JPH0281054A - Electrostatic photographic liquid developer - Google Patents

Abstract

PURPOSE:To enhance dispersion stability, redispersibility, and fixability of a developer by dispersing specified resin particles into a prescribed nonaqueous solvent. CONSTITUTION:The title developer is prepared by dispersing the resin particles, a colorant, and the like into the nonaqueous solvent having an electric resistivity of >=10<9>OMEGA.cm and a dielectric constant of <=3.5, such as an aliphatic hydrocarbon, and the resin particles are prepared by copolymerizing a monomer A, such as vinyl acetate, with a monomer B of formula II in the presence of a dispersion stabilizing resin obtained by combining the monofunctional monomer (A) with one end of the main chain of a monomer containing repeating structural units of formula I. In formulae I and II, X is COO, OCO, or the like; R<1> is 6-32C aliphatic group; each of a<1> and a<2> is H, halogen, or the like; R<3> is a >=8C aliphatic group; Y is COO, CONH, or the like; each of b<1> and b<2> is H, alkyl, or the like. Octadecyl methacrylate or the like can be used for the monomers of formulae I and II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a liquid developer for electrostatic photography, which has an electrical resistance of 109 Ωcm or more and a dielectric constant of 3.5 or less (made by adding at least 11 parts of a resin to a body fluid). In particular, it relates to a liquid developer with excellent redispersibility, storage stability, image reproducibility, and fixing properties.

(Prior art) The liquid developer for electrophotography (a) is made by combining organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue with 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 hydrocarbons, and further contains a polarity control agent such as a polymer containing metal, lecithin, linseed oil, higher fatty acids, or 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 insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, causing the particles to settle, aggregate, or accumulate, and the polarity to become unclear. In addition, the particles that have aggregated and accumulated cannot be redispersed (because of this, particles remain attached to various parts of the developing machine, leading to problems with the developing machine such as stains in 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 1- The problem is that the redispersion stability is insufficient for practical use, as the toner solidifies into a film, making it difficult to redisperse and also causing equipment failure and smearing of copied images. In addition, in the method for producing resin particles described above, in order to produce particles with a narrow particle size distribution, the dispersion stabilizer used,
There are significant restrictions on the combination of monomers that can be used to stabilize the particles, and the result is generally particles with a wide particle size distribution containing a large amount of large particles, or polydisperse particles with two or more average particle sizes. . Furthermore, it is difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 μm or more or very fine particles of 0.1 μm 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 types of polar components are used. A method of improving the dispersibility, redispersibility, and storage stability of particles by doing so is disclosed in JP-A-60-179751 and JP-A-62-151868. Also, in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction, the insoluble dispersed resin particles are made of a copolymer of a monomer that becomes insolubilized and a monomer containing a long-chain alkyl moiety. Methods for improving the dispersibility, redispersibility, and storage stability of particles are disclosed in JP-A-60-185963 and JP-A-6163855.

(Problems to be Solved by the Invention) On the other hand, in recent years, attempts have been made to print a large number of 5,000 or more sheets using an electrophotographic offset printing master plate. It has become possible to print more than 10,000 sheets in plate size. Further, progress has been made to shorten the operating time of electrophotographic engraving systems, and improvements have been made to speed up the development and fixation process.

JP-A-60-179751 and JP-A No. 62451868
Dispersed resin particles produced according to the method disclosed in No. 60-185963 and No. 61-63855 have a tendency to improve particle dispersibility, redispersibility, and fixation when the development speed increases. In cases where the time is shortened or in the case of a master 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 speeds up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in electrophotolithography system 4 using a large-size master plate. It is to be.

Another object of the present invention is to provide a liquid developer that enables the production of offset printing original plates having excellent printing ink oil sensitivity and printing durability by electrophotography.

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

Still another object of the present invention is to provide a liquid developer which can be used in any system where a liquid developer can be used, such as ink diene recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. The goal is to provide the following.

