JPH02302762A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To enhance dispersion stability by using as the resin particles to be dispersed, the copolymer resin particles obtained by copolymerizing at least a specified monofunctional monomer with a monomer having >=2 polar groups and/or polar connecting groups each contained in a solution. CONSTITUTION:The dispersed resin particles are made of the polymer having repeating units each represented by formula I in which T<1> is -COO-, -OCO-, or the like; Y<1> is a 6 - 32C aliphatic group; and each of a<1> and a<2> is H or halogen or the like. The main chain of the polymer is partially cross-linked and it is obtained by copolymerizing the monofunctional monomer soluble in a non-aqueous solvent but to be insolubilized by polymerization with the monomer having >=2 polar groups and/or polar connecting groups represented by formula II all contained in the same solution, in the presence of a dispersion stabilizing resin. In formula II, V is -O-, -COO-, or the like; Q is H, halogen, or the like; each of X1, X2, U1, and U2 is -O-, -S-, or the like; each of U4 and Q6 is a 1 - 18C hydrocarbon group; each of b1 and b2 is H, a hydrocarbon group, or the like; and each of m, n, and p is an integer of 0 - 4, thus permitting dispersion stability to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) 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 10" Ωcm or more and a dielectric constant of 3.5 or less. In particular, redispersibility, storage stability,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties.

(Prior art) General liquid developers for electrophotography include carbon blank, organic or inorganic pigment or dye such as nigrosine, phthalocyanine blue, acrylic resin, rosin, etc.
A polymer in which a natural or synthetic resin such as synthetic rubber is dispersed in a highly insulating and low dielectric constant liquid such as a petroleum-based aliphatic hydrocarbon, and further contains metal soap, lecithin, linseed oil, higher fatty acids, and vinylpyrrolidone. Added a polarity control agent.

In such developers, 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 insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, 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 problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble Latinx particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. This has the disadvantage that redispersion stability is insufficient for practical use, such as solidification, making redispersion difficult, and furthermore causing equipment failure and smudging of copied images. In addition, in the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle size distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized; The particles had a wide particle size distribution containing a large amount of coarse particles, or the particles had a polydisperse particle size with two or more average particle sizes. Furthermore, it was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1- or more or very fine particles of 0.1p 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, the degree of dispersion and redispersion of the particles can be improved by forming insoluble dispersion resin particles of a co-electric material of a monomer to be insolubilized and a monomer containing two or more types of polar components. A method for improving the properties and storage stability is disclosed in Japanese Patent Application Laid-Open No. 62-1518.
It is disclosed in No. 68, etc.

In addition, in the presence of a polymer using a bifunctional monomer or a polymer using a polymer reaction, insoluble dispersed resin particles of a monomer that becomes insolubilized and a coelectric material with a monomer containing two or more types of polar components. A method for improving the dispersity, redispersibility, and storage stability of particles by
No. 62, No. 63-66567, etc.

(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-62-151868 and JP-A No. 62-16636
No. 2, No. 63-66567, the dispersion resin particles produced according to the method disclosed in No. 2, No. 63-66567, have problems when the development speed increases or the maintenance period is extended.
Performance was still not necessarily satisfactory in terms of particle dispersibility and redispersibility.

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 electrophotographic production of offset printing plates having excellent printing ink oil sensitivity and stiffness resistance.

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

Still another object of the present invention is to provide a liquid developer that can be used in any system where a liquid developer can be used, such as inkjet recording, shadow-wound tube recording, and recording of various change processes such as pressure changes or electrostatic changes. It is to be.

(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 109 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), and a portion of the main chain of the polymer is crosslinked, in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. , a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and the following general formula (I[
) Copolymer resin particles obtained by polymerizing a solution containing at least one monomer (B) containing at least two or more polar groups and/or polar linking groups. This was achieved by an electrostatographic liquid developer characterized by the following.

General formula N)
Il□0CO-1-CI (, COO-2-〇- or -S
Represents O□-.

