JPH0445455A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain the liquid developer superior in dispersion stability and redispersibility and fixability by polymerizing a monofunctional monomer and a specified monomer contained in a solvent in the presence of a dispersion stabilizing resin specified in repeating units to form copolymer resin particles. CONSTITUTION:The monofunctional monomer to be insolubilized by polymeriza tion and the monomer represented by formula II both contained in the solvent are copolymerized in the presence of the dispersion stabilizing resin comprising the repeating units each represented by formula I and the repeating units each having an acid group, thus permitting the copolymer particles for use in the liquid developer to be obtained. In formulae I and II, V0 is -COO-, -OCO-, -(CH2)- or -O-; R0 is an aliphatic group; each of a1 and a2 is H, halogen, cyano a hydro carbon group, or -COO-D1; E<1> is an aliphatic group; U is -COO-, -CONH-, -CON-E<2>, -OCO-, -CH2COO-, or -O-; and each of e<1> and e<2> is H, alkyl, -COO-E<3>, or -CH2-COO-E<3>-.

Description

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

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

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

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble 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 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 is difficult to obtain a desired average particle size with monodispersed particles having a narrow particle size distribution, and large particles of 1 or more or very fine particles of 0.1 or less are formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components are used. A method for improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A No. 1797-1987 and No. 151-868-62. In addition, in the presence of a polymer using a bifunctional supermer or a polymer using a polymer reaction, an insoluble dispersion of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety can be used. A method for improving the dispersibility, redispersibility, and storage stability of particles by forming them into resin particles is disclosed in JP-A-60-185963.
No. 61-63855, etc.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing 5,000 or more sheets using a master plate for offset printing using an electrophotographic method has been attempted, and improvements in the master plate in particular have been progressing. It has become possible to print more than 10,000 sheets in plate size. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and 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. 62-15186
No. 8, No. 60-185963, and No. 61-63855, the dispersion resin particles manufactured according to the method disclosed in No. 8, No. 60-185963, and No. 61-63855 have a tendency to deteriorate when the particles are used for a long period of maintenance or when the development speed is increased. In terms of dispersibility and redispersibility, and in the case of large-sized master plates (for example, A-3 size or larger), particle dispersibility, redispersibility, and printing durability are still not necessarily satisfactory. It wasn't about performance.

This is especially true when trying to improve operability by extending the maintenance period of the plate-making machine, or when using a large-scale plate-making machine for large-size master plates without staining the developing device and making it possible to improve the quality of copied images. When trying to improve image quality, it has been a major challenge to improve the redispersibility of dispersed resin particles.

The present invention provides tJB of the conventional liquid developer as described above.
This is to solve the problem.

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 can speed up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in an electrophotographic engraving system using a large-sized master plate. 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, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. That's true.

(Means for Solving the Problems) The above-mentioned method is for electrostatic photography made by dispersing at least resin particles in a non-aqueous solvent having an electrical resistance of 10'Ωcm or more, or -'') and a dielectric constant of 3.5 or less. In the liquid developer, the dispersed resin particles include a block A containing at least a polymer component represented by the following general formula (I), a carboxyl group, a sulfo group, a hydrocoxyl group, a formyl group, an amine group, a phosphono group, and A polymer component containing at least one polar group selected from -P-Q, group (Q represents -Q, group or H represents -OQ, group, and Q represents hydrocarbon group); / or - block B consisting of a polymer component corresponding to the functional monomer (A), having a weight average molecular weight of 1X10' to 5X10' and soluble in the non-aqueous solvent; In the presence of a dispersion stabilizing resin made of a polymer, a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a monomer of the following general formula (II
), a monomer (B) containing an aliphatic group having 8 or more carbon atoms and copolymerizing with the monomer (A) through a polymerization reaction.
This was achieved by an electrostatic photographic liquid developer characterized by being copolymer resin particles obtained by polymerizing a solution containing at least one of the following.

General formula (I) +CH-C)-v. -Ro In formula (I), vo is -COO--0CO-1-(C)I
zhCOO-1- (represents CHz hOCO-1 or -〇- (l represents an integer from 1 to 3).

Ro represents an aliphatic group having 10 or more carbon atoms.

a and at may be the same or different, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO
-D+ or -C00-D+ (D+
represents a hydrogen atom or a hydrocarbon group which may be substituted.

General formula (II) e I' e 2 C) l=c -E In general formula (II), El represents an aliphatic group having 8 or more carbon atoms.

U is -C00-1-CON11-1-CON- (E" represents an aliphatic group), -0CO--CH2COO-1
Or represents -〇-.

e! , et may be the same or different, and each represents a hydrogen atom, an alkyl group, -COOE' or -CH, -COO
E' (El represents an aliphatic group).