(Means for Solving the Problems) An object of the present invention is to provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 109 Ωam or more and a dielectric constant of 3.5 or less. In this case, the dispersed resin particles are copolymerized with a -functional monomer (A) only at one end of the main chain of a polymer having at least one repeating unit represented by the following general group (I). A monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization in the presence of a dispersion stabilizing resin comprising a polymerizable double bond group to be obtained, and the following General formula (II
), a monomer (B) containing an aliphatic group having 8 or more carbon atoms and copolymerizing with the monomer (A) in a polymerization reaction.
This has been achieved by a liquid developer for electrophotography, which is characterized in that it is copolymer resin particles obtained by polymerizing a solution containing at least -.

General formula (I) %Formula% In general formula (I), X is -COO-1-OCO-1-C1
120CO-5CIl□COO-1-〇-1 or -SO
□ Represents -.

R1 represents an aliphatic group having 6 to 32 carbon atoms.

a+ and R2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, C00-R'' or a hydrocarbon group having 1 to 8 carbon atoms. -C00-R''(I?'' represents a hydrocarbon group having 1 to 22 carbon atoms).

- General formula (II) bl b2 CII=C -R3 In general formula (II), R3 represents an aliphatic group having 8 or more carbon atoms.

Y represents -C00-1-CONI-1CON- (R' represents an aliphatic group), -0CO--CIl□000-1 or 0-.

bl and b2 may be the same or different, and each represents a hydrogen atom, an alkyl group, -C00R' or barC112-CO
0I? ' (R5 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 109 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, and a halogen thereof. 216 bodies can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, Hensen, toluene, xylene, mesitylene, isopar E1
Isopar G1 Isopar L (A, Isopar: Exxon's product name), Shelzol 70, Shelzol 71 (Soerzur: Siel Oil's product name), Amsco OMS, Amsco 460 solvent (Amsco; Spiritotsu's product name) (product name) etc. may be used alone or in combination.

Non-aqueous excess 11, which is the most important component in the present invention
Polymerizable resin particles (hereinafter sometimes referred to as latex particles) have polymerizable double bonds that can be copolymerized with a monofunctional monomer (A) only at one end of the polymer main chain in a nonaqueous solvent. Qi having a monofunctional monomer (A) and an aliphatic group having 8 or more carbon atoms in the presence of a dispersion stabilizing resin formed by bonding a bonding group.
It is produced by polymerization and granulation by copolymerizing with ffi form (I3).

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. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, Isopar E, Isopar G, Isopar H, Isopar 2 Shelzol 70, Shelzol 71, Amsco OMS, Amsco 460? 8 agents are used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, 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. dienal ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methyl chloroform, etc.).

After polymerization and granulation, the well water) 8 medium to be mixed and used is
Although it is preferable to remove the latex particles by heating or under reduced pressure, there is no problem even if they are brought into the liquid developer as a latex particle dispersion, as long as the liquid resistance of the developer can satisfy the condition of 10 9 Ωcm or more.

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

Stable the solvent-insoluble copolymer produced by copolymerizing a monofunctional monomer (A) and a monomer (B) having an aliphatic group having 8 or more carbon atoms in a non-aqueous solvent. The dispersion stabilizing resin of the present invention used to form a resin dispersion contains a monofunctional monomer only at one end of the polymer main chain containing at least one type of repeating unit represented by the general formula (I). It is a polymer formed by bonding a polymerizable double bond group that can be copolymerized with (A).

In the repeating unit represented by general formula (I), the aliphatic group and the hydrocarbon group may be 11M.

In the general formula (+), X is preferably -COO-1O
CO-~C1l, OCO~, -c++zcoo- or -
Represents 0-, more preferably -000-5-C11□
Represents COO or -0-.

R1 preferably has 8 to 22 carbon atoms and may be substituted,
Represents an alkyl group, alkenyl group or aralkyl group.

Examples of the substituent include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-R', -CO
O-R''-0CO-R"(I?' is a carbon number of 6 to 22
represents an alkyl group such as a hekynyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, and the like. More preferably, R1 represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. Examples include octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, octadecenyl group, and the like.

a, , ag may be the same or different from each other, preferably a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a carbon number of 1 to
3 alkyl group, -COO-R'' or ClICoo-
1? ” (R2 preferably represents an aliphatic group having 1 to 18 carbon atoms).More preferably, al and R2 are
May be the same or different from each other, hydrogen atom, carbon number 1~
3 alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), -Coo-R2 or CH2C00-R"
(R2Hayo?) Preferably represents an alkyl group or alkenyl group having 1 to 18 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, butenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group,
Examples include a tetradecenyl group and an octadecenyl group, and these alkyl groups and alkenyl groups may have the same substituents as those represented by ill above.