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

al and at may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -coo-z', or a hydrocarbon group having 1 to 8 carbon atoms. one COO-Z' (here, 21 is the number of carbon atoms from 1 to
22) represents a hydrocarbon group.

General formula (II) b, bt CIlmiC V-4-U, -Xl+t12-x, )-, q General formula (U
), ■ is -o-, -coo-1-OCO-1■ -cogoco-2-8bushi-, -CONH-2-5O1
NH~, -CON-, En or -5O,N- (W is a hydrocarbon group or general formula (II
) in the bonding group: +Ur-X + +Ur-X
represents the same content as YO+T-Q).

Q, hydrogen atom or halogen atom, -0)1, -CN
, -NH,, -COOII, -5o, )l or -
Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with POzHz.

X and X may be the same or different, respectively -0-1-S-, -CO-1-CO! -, -0CO-,
-5Ot-1 or -NIICONII- (Ql
, 02, Ql, G4 and Q indicate the same content as Q above).

U, and U! may be the same or different from each other, each may be substituted, or -CH-x, +U4-x4-
)-T-06 may be interposed in the bond of the main chain [χ1 and ×4 may be the same or different from each other and have the same contents as X1 and X above, and U is substituted represents a hydrocarbon group having 1 to 18 carbon atoms, and Q represents the same content as Q above]
Represents a hydrocarbon group having 1 to 18 carbon atoms.

bl and b2 may be the same or different, and each is a hydrogen atom, a hydrocarbon group, -Coo-1+, or -CQO-R+ via a hydrocarbon (R+ is a hydrogen atom or an optionally substituted hydrocarbon group) ).

m, n and p may be the same or different, and each is O~4
represents an integer.

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

The carrier liquid having an electrical resistance of 109Ωc11 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, and halogen-substituted hydrocarbons thereof. You can use your body. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isopar E1
Isopar G1 Isopar H, Isopar L (Isopar; trade name of Exxon), Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Co.)
, Amsco OMS, Amsco 460 i agent (Amsco;
Spirits Co., Ltd.'s product name) etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as Latinx 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. -Functional monomer (A
) and a monomer (B) containing at least two scratchable groups and/or polar linking groups, and are produced by polymerization and granulation.

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, Isopar E, Isopar G1 Isopar H1 Isopar L1 Scherzol 70, Scherzo-
Lua 1, Amsco OMS, Amsco 460? Container 1 etc. may be used alone or in combination.

Solvents that can be mixed with these aWj media include alcohols (for example, methyl alcohol,
ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone, etc.), carboxylic acid esters (e.g. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propion ethyl acid, etc.), ether I! (eg diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbon M (eg, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methyl chloroform, etc.), and the like.

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

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

This book is used to make a stable resin dispersion of a solvent-insoluble copolymer produced by copolymerizing a -functional monomer (A) and a monomer (B) in a non-aqueous solvent. The dispersion stabilizing resin of the invention is a polymer soluble in the nonaqueous solvent, in which a portion of the polymer chain is crosslinked with a polymer containing a repeating unit represented by the general formula (I).

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

-m In the repeating unit represented by formula (I), the aliphatic group and the hydrocarbon group may be substituted.

In general formula (I), T1 is preferably -000-1
-OCO-1-CLOCO-1-CH,COO- or-
0-, more preferably -COO-1-cozc
Represents oo- or -〇-.

y+ is preferably substituted with 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'', -
Coo-Z", -0CO-Z"(,::,:'?
? Z'' represents an alkyl group having 6 to 22 carbon atoms, such as hexyl group, octyl group, decyl group, dodecyl group,
Examples include substituents such as hexadecyl group, octadecyl group, etc.). More preferably, Yl has 8 to 2 carbon atoms.
0 representing an alkyl group or alkenyl group of 2, such as octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group , octadecenyl group, etc.

al and a2 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 -CLCOO-
23 (here, 23 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, 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, aI and a2 each represent a hydrogen atom,
Alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), -coo-z' or -CHIC
oo-Z' (Kokote Z' represents an alkyl group or alkenyl group having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl 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 Yl above.