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

The carrier liquid having an electrical resistance of 109ΩC 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 E,
Isopar G1 Isopar H1 Isopar L (Isopar: Exxon product name), Shellzol 70, Shellzol 71 (Shellzol; Shell Oil company product name)
, Amsco ○MS, Amsco 460 molasses (Amsco; a trade name of Spirinz Co., Ltd.), etc. are used alone or in combination.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are the dispersion stabilizing resin which is the A-B type block copolymer of the present invention in a non-aqueous solvent. In the presence of -functional monomer (
A) and a monomer CB containing an aliphatic group having 8 or more carbon atoms
It is manufactured by copolymerizing (so-called polymerization granulation method).

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

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic 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 solvent, etc. may be used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), Carboxylic acid esters (e.g. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons M (For example, 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 is within a range that satisfies the condition of 10<9 >[Omega]C- or more.

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

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 (If). , contains an aliphatic group having 8 or more carbon atoms, and contains a monomer (
They can be distinguished into monomers (A) and copolymerizable monomers (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, a monomer represented by the following general formula (I[l) may be mentioned.

General formula (Ill) b+ bz CH=C -R In formula (III), vl is -C00-1-0CO--CH
,0CO-2coxcoo-2-〇-1-CONHCO
O-1-CON)IOCO-1-SO□-1D2 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group,
Phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3
-methoxypropyl group, etc.).

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 L2゜2-dichloroethyl group, 2,2.2 -) IJ fluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group,
2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group, trimethoxysilylpropyl group, 3-bromopropyl group, 4
-Hydroxybutyl group, 2-furfurylethyl group, 2-
thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group,
2-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

b and b2 may be the same or different, and each represents the same content as a or R2 in the general formula (I).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. C1-C4 optionally substituted alkyl esters or amides of acids (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group) ,
Trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-henzenesulfonylethyl 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-human o-+cy3
-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); styrene derivatives (e.g., styrene, vinyltoluene , α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethylstyrene, vinyl benzenecarboxamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; acrylonitrile; methacriconitrile; polymerization Heterocyclic compounds containing a double bond group (specifically, for example,
"Polymer Data Handbook - Basic Edition", p175-1
84, compounds described in Baifukan (published in 1986), such as 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.

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

In general formula (II), preferably EI has a total carbon number of 1
0 or more optionally substituted alkyl groups or a total of 10 carbon atoms
represents the above alkenyl group, U is -COO-5CON
II-1-CON- (However, E8 preferably has 1 carbon number
~32 aliphatic groups (for example, aliphatic groups include alkyl groups, alkenyl groups, or aralkyl groups)
, -0CO--CHxOCO- or -0-.

el and e! may be the same or different, preferably a hydrogen atom, a methyl group, -COOE' or -CHzCOOE
3 (however, E3 preferably represents an alkyl group, an alkenyl group, an aralkyl group, or an alkyl group having 1 to 32 carbon atoms).

Furthermore, more preferably, in formula (II), U represents EI COO--CONH- or -CON-, el and C2 represent a hydrogen atom or a methyl group, which may be the same or different, and EI represents the above-mentioned It represents the same content as .

Specific examples of the monomer (B) represented by the above general formula (n) include aliphatic groups having a total of 10 to 32 carbon atoms, CMFi, halogen atoms, hydroxyl groups, amino groups, alkokene groups, etc. acrylic acid, methacrylic acid, crotonic acid, which may contain a substituent, or a carbon-carbon bond in its main chain may be mediated by a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom) , maleic acid, esters of unsaturated carboxylic acids such as itaconic acid (aliphatic groups such as decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, dodecenyl, hexadecenyl, oleyl) , lylyl group, tocosenyl group, etc.); Amide 1 of the aforementioned unsaturated carboxylic acid! (The aliphatic group represents the same thing as shown for esters); vinyl esters or allyl esters of higher fatty acids (higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid,
linoleic acid, behenic acid, etc.); or vinyl ethers substituted with an aliphatic group having a total of 10 to 32 carbon atoms (the aliphatic group represents the same range as the aliphatic group of the unsaturated carboxylic acid mentioned above), etc. I can do it.

The dispersion stabilizing resin used in the present invention is an AB type block copolymer, and one block (referred to as block A) is composed of a polymer component consisting of repeating units represented by general formula (I). and the other block (referred to as block B) is a polymer component containing at least one kind of polar group selected from the above-mentioned specific polar groups and/or the above-mentioned functional monomer (A). and has a weight average molecular weight of 1X10' to 5X
It is characterized by being 10'.

