JPH03225353A - Liquid developer for electrostaticphotography - Google Patents

Abstract

PURPOSE:To obtain the developer having excellent dispersion stability and fixability by constituting dispersing resin particles of a block A contg. a monofunctional monomer and the polymer component expressed by specific formula and a block B consisting of a polymer component selected from a carboxyl group, sulfo group, etc. CONSTITUTION:The block A contains the monofunctional monomer (A) which is soluble in a nonaq. solvent but is insolubilized therein when polymerized and the polymer component expressed by the formula I. The block B consists of the polymer component contg. at least one kind of the polar group selected from a carboxyl group, sulfo group, hydroxyl group, formyl group, etc., and/or the polymer component corresponding to the monofunctional monomer (A). The resin particles are the polymer resin particles which are constituted of the blocks A, B and are obtd. by bringing a soln. contg. respectively one kind of the resins for stabilizing dispersion consisting of the A-B type block copolymers having 1X10<4> to 1X10<5> weight average mol. wt. and the solubility in the nonaq. solvent into a polymn. reaction. Distinct image quality is obtd. by this developing soln.

Description

Detailed Description of the Invention (Industrial Field of 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'ΩC1m or more and a dielectric constant of 3.5 or less. In particular, it relates to a liquid developer with excellent redispersibility, storage stability, stability, image reproducibility, and fixing properties.

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

In such 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 an insoluble latex are dispersed. Due to insufficient bonding with the particles, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. 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 dispersity, redispersibility, and storage stability of particles by
It is disclosed in No. 62-151868 and the like. In addition, a monomer that becomes insolubilized in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction,
By forming insoluble dispersed resin particles of a copolymer with a monomer containing a long-chain alkyl moiety, the degree of dispersion, redispersibility,
A method for improving storage stability is disclosed in JP-A-62-16636.
No. 2, No. 63-66567, 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.

JP-A-60-179751 and JP-A No. 62-15186
8, No. 62-166362, and No. 63-66567, the dispersion resin particles produced according to the means disclosed in No. 8, No. 62-166362, and No. 63-66567 have problems in terms of particle dispersibility, redispersibility, and fixation when the development speed increases. In the case where the time is shortened or in the case of a mask-plate of large size (for example, A-3 size or larger), the performance is still not necessarily satisfactory in terms of rigidity resistance.

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 can speed up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in an electrophotolithography system using a large-sized master plate. That's true.

Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of offset printing masters 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 liquid developer for electrostatic photography is formed by dispersing at least resin particles in a non-aqueous solvent having an electrical resistance of 10 drops Ωcm or more and a dielectric constant of 3.5 or less. In the above, the dispersed resin particles contain: (1) a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization; and (2) a monomer having the following general formula (1).
), a block A containing at least a polymer component represented by
group or H represents -OQ, a group, and Ql represents a hydrocarbon group] corresponds to a polymer component containing at least one polar group and/or the -functional monomer (A) block B consisting of a polymer component, and at least one type of dispersion stabilizing resin each consisting of an A-B type block copolymer having a weight average molecular weight of 1X10' to 5X10' and soluble in the non-aqueous solvent; This was achieved by an electrostatic photographic liquid developer characterized by polymer resin particles obtained by polymerizing a solution containing the same.

General formula (1) % formula %) In formula (1), vo is 1000--0CO-2-(CHt
hCOO-1-4C11,) represents tOCO-1 or -0- (l represents an integer from 1 to 3).

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

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

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

The carrier liquid having an electrical resistance of 10"ΩCm or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon; These halogen substitutes can be used.For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isopar E1
Isopar G, Isopar H, Isopar L (Isopar: Exxon product name), Shellzol 70, Shellzol 71 (Shellzol; Shell Oil company product name)
, Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirinz), 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 (
It is produced by polymerizing A) (so-called polymerization granulation method).

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

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic carbons. Examples include hydrogen and halogen-substituted products thereof. For example, hexane, octane, isooctane,
Decane, Isodecane, Decalin, Nonane, Dodecane, Isododecane, Isopar E1 Isopar G1 Isopar H, Isopart 1 Schiersolf 0. Ciel Sol 7
1. Use Amsco OMS, Amsco 460 solvent, etc. or in combination.