The dispersion stabilizing resin of the present invention used for making a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing monomers (A) and CB) in a non-aqueous solvent is: A resin that does not contain a graft group that polymerizes with monomers (A) and (B), and a polymer that contains at least one type of repeating unit represented by the general formula N), in which a portion of the polymer main chain is It is a crosslinked resin that is soluble in the non-aqueous solvent.

The polymer component of the dispersion stabilizing resin of the present invention has the general 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 derivatives 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, 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: CONHCIhO
Z' (here, 25 represents a hydrogen atom or an alkyl group)
Alternatively, a crosslinking reaction by polymerization is effective.

In the polymerization reaction, preferably, a method of cross-linking polymer enzymatic release 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 is CHt=CH-1OC
R.

CHx=CH-CHt-, CL=C) I-C-0-, C
Hx=C-C-0-1■ CI, CHt3 CH2=C-CONHCoo-1C1lZ=C-CON
HCONII-1CH, OCL 0 CII=CH-CONH-, CHz・CI(-0-C-
, CHz-C-0-C-1I CH, ENGCH-CH! -0-C-, CHt・Cl1-N
HCO-1CL・C11-CH□-N)ICO-1CH
,,Cll-802-1CI+! =CH-GO-1CH
z:CH-0-, C1l□, C)I-5-, etc., but monomers having two or more of the above polymerizable functional groups may have these polymerizable functional groups in the same group. Any monomer having two or more of the same or different types may be used.

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,
methacrylic acid of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives) , acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers; dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid,
Vinyl esters, allyl esters, vinylamides or allylamides of phthalic acid, itaconic acid, etc.; polyamines (e.g. ethylenediamine, 1,3-propylene diamine, 1,4-butylene diamine, etc.) and carboxylic acids containing vinyl groups. (For example, condensates with 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 acid anhydride and alcohol or amine (e.g. allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic 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, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl acrylate ethylene ester, N-allylacrylamide, N-allylacrylamide, N-allylitaconamide, allylmethacryloylpropionate, etc.); and amino alcohols Examples include condensates of amines such as ethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc. and carboxylic acids containing vinyl groups.

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 8% 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 1×104
~2×10′ is preferred, more preferably 2.5×10
It is 4 to 1×10 seconds. When the weight average molecular weight is less than 1×10 4 , 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. Moreover, when it exceeds 2X105, 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. Therefore, it may be difficult to adjust the average particle size to a preferable range of 0.15 to 0.4.

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 convenient and preferred.

The amount of the polymerization initiator used here is 0.5 to 15% by weight, preferably 1% by weight, based on 100 parts by weight of the total monomers.
~10% by weight.

The dispersion stabilizing resin of the present invention produced as described above is
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 that is soluble in nonaqueous solvents is crosslinked. 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 include a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a monomer represented by the general formula (n) above. A monomer containing at least two or more polar groups and/or polar linking groups and copolymerizing with the monomer (A) (
B) can be distinguished.

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

General formula (I[[)% formula% In general formula (I[1), Bl is -C00-5-OCO-1
- Represents to CIl□OCO. Here, R3 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, hensyl group, chlorobenzyl group, methylhensyl group, methoxyhensyl group,
Phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorohensyl group, 2-methoxyethyl group, 3
-methoxypropyl group, etc.).

R1 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2゜2-dichloroethyl group, 2,2 .2-) Dichloroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxyethyl group, 2.3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
-Cyanethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethylamino Ethyl group, trimethoxysilylpropyl group, 3-bromopropyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-chenylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group,
cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

dl and R2 may be the same or different, and each represents the same content as al or R2 in the general formula (I).