The abundance ratio of block A and block B in the A-B type block copolymer is 99/1 to 50150 (weight ratio)
It is preferable that

The specific polar group-containing polymer component contained in block B is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the dispersion stabilizing resin. Further, when a specific polar group-containing polymer component is not present in block B, the polymer component corresponding to the -functional monomer (A) is preferably 5 to 50 parts by weight based on 100 parts by weight of the resin. and more preferably 10 to 40 parts by weight.

The weight average molecular weight of the AB type block copolymer is preferably 2×10′ to 1×1O5.

The repeating unit represented by general formula (I) constituting block A will be explained in detail.

-C In formula (I), ν. is preferably -COO-1
Represents OCO- or -〇-.

Ro represents an alkyl group or alkenyl group having 10 or more carbon atoms, and these may be linear or branched.

Specific examples include decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, ryl group, etc. .

a and ag 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-or or -GHzCOO-D+ (D+ is a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (e.g., alkyl group, alkenyl group, aralkyl group, alicyclic group, aryl group, etc.) represents].

Specifically, Dl is a hydrogen atom, and preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 22 carbon atoms, I (for example, a methyl group, an ethyl group, a propyl group,
Butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl i, 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, -butenyl group, 2-pentenyl group, 3-mer J-71/2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2
-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, rilur group, etc.), carbon number 7-1
2 optionally substituted aralkyl groups (e.g., benzyl group, phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
bromobenzyl group, methylhensyl group, ethylhensyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group) , 2-cyclopentylethyl group, etc.), and an optionally substituted aromatic group having 6 to 12 carbon atoms (for example,
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butquincarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobusoylamidophenyl group, etc.) .

Further, in the block A of the dispersion stabilizing resin used in the present invention, other repeating units may be contained as copolymerization components together with the repeating unit represented by the general formula (I). As the other copolymerization component, any compound may be used as long as it consists of a monomer copolymerizable with the monomer corresponding to the repeating unit of general formula (I).

However, it is preferable not to contain other components, and the amount used does not exceed 1 part of 2 parts in block A at most. If it exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles will deteriorate.

In block A, two or more repeating units represented by general formula (I) may be used in combination.

Next, the polymer component constituting block B of the block copolymer of the present invention will be explained in detail.

Block B is composed of a polymer component corresponding to the -functional monomer (A) and/or a specific polar group-containing polymer component described above.

As the polymer component corresponding to the monofunctional monomer (A),
Examples of the monomer (A) to be insolubilized include those described above.

Preferably, a monofunctional monomer (A) that becomes dispersed resin particles
It is composed of the same monomer as.

In addition, in a specific polar group, -P-Q, Qo is Q
The hydrocarbon group of sQI, where Ql represents a hydrocarbon group having 1 to 10 carbon atoms, is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group, 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 (eg, 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 -NH,,1-1
It represents a hydrocarbon group of 0, preferably a hydrocarbon group having 1 to 7 carbon atoms, and specifically represents the same content as the hydrocarbon group of Ql described above.

Even more preferably, the hydrocarbon groups of Ql, D, and D include 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.

The monomer corresponding to the above specific polar group-containing polymer component may be any functional monomer containing at least one specific polar group. For example, it is described in the Polymer Science Society of Japan gr. Polymer Data Non-Doburi [Basic Edition] J Baifukan (published in 1986). in particular,
Acrylic acid, α- and/or β-substituted acrylic acid (e.g. “-acetoxy form, α-acetoxymethyl form, α-(2
amino) methyl form, α-chloro form, α-bromo form, α-
Fluoro body, α-tributylsilyl body, α-777 body, β
-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides,
Crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid , maleic acid half esters,
Half-ester derivatives of vinyl or allyl groups of maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, and dicarboxylic acids, and ester derivatives and amide derivatives of these carboxylic acids or sulfonic acids. Examples include compounds containing the polar group in the substituent.

Specific examples of these compounds include the following. However, on each side below, e is -H1-C
M,, -CI, -Br, -CN, -CH,COOCH
3 or CH,C00)I, r is -H or -CH3
, n is an integer from 2 to 1O, and -1 is from 1 to 10.
represents an integer of 1 to 4, and 1 represents an integer of 1 to 4. Xl is -Co
ol, -0-P-OH1H (R, represents an alkyl group of CI-a).

xl represents -COOH or -OH.

C)1. =C 0OH CH.