Alcohol 1! is a solvent that can be used in combination with these organic solvents. (e.g. methyl alcohol,
ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketone I! (e.g. acetone, methyl ethyl ketone, cyclohexanone, etc.), carboxylic acid esters (e.g. methyl acetate, ethyl acetate,
propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. methylene dichloride, chloroform, carbon tetrachloride, dichloroethane) , methyl chloroform, etc.).

It is preferable that the non-aqueous solvent used in the mixture be removed by heating or distillation under reduced pressure after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, it will not affect the liquid in the developer. There is no problem as long as the resistance is within a range that satisfies the condition of 109ΩclI 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 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 bottom (U) below may be mentioned.

General formula (n) b+ bt CH=C V+ R+ In formula (n), V is -COO-1-0CO--CHzO
CO-1CLC00-1-0-1-CON)IC00-
1-C011+10CO-1-3Oz-1Dχ
Dt Dt is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group,
Butyl group, 2-chloroethyl L2-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 group, 2゜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 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-carboxybrobyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-carboxyamidoethyl group, 3-sulfoamidopropyl group group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group (11).

bl and b2 may be the same or different, and each represents the same content as al or a2 in the above-mentioned boat formula (1).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, acetic acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Acid C1-4 optionally substituted alkyl esters or amides M (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-benzenesulfonylethyl group, 2-(N,N-dimethyl amino)ethyl group, 2-(N,N-diethylamino)ethyl group, 2
-Carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2carboxyamidoethyl group, etc.);
Styrene derivatives (e.g. Eva, styrene, vinyltoluene,
α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dimethylaminomethylstyrene,
(vinylbenzenecarboxamide, vinylbenzene sulfamide, 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: Heterocyclic compounds containing a polymerizable double bond group (specifically, for example, edited by The Society of Polymer Science [Polymer Data Handbook - Basic Edition], p. 175-184,
Compounds described in Baifukan (1986), for example, N-
vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

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

The dispersion stabilizing resin used in the present invention is an A-B type block copolymer, and one block (referred to as block A) is composed of a polymer component consisting of a repeating unit indicated by -bottom (1). 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 proportion of block A and block B in the block copolymer is preferably 99/l to 50,150 (weight ratio).

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 2X10' to 1X10'.

The repeating unit represented by the general formula (1) constituting block A will be explained in detail.

- in the bottom (1), V is preferably -000-1
Represents 0CO- 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 a 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 Flohir 15, etc.),
-COO-D, or -C1 (tcOo-D+ CD+ 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) (e.g., groups);

Specifically, in addition to a hydrogen atom, D is a preferable hydrocarbon group such as an optionally W-substituted alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a 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 group, 2-bromoethyl group, 2cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl groups having 4 to 18 carbon atoms (for example, 2-methyl-1-propenyl group, 2-butenyl group) , 2-pentenyl group, 3-methyl 2-pentenyl group, 1-pentenyl group, 1-hexeny/L'L 2-hexenyl!, 4-J thyl-2hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, rillyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. benzyl group,
Phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group, methylbenzyl group, ethylbenzyl group,
methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), An optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group,
Dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxy carbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

In addition, in block A of the dispersion stabilizing resin provided in the present invention, other repeating units may be contained as copolymerization components together with the repeating unit represented by general formula (1). , any compound may be used as long as it is made of a monomer copolymerizable with the monomer corresponding to the repeating unit of the bottom (1).

However, it is preferable not to contain other components, and the amount used does not exceed 20 parts by weight 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 types of repeating units indicated by -bottom (1) 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.

Also, among the specific polar groups, in the P-Qo group, Q is 0
H Q1 group or -〇〇, represents a group, and the mouth has 1 to 10 carbon atoms
represents a hydrocarbon group. The hydrocarbon group for Ql is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group). (2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.),
or an aromatic group that may be substituted (e.g. phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group,
bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Moreover, among the polar groups of the present invention, the amino group is -NO,,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 Q above.

Even more preferably, the hydrocarbon group of Qls as and 04 is an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted Hensyl group, or an optionally substituted phenyl group.