The polymerizable double bond group bonded to one end of the polymer main chain is a group copolymerizable with the monofunctional monomer (A), specifically, 0 CL Cll3
0II 1111 C11□=C1l-C-0-1C1l□・C-C-0-
1CII=CI(-C-0-3CIl□C00C113
CI! 3 CIl□・C-C-0-C112・C11-CONH-
5CIl□・C-C0N11Clh
OI C1l-Cll-CQNI(-CL=Ctl-G-Co
CH30 II 1 11 CIl□・CII -CIIA〇-C-, CI+25
C-0-C-5C)1! =C)! -3o□-, CIl□
・Cl1-C-1CH2・cn-.

CHg=C1l-5-Clf□-C11-1CI+2=
Examples include CIl-CI+□.

These polymerizable double bond groups have a chemical structure in which they are directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

As a linking group, carbon-carbon bond (-double bond or double bond), carbon-hetero atom bond (as a petro atom,
For example, it is composed of any combination of atomic groups such as oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and Peter atom-Peter atom bonds. For example, (-C)(R',
Re is a hydrogen atom, a halo B gene atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (e.g.,
(methyl group, ethyl group, propyl group, etc.) The polymer component of the dispersion stabilizing resin of the present invention is a homopolymer component or copolymer component selected from repeating units represented by the general formula (+), or a general It is composed of a copolymer component obtained by polymerizing a monomer corresponding to the repeating unit represented by formula (I) and another polymerizable monomer. Other monomers that can be used as copolymer components together with the polymer component of general formula (I) include, for example, compounds represented by the following general formula ([1)].

General formula (Ill) dl R2 C1l=C T-R' In general formula (III), T is -C00-1-OCO-5-
C) 1.0CO-1 (R9, Rlo is a hydrogen atom, the above -
Examples include a single linking group selected from atomic groups such as a catalytic group (representing a hydrocarbon group having the same meaning as R2 shown in I1), or a linking group composed of any combination thereof.

, where R12 is a hydrogen atom or a carbon number of 1 to 1
8 optionally substituted aliphatic groups (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group,
2-bromoethyl group, 2-cyanethyl group, 2-hy)oxyethyl group, hensyl group, chlorobenzyl group, methylhensyl group, methoxyhensyl group, phenethyl group, 3-
phenylpropyl group, dimethylhensyl group, fluorohensyl group, 2-methoxyethyl group, 3-me-xypropyl group, etc.).

R port is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 22-dichloroethyl group, 2.2. 2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2.3-dihydroxyethyl group, 2-hydroxy-3-chloropropyl group, 2-
Cyanoethyl group, 3-anopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, NN-dimethylaminoethyl group, N,N-diethylaminoethyl group, trimethoxy Silylpropyl group, 3-bromopropyl group, 4-
Hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypa/propyl group, 4-carboxybutyl group, 2- Phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group,
2-carboxamidoethyl group, 3-sulfoamidopropyl, l,2-N-methylcarboxamidoethyl group,
cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

d' and d' may be the same or different, and each represents the same content as al or a2 in the general formula (+).

Specific monomers represented by general formula (I1) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid trifluoropropionic acid, etc.); Allyl esters, optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and mal/inic acid (as an alkyl group, for example, Methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2
-fluoroethyl group, trifluoroethyl 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, 1-(N,N-diethylamino)ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloro propyl group,
2-Hydroxy-3-chloro-propyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group,!・Rimethoxin rilbrovir group, 2-power!
1 wood diamide ethyl group, etc.), styrene derivatives (e.g., styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene,
Bromostyrene, vinylhenzenecarboxylic acid, vinylhenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N,N-dinothylaminomethylstyrene, vinylhenzenecarboxamide, vinylhenzenesulfotemi, etc. ), acrylic acid, methacrylic acid, crotonic acid, unsaturated carboxylic acids such as maleic acid and itaconic acid, or cyclic anhydrides of maleic acid and itaconic acid, acrylonitrile, methacrylic monoconitrile, and heterocyclic compounds containing polymerizable double bond groups. (Specifically, for example, edited by the Polymer Science Society [Polymer Data Handbook Basic Edition-], p. 175-184, Mound 8 Kan (I9)
(published in 1986), such as N-vinylpyridine, N-vinylthiazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxaprine, vinylthiazole, N-vinylmorpholine, etc.).