CH=C1(coot+coz=c COO(CHz)ri-i-L CH,,C C0NH(CHaYcutL cut,c C00(CH2)Ti-OCO(CH2)-ri-xl
Clh,C C0NH(CHz)Ti-0CO(C1h)17-x
lCL=C CONHCOO(CHa■璽L cut=c CONICONH(CH,)-fi-X.

cnz=c CONHCHCH, C00FI cutcoon C)1. ,,C Coo(CH2)ri-NHco(CH2)-t+7-
X (-1 may be the same or different) cnz=c CONH(CHz)r-NHCOO(CHz)Ti-X
+CH2CH2 CHt=C H COOCHzCHCHz(C)Iz)v7- XCH2
=C CI(2=C COO(CHz)Ti-CON-(CH2CH2X2
)2 The AB type block copolymer of the present invention can be produced by a conventionally known polymerization reaction method.

Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is previously protected as a functional group, and an organometallic compound (for example, alkyl lithiums, lithium diisopropylamide, alkyl magnesium A-B type block copolymers are produced by known so-called living polymerization reactions such as halides, etc.) or ionic polymerization reactions using hydrogen iodide/iodine systems, photopolymerization reactions using porphyrin metal complexes as catalysts, or group transfer polymerization reactions. After synthesizing, the functional group with a protected polar group is deprotected by hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, photolysis reaction, etc. to form a polar group. One example is shown in the reaction scheme below (
I).

(Left below) For example, P, Lutz, P, Masson et
al, Polym.

Bull,, 14. 79 (I984), B
, C., Anderson, G., D.

Andrews et al, Macrosole
cules+ L4+ 1601 (I981),
K, Flatada, K, Ute+
et al. Polym, J., L.

977 (I985), 1fi, 1037 (I9
86), Hiroshi Miguchi - 1 Ko Hatada - "Polymer processing" plate, 36
6 (I9B?), Toshinobu Higashimura, Mitsuo Sawamoto "Collection of Polymer Papers", 189 (I989), HlKuroki,
'r, Aida, J, Am, Che
w, Soc, + -1 engineering Lσ+4737 (I9
87), Takuzo Aida, Shohei Inoue “Organic Synthetic Chemistry J 4.1
．． 300 (I985), D, Y, Sogah,
L R.

Fletler et al, Macrowole
It is easily synthesized according to the synthesis method described in eg.

Another method for synthesizing A-B type block copolymers is the photoiniferter polymerization method using a monomer with its polar group unprotected and using a dithiocarbament compound as an initiator. .

For example, Yokiyuki Otsu's "polymer" nail, 24B (I988
), Shun Himori-1 Takashi Otsu-5 Polym, Rep, J
ap, , , II, 3508 (I988), JP-A-6
It is synthesized according to the synthesis method described in No. 4-111, JP-A No. 1-26619, etc.

In addition, the protecting group that protects the specific polar group of the present invention and the removal (deprotection reaction) of the protecting group can be easily carried out using conventionally known knowledge. There are various descriptions in ``Reactive Polymers'' by Takao Iwakura and Keisuke Kurita, published by Kodansha (1977).
,T,! 1. Green+rProtecti
ve Groups in Organic 5ynt
hesis” + John Wiley & 5ons
(I981), J, F, H, McOmie+rPr
otective Groups in Org
anic ChemistryJ.

The method described in detail in the review of PIenu* Press, (1973) etc. can be suitably selected and carried out.

The dispersion resin of the present invention consists 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 there is,
A desired dispersed resin can be obtained. More specifically,
It is preferable to use 0.1 to 20% of the monomer (B) represented by the general formula (I[) based on the monomer (A) to be insolubilized, more preferably 0.3 to 8%. Weight%. Further, the molecular weight of the dispersion resin of the present invention is preferably 103 to 1.
06, more preferably 10' to 106.

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 non-aqueous 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 3 to 20 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. It has good dispersibility and is easy to re-disperse even if the development speed is increased, and no stains are observed on various parts of the device.

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

Furthermore, the liquid developer of the present invention has excellent dispersion stability, redispersibility, and fixing properties even when the development and fixation process is accelerated and the maintenance interval is extended for a long time.

In particular, JP-A-60-185963 or JP-A-61
In the non-aqueous dispersion resin described in No. 63855, the total number of atoms from the main chain of the polymer is 8. Resin particles (latex particles) are polymerized and granulated using a random copolymer soluble in the non-aqueous solvent, which contains a copolymer component with a polymerizable double bond group bonded to a site separated by at least 10 minutes, as a dispersion stabilizing resin. ), the dispersibility and printing durability of these particles have been greatly improved compared to conventional particles, but plate making machines using large-size offset printing master plates (e.g. Fuji Photo If the processing speed of the plate making machine is increased, there is still a problem with the dispersibility of the particles, and the plate making machine becomes dirty (particularly the developing device gets dirty). or agglomeration/sedimentation of particles occurred, or when the master plate was stamped, the strength of the image area was still insufficient and the rigidity resistance decreased. When the resin particles provided by the present invention are used, no problems occur even under such severe conditions.