Specific examples of the Ichinomiya functional monomer (A) include vinyl esters or allyls of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.). 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 (as an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl 1.2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2- Benzenesulfonylethyl group, 1-(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-chenylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); Styrene derivatives (e.g. styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromo Styrene, vinylbenzenecarboxylic acid, vinylbenzenecarboxylic acid,
Chloromethylstyrene, hydroquinemethylstyrene, methoxymethylstyrene, N.

N-dimethylaminomethylstyrene, vinylhenzenecarpoxyamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic anhydrides of maleic acid and itaconic acid Acrylonitrile; Methacriconitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook - Basic Edition - J, P L75-184, Baifu," edited by The Polymer Science Society of Japan, Tate (I98
For example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone,
vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

- Two or more functional monomers (A) may be used in combination.

Next, the monomer (B) represented by the general formula (n) used in the present invention will be further explained.

In general formula (II), ■ is preferably 10-1 [W
is preferably an optionally substituted alkyl group having 1 to 16 total carbon atoms, an optionally substituted alkenyl group having 2 to 16 total carbon atoms, an optionally substituted alicyclic group having 5 to 18 total carbon atoms, or a general Bonding group n←u1−×1+r−+−U in formula (n)
represents the same content as t-X2→1-Q.

Q is preferably a hydrogen atom, a halogen atom (eg, a chloro atom, a bromo atom, etc.), -0H2-CN.

It represents an aliphatic group having a total of 1 to 16 carbon atoms (for example, an alkyl group, an alkenyl group, or an aralkyl group is shown as an aliphatic group) which may be substituted with -COOH.

×1 and L may be the same or different, preferably 10-1-S-, -CO-1-coo-, -oco
-1- indicates the content).

uI and u2 may be the same or different from each other, preferably substituted, or with -CH- interposed in the bond of the main chain, to 1,000 U "χ4 total Q.

A hydrocarbon group having 1 to 12 carbon atoms (the hydrocarbon group includes an alkylene group, an alkenylene group, an arylene group, or a cycloalkylene group).

However, X3 and X4 may be the same or different.
X! , U4 preferably represents an optionally substituted alkylene group, alkenylene group or arylene group having 1 to 12 carbon atoms, and Q has the same meaning as Q above.

bl and b8 may be the same or different (preferably a hydrogen atom, a methyl group, -COO-R, or -CH
zCOO-R+ (R+ preferably represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, or a cycloalkyl group).

Furthermore, m, n and p may each be the same or different,
Preferably it represents a number of 0.1.2.3.

Furthermore, more preferably, in formula (II), ■ is -C00-1
may also be different hydrogen atom, methyl group, -Coo-R+
or -CHgCOO-R+ (R+ more preferably represents an alkyl group having 1 to 12 carbon atoms).

Furthermore ul and U! To give a specific example, R
4 s represents a group, a halogen atom, etc.), -+CH=CH)-
1 and p have the same meanings as the above symbols). .

Also, the bonding group in general formula (n): V+U, -Xl-h-÷U! X! It is preferable that the connecting main chain consisting of 10 rQ and Q to Q (i.e., ■, Ul, xl, U2, ×2 and Q) has a total number of atoms of 8 or more. , +U+ X++T-(-
When Uz X1hrQ is represented, a connecting main chain composed of W is also included in the connecting main chain. Furthermore, U7, U2
-X in the case of a hydrocarbon group in which -C1l- is interposed in the bond of main chain x3÷t+, -X4h-Q4
x,00r-Xah-Q& is also included in the linking backbone. As for the number of atoms in the connecting main chain, for example, ■ is -COO-
When representing or -CONH-, an oxo group (=0 group) and a hydrogen atom are not included in the number of atoms, but carbon atoms, ether type oxygen atoms, and nitrogen atoms constituting the connecting main chain are included in the number of atoms. Therefore, -COO- and -CONH- are counted as having two atoms. Similarly, for example, Q is -C9H
When representing 19, hydrogen atoms are not included in the number of atoms, but carbon atoms are included.

Therefore, in this case, the number of atoms is counted as 9.

More specifically, monomer (B) can be exemplified by the following compounds.