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 "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science and Technology, Baifukan (published in 1986). in particular,
Acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoxy form, α-acetoxymethyl form, α-(2
amino) methyl form, α-chloro form, α-bromo form, α-
Fluoro body, α-tributylsilyl body, α-cyano 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-2octenoic acid, etc.), maleic acid, Half ester derivatives of vinyl or allyl groups of maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids, and these carboxylic acids or sulfonic acids Examples include compounds containing the polar group in the substituent of ester derivatives and amide derivatives.

Specific examples of these compounds include the following. However, on each side below, e is -H1-C
H5, -CI, -Br, -CN, -CIlzCOOC
Indicates Hi or cutcoon, f is -H or -CH,
, nl is an integer from 2 to 10, and 111 is from 1 to 1.
It represents an integer of 0, and 11H represents an integer of 1 to 4. xl is -COOII, -0-
P-O)1,1OH (R5 represents a C34 alkyl group).

X, is C0OH or OH represents.

(1) cot=coon (2) OH3 CH=CH COO)! (3) CH2=C Coo((Jh)rr7 xi (4) 6-mouth 2=C CONH(CH0f璽X+ (6) f (7) CH1=C Coo (reject CH rOCO(Cl z'hiT-X
+(8) co,,c CONH(CHt)77-OCO(C1(z)17-X
+(9) CHg=C C0NHCOO(CL)VIT-X+ (10) CHg=C CON)ICONH(C1h')-F-VX+(11) (12) CH,,,,C C0NHCHCHzCOOH cuzcoon (13) (CHg =C COO(CHg>1i-7NHCO(CHJr7
+ (m+ may be the same or different) (14) cnz=c CONH(CHt)TNHCOO(CHz') TVL(
15) CHg=C)I-CHtOCO(CHg)r7-L(
16) CH,=CH COOC)1. CHC)It(Cud-r7-X+(1
8) (20) CH2=C C00(CHz)-i-i-CONOCOzCHz-X
z)z 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 (
Shown in 1).

(Margin below) Reaction scheme (1) CH3 CH3 CH3 R: b: (JI3 0OCHs 0OCR3 (ii) Termination reaction alkyl group, porphyrin ring residue etc.

: Protecting group, e.g. C(CJS)s, 5t(CJt)i etc.

Shows block binding.

For example, P. Lutz, P. Masson et.
al+ Polym.

Bull,, 12. 79 (1984), B
, C., Anderson, G., D.

Andrews et al, Macroso
lecules+ 14+ 1601 (198
1), K, Hatada+ K, Ute+
et al+ Polym, J-I 1.

977 (1985), 1fi, 1037 (19
86), Hiroshi Miguchi - 1 Ko Hatada - "Polymer processing" parallel, 36
6 (1987), Toshinobu Higashimura, Mitsuo Sawamoto [Kobunshi Paper Collection J 46.189 (1989), Mon.

Kuroki, T., Aida, J., Am, C.
hell, 5oc-+ 109+4737(198
7), Takuzo Aida, Shohei Inoue “Organic Synthetic Chemistry J 43.3
00 (1985), D. Y., Sogah, W.
R.

Hertler et al., Macromolec
It is easily synthesized according to the synthesis method described in Ules+ 20+ 1473 (1987) and others.

Another method for synthesizing A-B type block copolymers is the photoiniferter polymerization method using monomers with unprotected polar groups and a disiocarhament compound as an initiator. can.

For example, Takayuki Otsu "Polymer" Nail, 248 (198B
), Shun Himori-1 Takashi Otsu-1 Po1y+w, Rep,
Jap, 3J-, 3508 (198B), Japanese Patent Publication No. 6
It is synthesized according to the synthesis method described in No. 4-111, JP-A No. 1-26619, etc.

Furthermore, 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. For example, there are various descriptions in the above-mentioned cited literature, and furthermore, Giyu Iwakura and Keisuke Kurita, "Reactive Polymers J" published by Kodansha (1977)
, T, L Greene+rProtective
Groups in Organic 5ynthe
sisJ.

John Wiley & 5ons (1981)
, J., F., H., McOmie.

rProtective Groups in Org
anic Chemistry” Plenum Pre
The method described in detail in reviews such as ss+ (1973) can be appropriately selected and carried out.