As described above, the high redispersibility of the latex particles of the present invention is due to
It depends on the soluble A-B type block copolymer used together with the monomer (A) to be insolubilized and the monomer (B) having an aliphatic group having 8 or more carbon atoms.

That is, the dispersion stabilizing resin of the present invention consists of a block A composed of a polymer component containing a long-chain aliphatic group that has a high affinity for the non-aqueous solvent, and a monomer that has a low affinity for the non-aqueous solvent and makes it insolubilizable. It is characterized by being an A-B type block copolymer in which a block B composed of a polymer component having an affinity for the polymer (A) is bonded.

As a result, the block 8 portion is sufficiently adsorbed to the dispersed resin particles through physicochemical interaction during polymerization and granulation, and the block A portion, which has a high affinity for the non-aqueous dispersion medium, is adsorbed to the solvent. It is presumed that the effects of the present invention have been achieved because it is possible to sufficiently solvate and to have a sufficient steric repulsion effect (so-called tail-like adsorption).

On the other hand, in the conventionally known random copolymer of the polymer component used in block A and the polymer component used in block B, the adsorption part is in the polymer chain composed of the solvated component. Because it is randomly combined with
Adsorption to the dispersed resin particles was not sufficient, and furthermore, the pattern of adsorption was loop-like, so the steric repulsion effect was also negated, resulting in insufficient dispersion stability.

In addition, high printing durability that does not cause deterioration of the toner image area when printed as an offset master original plate is achieved by using an insolubilizing monomer (A) and a monomer having an aliphatic group having 8 or more carbon atoms (B).
It is presumed that this is achieved by the copolymer with the copolymer and the dispersed polymer adsorbed on it having good compatibility with each other and being sufficiently compatible even under mild fixing conditions to form a uniform and strong film. Ru.

A coloring agent may be used in the liquid developer of the present invention 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 blank, nigrosine, alkali blue, Hanzaiero, quinacridone red, and phthalocyanine blue.

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

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

Examples include EVA, di-2-ethylhexyl sulfosuccinic 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 coloring 1f1) are preferably 0.5 parts by weight to 50 parts by weight based on 1000 parts by weight of the carrier liquid, and if it is less than 0.5 parts by weight, the image density increases. If the amount exceeds 50 parts by weight, fogging tends to occur in non-image areas.Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization is also used if desired, and the amount is 0.5 parts by weight per 1000 parts by weight of the carrier liquid. About 100 parts by weight can be added.

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on 1000 parts by weight of the carrier liquid.Additionally, various additives may be added as desired. Its upper limit is regulated by the electrical resistance of That is, if the electrical resistance of the liquid developer with toner particles removed becomes lower than 109 ΩC-, 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. is necessary.

(Example) Synthesis examples of dispersion stabilizing resins, production examples of latex particles, and examples according to the present invention are illustrated below, but the content of the present invention is not limited thereto.

-○mu:P- A mixed solution of 95 g of dodenyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, and -7
Cooled to 8°C. I,I-diphenylbutyllithium 1
．． 0 g was added and reacted for 12 hours. Furthermore, a mixed solution of 5 g of triphenylmethyl methacrylate and 25 g of tetrahydrofuran was added to this mixed solution after sufficient degassing under a nitrogen stream, and the mixture was reacted for further 8 hours. This mixture is o'
After the temperature was reduced to c, 10 d of methanol was added and the reaction was carried out for 30 minutes to terminate the polymerization. The resulting polymer solution was brought to a temperature of 30"C with stirring, and 15af of 30% hydrogen chloride ethanol solution was added thereto and stirred for 1 hour. Next, the solvent was removed from the reaction mixture under reduced pressure until the total volume was reduced to half. After distilling off, it was reprecipitated in methanol 1! The precipitate was collected and dried under reduced pressure, and the resulting polymer had a weight average molecular weight of 4.5 x 1.
The yield at 0' was 70 g.

CH ko 　　　　CH.

ACH! -C) yr-b ACHt -C (weight ratio) C00C+tHzs C00H b indicates a block bond (the same applies below).

No.: P A mixed solution of 46 g of octadecyl methacrylate, 0.5 g of aluminum methyl (tetraphenylborufinate) and 60 g of methylene chloride was heated at 30''C under a nitrogen stream.
And so. This was irradiated with 300 W-xenon lamp light from a distance of 25 cm through a glass filter, and 12
Time reacted. After further adding 4 g of benzyl methacrylate to this mixture and irradiating it with light for 8 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction.Next, Pd-C was added to this reaction mixture. A catalytic reduction reaction was carried out at a temperature of 25°C for 1 hour.