(■-1) CH3 CH2=C "Coo(CIl□)zOcOcJ+q CI3 CH,=C C00(CHzhOCOC++Hz* (II-3) CH3 CI(,=C Coo(CHI) zOcO(C)It) 5OCOC
H3(n-4) C11゜teCI□-〇Coo(CL) IoOcOcaLko(II-5) CHl CIl□=C 薯Coo(CHz)+aCOOCeH+t(n-6) CIl□C00CIh CH2=C " C00(CL )zcOOcJq (■-7) C(I゜■ CH,=C C0NH(CH2)6COOC1lHI7(n-8) C11,=C C00(CHI)!NHCO(C)If)3COOCH
3(n-9) CHz=C Coo(CIri JCOCH:(Jl-COOCall+
5(n-10) CHl CIl□-〇” C00CHxCHCHzOCO(:sli++0COC
sH++ (II-11) CH3 coz=c C00CHzCHCLOCOCaH+, lC0CJt (II-12) CHI.

― cuz=c COMCII□CHzOCOCsH++CIlgCHz
OCOCsl(z (n-13) CH.

(II-14) CH3 ■ CH=CH C00(C11□)+oOCOC6H+3(II-15
) CH.

CH,=CC)13 CONHCCHzOCOCJ.

CIl□0COC4119 (■-16) ■ CH,=C Coo(C)It)zOcO(CHz)*COOCC0
0CHzCLC7(II-17)CH 0CO(C)lx)+oOCOCJt (n-18) CH.

CH2=C TomiC00(jltcHxcHOcOcsH++0COCs
H++ (II-19) CHz C11t C C00CHzCtl□CHzCHOCOC-H+:+0
COCJl 3 (n-20) CH.

CH,=C (n-21) C00(CHz)xOco(Cut)zcOOczll
.

(n-22) “ CC00CHz (JICHzOOCCIhCHzCOO
CJ le coc mountain (II-23) CH3 CIl, =C C00CHzCLC1lCHzOCOCaL00CCH
-OCOCsHt CL-OCOCIII.

(II-24) C) 12 CJ (n-25) (n-26) CL=CHCHr-OCO(C1h)zcOOclhc
IIctlzOcOc-Hq0COCat! w (II-27) C00CHzC)lclhNHcIl□CH20COC
I+3JCOCsH++ (II-28) CH3 CH,=^ C00CHtCHxNHCOOCa)l*(II-29
) CHs CH-CH C00CII□CHCtlz00CCHOCOCsH+
+JCOC3H? CHzOCOCsH++ The dispersion resin of the present invention is composed of at least one each of monomer (A) and monomer (B), and the important thing is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. If so, a desired dispersed resin can be obtained. More specifically, it is preferable to use 0.1 to 10% by weight of the monomer (B) represented by the general formula (I[) with respect to the monomer (A) to be insolubilized, and more preferably It is 0.2 to 8% by weight. Further, the molecular weight of the dispersion resin of the present invention is preferably 10' to 10h, more preferably 104 to 10'.

In order to produce the dispersion resin (latex particles) used in the present invention, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and monomer (B) are mixed in a clear water solvent and subjected to filtration. The polymerization may be carried out by heating in the presence of a polymerization initiator such as benzoyl oxide, azobisisobutyronitrile, or butyllithium.

Specifically, (1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, monomer (A), and monomer (B), (2)
A method in which monomer (A) and monomer (B) are dropped together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved; A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing a part of the mixture of monomers (B),
Furthermore, there are methods such as (1) optionally adding a mixed solution of a dispersion stabilizing resin and a monomer together with a polymerization initiator to a non-aqueous solvent, and any method can be used for production.

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

The amount of the soluble resin as a dispersion stabilizer is 1 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the total monomers used above.

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, and the reaction time is preferably 1 to 15 hours.

When the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the nonaqueous solvent used in the reaction, or when the monomer (A) or monomer (B) to be polymerized and granulated is ) If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than its boiling point or distilling it off, 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. Even though the dispersibility is good and the development speed is improved, the redispersion is easy and no stains are observed on various parts of the device.