To produce the dispersed resin particles used in the present invention, generally, the above-mentioned dispersion stabilizing resin and monomer (A) are mixed with benzoyl peroxide, azobisisobutyronitrile, or butyl peroxide in a nonaqueous solvent. The polymerization may be carried out by heating in the presence of a polymerization initiator such as lithium. Specifically, (1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin and a monomer (A);
■ A method in which the monomer (A) is dropped together with a polymerization initiator into a solution in which the dispersion stabilizing resin is dissolved, or ■ A mixed solution containing the entire amount of the dispersion stabilizing resin and a part of the monomer (A). A method of optionally adding the remaining monomers together with a polymerization initiator; There are a number of methods, such as adding it to a compound, and it can be produced using any of the methods.

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

The amount of the soluble resin which is the dispersion stabilizing resin is 1 to 100 parts by weight, preferably 5 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. The reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers, and esters is used in combination with the nonaqueous solvent used in the reaction, or when unreacted monomers (A) to be polymerized and granulated are If it remains, it is preferable to remove it by heating it to a temperature above the boiling point of the solvent or monomer or distilling it off under reduced pressure.

The non-aqueous dispersed resin particles produced according to the present invention as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, and can be used repeatedly for a long time, especially in a developing device. The dispersibility is good even when the developing speed is increased, and redispersion is easy even when the developing speed is increased, and no stains are observed at all on various parts of the device.

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

Furthermore, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-sized master plate is used.

In particular, JP-A-62-166362 or JP-A-63
In the non-aqueous dispersion resin described in No.-66567, the main polymer is a monomer containing at least two or more ester bonds, etc. in the molecule, which can be copolymerized with the monomer that polymerizes and becomes insolubilized. Polymerization and granulation using a random copolymer soluble in the non-aqueous solvent containing a copolymer component with a polymerizable double bond group bonded to a site separated by a total number of atoms of 8 or more from the chain as a dispersion stabilizing resin. The dispersibility and rigidity resistance of these particles have been greatly improved compared to conventional particles, but plate making using a large-sized offset printing master plate machine (for example, manufactured by Fuji Photo Film ■, ELP-560, EL
P-820, etc.), or when the processing speed of the plate making machine is increased, there are still problems with the dispersibility of the particles, resulting in staining of the plate making machine (particularly staining of the developing device) and agglomeration and sedimentation of particles. Or, when the master plate was printed, the strength of the image area was still insufficient, resulting in a decrease in printing durability. 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
Soluble A-B used with monomer (A) to be insolubilized
It depends on the type of block copolymer.

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 insufficient (furthermore, since the adsorption pattern was loop-shaped, the steric repulsion effect was also negated, resulting in insufficient dispersion stability).

In addition, the high rigidity that does not cause deterioration of the toner image area when printed as an offset master original plate is due to the fact that the monomer (A) to be insolubilized and the dispersed polymer adsorbed to it have good compatibility with each other and are mild. It is presumed that this is achieved by sufficiently compatibilizing under fixing conditions and forming a uniform and strong film.

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 black, nigrosine, alkali blue, Hanzai Elo, quinacridone red, and phthalocyanine blue.

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

If 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 carrier liquid soluble resin for dispersion stabilization may be used as desired, and may be added in an amount of about 0.5 to 100 parts by weight per 1000 parts by weight of the carrier liquid.

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. 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, if the electrical resistance of the liquid developer with toner particles removed is lower than 10'Ωcm, it will be difficult to obtain a high-quality continuous tone image, so the amount of each additive added should be controlled within this limit. is necessary.

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

No. 8 1: A mixed solution of 95 g of dodecyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream, and -7
Cooled to 8°C. 1.0 g of 1.1-diphenylbutyllithium 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. Add this mixture to O
'C, 10M1 of methanol was added, the reaction was carried out for 30 minutes, and the polymerization was stopped. The resulting polymer solution was brought to a temperature of 30° C. with stirring, and 15 d of a 30% hydrogen chloride ethanol solution was added thereto and stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total volume was reduced to half, and then methanol II! , re-sinked inside. The polymer obtained by collecting the precipitate and drying it under reduced pressure has a weight average molecular weight of 4.5.
The yield was 70 g at X 10'.

CP)-1 co, CH.

-ecHz-C)yr-b-(CHz-C (weight ratio) COOC+zHzs C00H b indicates a block bond (the same applies hereinafter).