After filtering off insoluble matter, it was reprecipitated in methanol 50 (IMi), and the precipitate was collected and dried. The obtained polymer had a yield of 3.
At 3g! It was the quantum equimolecular molecule f3XIO'.

P-2 A mixed solution of 90 g of CB 3 CH 3 tridecyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream,
Cooled to -78°C. 0.8 g of 1.1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Furthermore, 10 g of 4-vinylphenyloxytrimethylsilane was added to this mixture and stirred for 6 hours, and then 3 g of methanol was added and stirred for 30 minutes.

Next, add 1 part of 30% hydrogen chloride ethanol solution to this reaction mixture.
After stirring at 25°C for 1 hour, methanol l
The precipitate was collected. The precipitate was washed twice with 300ml of methanol and dried. The obtained polymer had a yield of 58 g and a weight average molecular weight of 3.5 x 104.

Hx Hexadecyl methacrylate 95g, benzyl N, N-
A mixture of 2.0 g of diethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 60°C. This was irradiated with light for 10 hours using a 400 W high-pressure mercury lamp from a distance of 10 cm through a glass filter for photopolymerization. Add to this 5 g of acrylic acid and 11,110 g of methyl ethyl ketone.
After adding , the atmosphere was replaced with nitrogen and light was irradiated again for 10 hours.

The resulting reaction mixture was reprecipitated in 1.5 ml of methanol, collected, and dried. The resulting polymer had a yield of 68 g and a weight average molecular weight of 4 x 10'.

I13 @ CHt -C)-vT-b -1-(CHt -C
H) rCOOC+Jss(n) A of C0OH
5: P- A mixed solution of 80 g of stearyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream, and -
It was cooled to 78"C. 1.0 g of 1.1-diphenyl-3-methylpentyl potassium was added and stirred for 10 hours. Furthermore, 20 g of styrene was added to this mixture and stirred for 8 hours, and the reaction mixture was converted to O"C. Next, this was reprecipitated in methanol 1.51, the precipitate was collected by filtration, and the resulting polymer was dried, yielding 68 g.
The weight average molecular weight was 3 x 10'.

CH)--Cus:D-1 15g of dispersion stabilizing resin P-1, 100g of vinyl acetate,
Octadecyl methacrylate 1.0g and Isopar H
A mixed solution of 4 g of 3B was heated to a temperature of 70°C while stirring under a nitrogen stream.
Warmed to °C. Add 0.8 g of 2,2'-azobis(isovaleronitrile) (abbreviation A, 1.V, N,) and add 6
Time reacted. 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, 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 90% and an average particle size of 0.24.

2 to 4: D-2 to D latex particles In Production Example 1, the same procedure as Production Example 1 was carried out, except that the dispersion stabilizing resin P-1 was replaced with each resin in Table 1 below.
Each Latinx particle D-2 to D-4 was manufactured.

In production example 1 of surface latex particles, dispersion stabilizing resin P
Latex particles D-5 to D-9 were produced in the same manner as in Production Example 1, except that -1 was replaced with each resin shown in Table 2 below. The polymerization rate of each latex was 83 to 88%.

(Margin below) ---S's θ~ 5: D-10~D-
5 In the production example of latex particles D-1, 0 each of the monomers in Table 3 was added instead of 1 g of octadecyl methacrylate.
．． Each latex particle was produced in the same manner as Production Example 1 except that 8 g was used.

(Left below) ---S 6: 10g of D-16 dispersion stabilizing resin-10, poly(octadecyl methacrylate)
)), 100 g of vinyl acetate, 0.8 g of tridecyl methacrylate), and 400 g of Isopar H were heated to 75° C. with stirring under a nitrogen stream. 2.2
'-azobis(isobutylnitrile) (abbreviation ^, 1.B
, N, ) 0.7 g was added and reacted for 4 hours, and then A, 1
．． 0.5g of B and N were added and reacted for 2 hours. After cooling 2
The white dispersion obtained through the 0.00 mesh nylon cloth was a latex with an average particle size of 0.20-.

--S 1:D-1 14g of dispersion stabilizing resin P-11 with the following structure, 90g of vinyl acetate, N
- A mixed solution of 10 g of vinylpyrrolidone, 1.5 g of octadecyl methacrylate, 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. 20 minutes after cooling
The white dispersion obtained through the 0 mesh nylon cloth was a latex with an average particle size of 0.25-.