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

Furthermore, the liquid developer of the present invention 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 colorant may be used if desired. The coloring agent is not particularly limited.
Various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. There is. Examples 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.
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 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 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 preferably used in an amount of 0.001 part by weight to 1.0 part by weight based on 1000 parts by weight of the carrier liquid. 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, the electrical resistance of the liquid developer with toner particles removed is 10! If it is lower than Ωcm, it becomes difficult to obtain a continuous tone image of good quality, so it is necessary to control the amount of each additive added within this limit.

(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 thereto.

A mixed solution of 100 g of dioctadecyl methacrylate, 2 g of divinylbenzene and 200 g of toluene was heated to a temperature of 85'C while stirring under a nitrogen stream. 3.0g of 2゜2゜-azobis(isobutyronitrile) (abbreviated as A, 1.B, N) was added and reacted for 4 hours, and then A, 1. Add B and N, add Og and react for 2 hours, and then add A, 1. Add 0.5g of B and N to 2
Time reacted. After cooling, this mixed solution was reprecipitated in 1.5 ml of methanol, and the white powder was filtered and dried to obtain a powder of 88 ml.
I got g. The weight average molecular weight of the obtained polymer was 3.3
It was 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 3.0X10' to 5X10'
Met.

Table 1: 15-11' Notice 115-27:
\11 In Production Example 1, 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 as in Production Example 1.

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

Table-2 No. 15-11' Announcement 28: -''
+15p-octadecyl methacrylate 95g,
N-methoxymethylacrylamide 5g, toluene 15
A mixture of 0 g and 50 g of isopropanol was heated to a temperature of 75° C. under a nitrogen stream. A.1. B, N, 3, O
g and reacted for 8 hours. Next, Dean-5tark
The mixture was heated to 110° C. and stirred for 6 hours. The solvent used, isopropanol, and methanol, a by-product of 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. The yield was 82 g and the weight average molecular weight was 5.6 x 10'.

20g of dispersion stabilizing resin P-1, 100g of vinyl acetate,
A mixed solution of 1.5 g of Compound Example 11-19 of monomer (B) and 384 g of Isopar H was heated to a temperature of 70° C. with stirring under a nitrogen stream. 2.2'-azobis(isovaleronitrile) (abbreviation: A, 1.V, N,) at 0.8
g and reacted for 6 hours. 20 minutes after the addition of the initiator, clouding occurred and the reaction temperature rose to 88°C. temperature to 100
The temperature was raised to °C and stirred for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, the resulting white dispersion was passed through 200 meshes of nylon cloth and was a latex with a polymerization rate of 86% and an average particle size of 0.20.

In production example 1 of latex particles, dispersion stabilizing resin P
-1 and monomer (B) Compound Example It-19, the dispersion stabilizing resin and monomer (B) described in Table 3 below
Each latex particle was produced in the same manner as in Production Example 1, except that .

The polymerization rate of each particle was 85 to 90%.

Table-3 Table-3 (vt) 8 g (as solid content) of dispersion stabilizing resin P-25, 837 g of poly[dodecyl methacrylate]2 100 g of vinyl acetate
A mixed solution of 1.5 g of Monomer (B) Compound Example 1-15 and 380 g of n-decane was heated to 75° C. with stirring under a nitrogen stream. 2゜2'-azobis(isobutyronitrile) (abbreviations: A, 1.B, N,) in 1.
0g was added and reacted for 4 hours, and then A, 1. B, N, 0.
5g was added and reacted for 2 hours. Raise the temperature to 110°C2
The mixture was stirred for hours and the low boiling point solvent and residual vinyl acetate were distilled off. After cooling, the resulting white dispersion was passed through a 200-molecular-weight nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.20.

