9 and 380 g of n-decane, The mixture was heated to 75°C while stirring under a nitrogen stream.

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

0.5g of was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.20.

--S: --S D-9 20g of dispersion stabilizing resin P-12, methyl methacrylate 10
A mixed solution of 470 g of Og and n-decane was heated to 70° C. with stirring under a nitrogen stream. A.1. B, N, 1. Og was added and the mixture was reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.45 m.

-- In Production Example 1 of A latex particles of A, the same procedure as in Production Example 1 was carried out except that oligomer B-1 was removed. The obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.25.

In Production Example 1 of B latex particles, poly(octadecyl methacrylate H8 g, vinyl acetate 100 g, octadecyl methacrylate) 1. Og and Isopar H 3
The procedure was the same as in Production Example 1 except that 85 g of the mixed solution was used.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.22.
- latex. (Unexamined Japanese Patent Publication No. 60-179751
latex corresponding to the issue)
43757, a mixed solution of 12 g of a dispersion stabilizing resin having the following structure, too much vinyl acetate, and 8 g of Isopar H3B was used, and the same process as in latex particle production example 1 was performed to obtain a polymerization rate of 88. A white dispersion of latex particles with an average particle size of 0.18% was obtained.

Dispersion stabilizing resin weight average molecular weight 43.000 Example 1 10 g of dodecyl methacrylate/acrylic acid copolymer (copolymerization ratio: 9515 weight ratio), 1 Gg of Nigrosine and 30 g of Shell Silua 1 were mixed with glass beads in a paint shaker (Tokyo Seiki ■). ) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30g of latex D-1 of latex particle production example 1
5 A liquid developer for electrostatography was prepared by diluting 2.5 g of the above nigrosine dispersion and 0.08 g of the octadecene-half-maleic acid octadecylamide copolymer to 12 parts of Shell Sol 71.

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

Comparative liquid developer A Latex of Nilatex particle production example 40 Comparative liquid developer B Latex of Nilatex particle production example 41 Comparative liquid developer C Latex of Nilatex particle production example 42 These liquid developers was used as a developer in a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film ■), and an electrophotographic light-sensitive material, ELP Master ■ type (manufactured by Fuji Photo Film ■), was exposed and developed.

The plate making speed was 7 plates/min. Furthermore, after processing 3,000 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 plane a) was performed using 30% of the original. The results are shown in Table-8.

Table 8 When plate making was carried out using each developer under severe forced plate making conditions with extremely high plate making speeds as described above, as is clear from the results in Table 8, no staining of the developing device occurred and 30%
The developer for which the image on the 00th plate-making plate is clear is only the developer of the present invention, while offset printing master plates (ELP masters) obtained by plate-making from each developer are printed in a conventional manner, Missing characters in printed images,
Comparing the number of prints until fading of the solid area occurred, it was found that the master plates obtained using the developers of the present invention, Comparative Example A, and Comparative Example C did not produce this problem even after printing more than 10,000 sheets, compared with Comparative Example B. The problem occurred after 8000 mask plates were used.

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

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

In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 7.
11 sheets per minute! (Conventionally, the plate making speed was 2 to 3 sheets/min), the developing device (especially on the back electrode plate) became dirty, and after 3000 sheets,
The image quality of the copied image on the plate began to be affected (decreased D wax, fading of fine lines, etc.). There was no problem with the number of master plates printed in Comparative Example C, but
Comparative Example B had a decrease.

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

Example 2 White dispersion 100 obtained in latex particle production example 2
A mixture of 1.5 g of Sumikalon Black and 1.5 g of Sumikalon 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 0.2 On.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 15 g of higher alcohol FOC-1400 (manufactured by Nissan Chemical Company) to 11 of Shell Silua I.

This was developed using the same apparatus as in Example I, and the result was 300.
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

Furthermore, the image quality of the obtained offset printing master plate L/-t was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 3 White dispersion 10 obtained in latex particle production example 36
A mixture of 0 g and 3 g of Victoria Blue B was heated to a temperature of 70
The mixture was heated to 80°C to 80°C and stirred for 6 hours. After cooling to room temperature 2
The remaining dye was removed by passing the mixture through a 0.00 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.16.

32g of the above blue resin dispersion, zirconium naphthenate o
, os g , and a liquid developer was prepared by diluting 15 g of higher alcohol FOC-1600 (manufactured by Nissan Chemical Company) to 12 of Isopar H.

This was developed using the same device as in Example 1, and the result was 30
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 4 32 g of white resin dispersion obtained in latex particle production example 3
1 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-docosanylamidated product of a copolymer of diisobutylene and maleic anhydride into Isopar G In.

When this was developed using the same device as in Example 1, the result was 300
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Furthermore, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were both very clear.

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 aging.

Example 5 10 g of poly(decyl methacrylate), 30 g of Isopar H and 8 g of Alkali Blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of Alkali Blue.

30 g of white resin dispersion D-13 obtained in latex particle production example 13, and the above alkali blue dispersion 4.2.
A liquid developer was prepared by diluting 0.06 g of a semi-docosanylamidated copolymer of octadecyl vinyl ether and maleic anhydride, and 15 g of higher alcohol FOC-1400 to 11 of Isopar G.

When this was developed using the same device as in Example 1, the result was 300
Even after developing 0 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 image quality of the printed matter after printing 10,000 sheets were very clear.

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

Table 9 When this was developed using the same device as in Example 1, 300
Even after developing 0 sheets, almost no or no toner adhesion to the device was observed.

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

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device does not become contaminated, maintenance intervals can be extended for a long time, and the image quality of the obtained offset printing master plate is After printing 10,000 copies, the image quality of the printed matter was 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: 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 A carboxyl group, a sulfonate group 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). group, hydroxyl group, formyl group, amino group, phosphono group, and ▲ mathematical formula, chemical formula, table, etc. ▼ group (R^■ is -R^1 group or -O
R^1 group, R^1 represents a hydrocarbon group], each containing at least one oligomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding at least one polar group selected from A liquid developer for electrostatic photography, characterized in that it is copolymer resin particles obtained by subjecting a solution containing seeds to a polymerization reaction. General formula (I) In 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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), T^1 is -COO-, -OCO-, -
CH_2OCO-, -CH_2COO-, -O-, -S
O_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^3 is a hydrogen atom or carbon number 1 ~18 hydrocarbon groups. R^2 represents a hydrocarbon group having 1 to 22 carbon atoms. b^1 and b^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
represents a hydrocarbon group, -COO-R^4 or -COO-R^4 via a hydrocarbon group having 1 to 8 carbon atoms, where R^4 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. represent.