H3 weight average molecular weight: 7 XIO' m-x 18:D-18 A mixed solution of 16 g of dispersion stabilizing resin-4, 94 g of vinyl acetate, 6 g of crotonic acid, 2 g of hexadecyl methacrylate, and Aituba-G was prepared under a nitrogen stream. Temperature 6 while stirring
Warmed to 0°C. A.1. V, N, 1. Og addition 2
Time reacted. Furthermore, add 0.5 g of A, lν, N, and make 2
Time reacted. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.24a.

M-X 9: D-19 25g of dispersion stabilizing resin-7, methyl methacrylate)
A mixed solution of 100 g of dodecyl acrylate, 2 g of n-dodecyl mercaptan, 0.8 g of n-dodecyl mercaptan, and 688 g of Isopar H was heated to 60° C. with stirring under a nitrogen stream. A.1. 0.7g of V and N were added and reacted for 4 hours.

After cooling, the resulting white dispersion was passed through 200 meshes of nylon cloth and was a latex with an average particle size of 0.254.

A mixed solution of 20 g of dispersion stabilizing resin P-12 having the following structure, 100 g of styrene, 2 g of octadecyl vinyl ether, and 380 g of Isopar H was heated to 45° C. with stirring under a nitrogen stream. 1.0g of n-butyllithium hexane solution as solid amount of n-butyllithium
The following amount was added and reacted for 4 hours.

After cooling, the resulting white dispersion was passed through 200 meshes of nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.28 microns.

CH.

Weight average molecular weight: 8 XIO's: D A mixed solution of 20 g of dispersion stabilizing resin P-13 having the following structure and 470 g of n-dodecane was heated to 60° C. while stirring under a nitrogen stream. In this solution, add 100 g of methyl methacrylate and 71 g of n-dodecyl merca. Og
and A, 1. V, N, 0.8g (7) mixed solution, 2
It dripped in time. After 2 hours of reaction, A.1. V,
0.3 g of N was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.25.

CHl @ CHz -CH) w-II-b --iCHz -
Chl-COOC+ 5lby C00CI
(Weight average molecular weight: 6 was heated to a temperature of 70°C while stirring under a nitrogen stream. 0.8 g of A, 1.V, N, was added and reacted for 6 hours,
The temperature was raised to 100°C and the mixture was stirred for 1 hour to distill off the remaining vinyl acetate. After cooling, coarse particles were removed through a 200 mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.24 aw.

CH, C11゜-(CHz-C)Irr-b-□CH-CHtoC00C
+thHss C0OH weight average molecular weight:
3.3X10'-1x23:D-23 14g of dispersion stabilizing resin P-15 having the following structure, 100g of vinyl acetate, 4
- A mixed solution of 6.0 g of pentenoic acid and 380 g of Isopar G was heated to a temperature of 75° C. while stirring under a nitrogen stream. A.1. 0.7g of V and N were added and reacted for 4 hours. 0.5 g of V and N were added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had an average particle size of 0.23.
- latex.

COOCldhw OCOCH3OH Weight average molecular weight: 3.0 x 10'-24: A) In production example 1 of latex particles D-1, 20 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate and 38 g of Isopar H
The procedure was repeated in the same manner as in Production Example 1, except that 5 g of the mixed solution was used.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.20.
- latex. (Unexamined Japanese Patent Publication No. 60-179751
B) In production example 1 of latex particles D-1, 10 g of dispersion stabilizing resin R-1 having the following structure, 100 g of vinyl acetate, and a monomer ( The procedure was carried out in the same manner as in Production Example I, except that a mixed solution of 1 g of I) and 385 g of Isopar H was used.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.24.
- latex. (Latex particles described in JP-A-61-63855) Monomer (I) CHz cnz=c Coo(C1lt)zOcOcJ+*(n) Resin for dispersion stabilization: R-1 -fCH*-C)vy--HCHz -Ch-COOC+
5Hst C00(CHz)zOco(CHz)i
cOOctlzcH-Cut (weight composition ratio) Example 1 Dodecyl methacrylate/acrylic acid (copolymerization ratio: 95
15 weight ratio) copolymer, 10 g of nigrosine, and 30 g of Schersol 71 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30 g of the resin dispersion of latex particle production example 1, 2.5 g of the above nigrosine mat, 15 g of FOC-1400 (manufactured by Nichikagaku ■, tetradecyl alcohol), 0 of [octadecene-half-maleic acid octadecylamide copolymer]
．． A liquid developer for electrostatography was prepared by diluting 08 g of Shersol 71 to 11.

-B In the above production example, two types of liquid developers A and B were prepared for comparison by replacing the resin dispersion with the following resin particles.