14g of dispersion stabilizing resin P-14, 85g of vinyl acetate,
A mixed solution of 2.0 g of Monomer (B) Compound Example 1-23, 15 g of N-vinylpyrrolidone, and 400 g of isododecane was heated to 65° C. with stirring under a nitrogen stream. A.1. 1.5g of B and N were added and reacted for 4 hours.

After cooling, it was passed through a 200 mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.261M.

12g of dispersion stabilizing resin P-10, 100g of vinyl acetate
A mixed solution of 1.5 g of Compound Example 1-18 of monomer (B), 5 g of 4-pentenoic acid, and 383 g of Isopar G was heated to 60° C. with stirring under a nitrogen stream. A,
1. V, N, 1. Added Og and reacted for 2 hours, then A
, 1. 0.5 g of V and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.25-.

20 g of dispersion stabilizing resin P-7, 2 g of monomer (B) compound example ■-16, 1 g of n-dodecyl mercaptan, 100 g of methyl methacrylate, and 478 g of Isopar H.
The mixed solution was heated to 65°C under a nitrogen stream without stirring. A.1. 1.2g of V and N were added and reacted for 4 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had an average particle size of 0.28.
- latex.

18g of dispersion stabilizing resin P-13, 100g of styrene,
A mixed solution of 4 g of Monomer (B) Compound Example 1-25 and 380 g of Isopar H was heated to 50° C. with stirring under a nitrogen stream. An amount of n-butyllithium hexane solution having a solid content of 1.0 g was added and reacted for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.30-.

28A poly[octadecyl methacrylate] (weight average molecular weight 35,000)
The process was carried out in the same manner as in Production Example 1 for Latex Particles, except that a mixed solution of 20 g of vinyl acetate, 100 g of vinyl acetate, 1.5 g of compound example ■-19 of monomer (B) and 380 g of Isopar H was used, and the polymerization rate was 88%. A white dispersion of latex particles with an average particle size of 0.23 was obtained.

-・S1-1' Notice 29''B 14g of dispersion stabilizing resin with the following structure, 100g of vinyl acetate
The process was carried out in the same manner as in Production Example 1 of latex particles except that a mixed solution of 1.5 g of monomer (B) compound (B) -19 and 386 g of Isopar H was used to obtain a polymerization rate of 90% and an average particle size of 0. A white dispersion of 25- latex particles was obtained.

<Dispersion stabilizing resin> COOC+ mast Coo(CHx)+ oc
OOcH=cHz (weight! #Ji ratio) Weight average molecular weight 43,000 Example 1 10 g of dodecyl methacrylate-acrylic acid copolymer (copolymerization ratio, 9515 weight ratio), 10 g of nigrosine, and 30 g of Isoper G were added to glass peas. The mixture was placed in a paint shaker (Tokyo Seiki ■) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30 g of the resin dispersion of latex particle production example 1, 2.5 g of the above nigrosine dispersion, 0.07 g of octadecene-half-maleic acid octadecylamide copolymer, and higher alcohol F OC-1600 (manufactured by Nissan Chemical) 15
A liquid developer for electrostatography was prepared by diluting 11 g of Isopar C.

-CL school! Two types of liquid developers A and B for comparison were prepared by replacing the resin dispersion with the following resin dispersion in the production of the above liquid developer.

6゛　　　A ni Resin dispersion of latex particle production example 2 days.

6′ B Resin dispersion of latex particle production example 29.

These liquid developers were processed using a fully automatic plate making machine ELP404V (
ELP Master ■ type (manufactured by Fuji Photo Film ■), which is an electrophotographic window light material, was exposed and developed by using it as a developer for Fuji Photo Film ■. The plate making speed was 7 plates/min. In addition, 3 types of ELP master ■
After processing 000 sheets, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image is 30%
This was done using the original manuscript. The results are shown in Table-4.

As is clear from the results in Table 4, when plates were made using each developer under severe forced plate-making conditions with extremely high plate-making speeds as described above, no staining of the developing device occurred, and 30%
The developer of the present invention was the only developer that produced a clear image on the 00th plate making plate.