A mixed solution of 46 g of octadecyl methacrylate, 0.5 g of aluminum methyl (tetraphenylporphinate) and 60 g of methylene chloride was heated at 30'C under a nitrogen stream.
And so. This was irradiated with 300W-xenon lamp light from a distance of 25cm+ 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, and a catalytic reduction reaction was performed at a temperature of 25°C for 1 hour.

After filtering out insoluble matter, it was reprecipitated in 500 d of methanol,
The precipitate was collected and dried. The yield of the obtained polymer was 33g.
The weight average molecular weight was 3 x 10'.

CP)-2 CHI CH.

A CHt -C)rr-b -1-(CHz -Ch
rCOOCtaHst(n) C0OH output
A mixed solution of 90 g of 37 P-3 tridecyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream and cooled to -78°C. 1
．． 1-diphenyl-3-methylpentyl lithium 0.8
g 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, the precipitate was collected by re-precipitation in methanol. The precipitate was washed twice with 300 d of methanol and dried. The obtained polymer was ,
The yield was 58 g and the weight average molecular weight was 3.5 x 104.

CP) CH.

A mixture of 95 g of hexadecyl methacrylate and 2.0 g of benzyl NN-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. After adding 5 g of acrylic acid and 180 g of methyl ethyl ketone to this, the mixture was replaced with nitrogen and irradiated with light for 10 hours again.

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'.

CP) CHz A mixed solution of 80 g of stearyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream,
Cooled to -78°C. 1.0 g of 1,1-diphenyl-3-methylpentyl potassium was added and stirred for 10 hours.

Further, 20 g of styrene was added to this mixture and stirred for 8 hours, and then the reaction mixture was brought to 0°C and 10 d of methanol was added. Next, add this to methanol i, s! ! , the precipitate was filtered and dried, and the resulting polymer had a yield of 6.
The weight average molecular weight was 3×10′ at 8 g.

(P)-5 H3 -- A mixed solution of 10 g of H3--x's tan-yt dispersion stabilizing resin P-1, 100 g of vinyl acetate, and 380 g of Isopar H was heated to a temperature of 70°C while stirring under a nitrogen stream. . Add 0.8 g of 2,2゛azobis(isovaleronitrile) (abbreviation: A, B, V, N,) and react for 2 hours, and then add A, B, V, N, to 0.
．． 6g was added and reacted for 2 hours. 20 minutes after the addition of the initiator, clouding occurred and the reaction temperature rose to 88°C. The temperature was raised to 100°C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 86.
The latex had an average particle size of 0.21%.

M-x 2 to 4: In Production Example 1 of D-2 to D-4 latex particles, 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. Thus, latex particles D-2 to D-4 were 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 Production Example 1, except that -1 was replaced with each resin in Table 2 below. The zero polymerization rate of each latex was 83 to 88%. Ta.

(Left below) -10:I) -10 Vinyl acetate 8
5g, N-vinylpyrrolidone 15g, dispersion stabilizing resin P
A mixed solution of 12 g of -1 and 380 g of n-decane was heated to 75°C while stirring under a nitrogen stream. 2.2
' -Azobisisobutyronitrile (abbreviation: A, 1.
Add 1.7g of B, N, ) and react for 4 hours, then add A,
1. 0.5g of B 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 was latex with an average particle size of 0.254.

A mixed solution of 20 g of D-11 dispersion stabilizing resin-7 and 470 g of n-dodecane was heated to 60° C. while stirring under a nitrogen stream.

In this solution, 100 g of methyl methacrylate, n-
1.0 g of dodecyl mercaptan and A, B, V, N,
A mixed solution of 0.8 g was added dropwise over 2 hours. After 2 hours of reaction, A, B, V, N.

0.3g of was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200 mm nylon cloth, and the resulting white dispersion was a latex with an average particle size of 0.2B.

m-X 12:D-12 14g of dispersion stabilizing resin P-11 with the following structure, 100g of vinyl acetate, 5g of crotonic acid, and 468g of Isopar E.
The mixed solution of g was heated to 70℃ while stirring under a nitrogen stream.
It was heated to Add 0.8g of A, B, V, and N and react for 6 hours, then raise the temperature to 100°C and stir for 1 hour.
The remaining vinyl acetate was distilled off. 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-.