Comparative liquid developer A Resin dispersion of Nilatex particle production example 24 Comparative liquid developer B Resin dispersion of Nilatex particle production example 25 These liquid developers were processed using a fully automatic plate making machine ELP560 (Fuji Photo Film ■ E, an electrophotographic photosensitive material, is used as a developer for
LP Master ■ type (manufactured by Fuji Photo Film ■) was exposed and developed.

The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original.

Display the results 4.

(The following margins) When plate making was carried out using each developer under the above-mentioned plate making conditions, the developer of the present invention did not cause staining of the developing device and the image on the 2000th plate making plate was clear. Ta.

On the other hand, an offset 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 the printed image showed missing characters, fading in solid areas, etc. However, with the master plates obtained using the developer of the present invention, the problem did not occur even after 100 sheets or more, and with the master plates using Comparative Examples A and B, the problem occurred after about 500 sheets.

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.

In addition, in the case of Comparative Example A and Comparative Example B, the plate-making conditions are harsh (conventionally, the blackening rate of the copied image is about 8-10% at a plate-making speed of 2 to 3 sheets/min). This results in dirt on the developing device (especially on the back electrode plate), and 2
After 1,000 copies, the image quality of the copied image on the plate began to be affected (decreased Dsax, blurring of thin lines, etc.).

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 and Sumikaron black was heated to 10 g.
The mixture was heated to 0°C and stirred for 4 hours. After cooling to room temperature 20
A black resin dispersion with an average particle size of 0.24 was obtained by removing the remaining dye by passing it through a 0 mesh nylon cloth.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 20 g of FOC-1600 (manufactured by Nissan Chemical Company, hexadecyl alcohol) to 12 of Shersol 71.

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

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

Example 3 White dispersion 10 obtained in latex particle production example 22
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 it through a 0.00 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.23.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． 05g of Isopar H in 11. A liquid developer was prepared by diluting it to .

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

Example 4 32 g of white resin dispersion obtained in latex particle production example 6
, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-
1400 (manufactured by Nissan Chemical ■, tetradecyl alcohol) 2
0 g and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 1
A liquid developer was prepared by diluting the solution to 1:1.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after single-sheet printing were 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 5 Poly (decyl methacrylate) Log, 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.

White resin dispersion D obtained in latex particle production example 5
30g of -5, 4.2g of the above alkali blue rug,
15 g of isostearyl alcohol and 0 semi-docosanylamidated copolymer of diisobutylene and maleic anhydride
．． 06 g to 1 of Isopar C! A liquid developer was prepared by diluting it to .

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

Examples 6 to 11 Liquid developers were prepared in the same manner as in Example 5, except that each latex shown in Table 5 below was used in place of latex particles D-5.

Table 5 When this was developed using the same device as in Example 1, 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

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

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.

(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, and both the image quality of the obtained offset printing master plate and the image quality of the printed matter after single-sheet printing are very clear. Ta.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least resin particles dispersed in a nonaqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, the dispersed resin particles comprising: Block A containing at least a polymer component represented by the following general formula (I), carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and ▲ mathematical formula, chemical formula, table, etc. ▼ group (Q_0 is -
Q_1 group or -OQ_1 group, Q_1 represents a hydrocarbon group] and/or a polymer component corresponding to the monofunctional monomer (A) In the presence of a dispersion stabilizing resin consisting of block B consisting of A-B type block copolymer having a weight average molecular weight of 1 x 10^4 to 5 x 10^5 and soluble in the non-aqueous solvent. , a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and the following general formula (II)
A solution containing at least one monomer (B) which contains an aliphatic group having 8 or more carbon atoms and copolymerizes with the monomer (A) in a polymerization reaction is subjected to a polymerization reaction. 1. A liquid developer for electrostatic photography, characterized in that it is copolymer resin particles obtained by General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), V_0 is -COO-, -OCO-, ■C
H_2■_lCOO-, ■CH_2■_lOCO-, or -O- (l represents an integer from 1 to 3). R_0 represents an aliphatic group having 10 or more carbon atoms. a_1 and a_2 may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-D_1 or -COO-D_1 via a hydrocarbon group
(D_1 represents a hydrogen atom or a hydrocarbon group that may be substituted). General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In general formula (II), E^1 represents an aliphatic group having 8 or more carbon atoms. U is -COO-, -CONH-, ▲Mathematical formula, chemical formula, table, etc.▼(E^2 represents an aliphatic group), -OCO
-, -CH_2COO-, or -O-. e^1 and e^2 may be the same or different, and each represents a hydrogen atom, an alkyl group, -COOE^3 or -CH_2
-COOE^3 (E^3 represents an aliphatic group).