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

As shown in the above results, when the resin particles of the present invention are used as a developer, the developing device is not contaminated at all, and
The number of printed master plates was also good.

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

The staining of the developing device on the day of the comparative example was dramatically improved compared to the case of comparative example A, but when the developing conditions became severe, satisfactory performance was still not achieved.
The known dispersion stabilizing resin of Comparative Example B has a component containing a polymerizable double bond group that copolymerizes with the monomer (A) [vinyl acetate in this example] contained in the polymer.
It is characterized by being a random copolymer in which the polymerizable double bond group is present in a portion close to the polymer main chain, and for this reason, the redispersibility of latex particles is inferior to that of the dispersion stabilizing resin of the present invention. It seems that it is.

Example 2 White resin dispersion 1 obtained in latex particle production example 1
A mixture of 00g and 1.5g 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-molecular weight nylon cloth to obtain a black resin dispersion with an average particle size of 0.25 m.

30g of the above black resin dispersion, 0 zirconium naphthenate
．． 05g, FOC-1600 (manufactured by Nissan Chemical ■) 2
A liquid developer was prepared by diluting 0g to 11 parts of Shersol 71.

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 occurred on the device.

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

Example 3 Production of Latex Particles A mixture of 100 g of the white resin dispersion obtained in Example 25 and 3 g of Victoria Blue B was heated to a temperature of 70''C to 80C 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 a blue resin dispersion with an average particle size of 0.25.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． 05g, FOC-1400 (made by Nissan Chemical ■) 15g
A liquid developer was prepared by diluting the solution to 11 of Isopar H.

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. 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.

Further, after this developer was left to stand for three months, the same treatment as above was performed, but there was no difference at all from before the aging.

Example 4 Poly(decyl methacrylate) Log, Isopar 83
0 g and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

White resin dispersion 3 obtained in latex particle production example 1
0 g, 4.2 g of the above alkali blue dispersion, 15 g of higher alcohol F OC-1400 (manufactured by Nissan Chemical ■), and 0.06 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride were diluted to Isopar G 12. A liquid developer was prepared by doing this.

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 5 to 21 In Example 4, the latex particles shown in Table 5 were used in place of the white resin dispersion of Production Example 1 of latex particles in an amount of 6.0 g as a solid content. A liquid developer was prepared in the same manner as in 4.

Table 5 Table 5 (Continued) When this was developed using the same device as in Example 1, 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.

(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 very clear.

Ko Procedural correction divination April 12, 1990

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 monofunctional monomer (A) that is soluble but becomes insolubilized by polymerization, and the following general formula (II)
At least one monomer (B) containing at least two polar groups and/or polar linking groups represented by
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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), T^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), V is -O-, -COO-, -OCO
-, -CH_2OCO-, -SO_2-, -CONH-
, -SO_2NH-, -CON-, or ▲Mathematical formula, chemical formula, table, etc.▼(W is a hydrocarbon group or general formula (I
I) Bonding group in: ▲Represents the same content as ▼, which includes mathematical formulas, chemical formulas, tables, etc.). Q is a hydrogen atom, a halogen atom, -OH, -CN,
-NH_2, -COOH, -SO_3H or -PO
_3 Represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with H_2. X_1 and X_2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2-, -OC, respectively
O-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -NHCO
_2- or -NHCONH- (Q_1, Q_2
, Q_3, Q_4 and Q_5 indicate the same contents as Q above). U_1 and U_2 may be the same or different from each other,
Each may be substituted, or ▲There is a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [X_3, X_4 are
may be the same or different from each other, and have the same contents as X_1 and X_2 above, U_4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and Q_4 has the same contents as Q above] Represents a hydrocarbon group having 1 to 18 carbon atoms. b_1 and b_2 may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -COO-R_1, or -COO-R_1 via a hydrocarbon (R_1 is a hydrogen atom or a hydrocarbon group that may be substituted). ). m, n and p may be the same or different, and each is 0 to 4
represents an integer.