-1l CH,CH3 -(CHz -Chrr-b --HCHCHh-co
13:D-13 14 g of dispersion stabilizing resin P-12 having the following structure, 100 g of vinyl acetate, 6.0 g of 4-pentenoic acid, and Isopar G While stirring 380 g of mixed solution under nitrogen stream,
It was heated to a temperature of 75°C. 0.7g of A, B, V, N
Add and react for 4 hours, then add 0.5g of Sarani A, B, V, and N.
In addition, the reaction was continued for 2 hours. After cooling, coarse particles were removed through a 200-molecular-weight nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.23.

-12 COOC+aHgq 0COCHz OH
A mixed solution of 100 g of 14:D-14 styrene with a weight average molecular weight of 3.0 x 10' m-x, 16 g of dispersion stabilizing resin P-5, and 380 g of Isopar H was heated to 60 °C with stirring under a nitrogen stream. It was warm. A, B, V, N.

Add 0.6g of and react for 4 hours.
0.3g of was added and reacted for 3 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 about 0.18 ta.

m-x ts: 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 385 g of Isopar H
The procedure was carried out in the same manner as in Production Example 1, except that the mixed solution of g 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 1, except that a mixed solution of 1 g of 1) 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-63-66567) Monomer (1) CH3 coz=c COO(CHz)zOcOcJ+v(n) Resin for dispersion stabilization: R-1 CH, CH.

-(CH2-CH-→CHi-C)r-COOCIIH
3? C00(C)It)zOco(CHz)zcO
OcHzcH=cHt (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 Nissan Chemical Co., Ltd., tetradecyl alcohol), 0 of [octadecene-half-maleic acid octadecylamide copolymer]
．． A liquid developer for electrostatic photography was prepared by diluting 08g of the sample to Shersol 71 If.

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

Comparative liquid developer A Resin dispersion of Nilatex particle production example 15 Comparative liquid developer B Resin dispersion of Nilatex particle production example 16 These liquid developers were processed using a fully automatic plate making machine ELP404V (Fuji Photo Film ■ ELP Master ■ type (manufactured by Fuji Photo Film ■), which is an electrophotographic light-sensitive material, was exposed and developed. The plate making speed was 5 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original.

The results are shown in Table-3.

When plate making was carried out using each developer under the above-mentioned plate making conditions, the developer of the present invention was the only one that did not cause staining of the developing device and provided a clear image on the 2000th plate making plate.

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. As a result, the master plate obtained using the developer of the present invention did not cause the problem even after 10,000 sheets or more, and the master plate using Comparative Example A did not cause the problem.
This occurred at 000 sheets. In the case of Comparative Example B, the problem occurred after 8,000 sheets were printed.

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

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). Then, the developing device (especially on the back electrode plate) became dirty, and 2
After 1,000 copies, the image quality of the copied image on the plate began to be affected (decreased D+*ax, blurring of thin lines, etc.). Furthermore, the number of printed master plates was significantly reduced in Comparative Example A.

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
By passing the remaining dye through 0 mesh nylon cloth, the average particle size is 0.24t! A black resin dispersion of m was obtained.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． 05g, 20g of FOC-1600 (manufactured by Nissan Chemical ■, hexadecyl alcohol) and 11 of Shersol 71
A liquid developer was prepared by diluting it to .

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

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

Example 3 White dispersion 10 obtained in latex particle production example 13
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 m.

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

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

White resin dispersion D obtained in latex particle production example 5
30 g of -5, 4.2 g of the above alkali blue dispersion
A liquid developer was prepared by diluting 15 g of isostearyl alcohol and 0.06 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 11 of Isopar G.

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 4 below was used in place of latex particles D-5.

Table 4 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: (1) a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and (2) a block containing at least a polymer component represented by the following general formula (I) A, carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and ▲numerical formula, chemical formula, table, etc.▼ group (Q_0 is -Q_1
or -OQ_1 group, and Q_1 represents a hydrocarbon group] and/or a polymer component corresponding to the monofunctional monomer (A). 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, respectively. A liquid developer for electrostatic photography, characterized in that it is polymer resin particles obtained by polymerizing a solution containing at least one type of developer. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula (I), V_0 is -COO-, -OCO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. It represents ▼ 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).