-a The monomers represented by formula ([1)] may be used in combination of two or more.

The repeating unit represented by the above general formula (I) accounts for 30% by weight or more in the dispersion stabilizing resin polymer used in the present invention.
100% by weight is suitable, preferably 50% by weight ~l
OO Juyo%.

The dispersion stabilizing resin of the present invention, which has a polymerizable double bond group bonded only to one end of the polymer main chain, has various double bonds at the end of a living polymer obtained by conventionally known anionic or cationic polymerization. Reacting with a reagent containing a group or adding a specific reactive group '' (e.g. -011, -COO11, -5
o, I+, -Nil□, -311, /\ POJz, -NCO, -NC5, -C) I-CL,
-COCj! , -5o After radical polymerization using a polymerization initiator and/or chain transfer agent containing groups, a polymer reaction is performed using a specific reactive group bonded only to one end of the polymerizable main chain. It can be easily produced by a synthetic method such as a method of introducing a polymerizable double bond group by carrying out the following steps.

Specifically, P, Dreyfuss & R,P,
QuirkEncycle, Polym, Sci,
[ingl, 7, 551 (I987), Yoshiki Nakajo, Tatsuya Yamashita, "Dye and Medicine", 30.232 (I98
5), Uedama, Susumu Nagai 1 “Science and Industry” 1 Rule 57 (I
986), P., P., Rempp & E., Fra.
nta Advancesin Polymer 5
science, 58.1 (I984), Hiroshi Ige - “
Polymer Processing J, 35.262 (I986), V.
Percec Applied Polymer 5c
It can be produced according to the method described in the review article and the literature cited therein, such as J. Ience, 285, 97 (I984).

The weight average molecular weight of the dispersion stabilizing resin used in the present invention is lX
Preferably 10' to 5X10', more preferably 2X1
0' to 2X10'.

Specific examples of the dispersion stabilizing resin used in the present invention are shown below, but the present invention is not limited thereto.

(+-1) Cu3 (+-3) IL Cu2 Hs CI+.

aHq C11゜ C.I.

(I II) (I +2) CI+.

(I +6) COOII C11゜ (I +8) C11゜ (! C1+.

(■ (I [+10・〜Czi altol group (I L:l.

X knee OH.

■, Br.

C.N.

ONH2 J! 'Water-based content: 11 parts, used in the production of resin: 1 part
The "L-mer" is a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a carbon compound represented by the general formula ([1)]. A monomer containing an aliphatic group of number 8 or more and controlling copolymerization with the 11-monomer (A) (
B) can be distinguished.

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

General formula (instead e l e Z C1l=C R13 In the general formula (IV), Q is -000-1-OC 屹, -C1
Represents 1□0CO-1. Here, RI7 is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group) group, 2-hydroxybutyl group, hensyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, fethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorohensyl group, 2-methoxyethyl group, 3-methoxy propyl group, etc.).

R11 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, 22-dichloroethyl group, 2,2.2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxybutyl group, 2-hydroxyphylloyl group, 2 , 3-dihydroquinethyl group, 2-hy)roquine-3-chloropropyl%,
2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl L NN-dimethylaminoethyl group, N, N-diethylaminoethyl group,
trimethoxysilylpropyl group, 3-fluoroX thyl group,
4-hydroxybutyl group, 2-furfurylethyl group, 2
-Thousenylethyl group, 2-Biridylbutyl group, 2-morpholinoethyl group, 2-carboxy1thyl group, 3-carboxypropyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-carboxyl group diamidoethyl group; 3-sulfamidopropyl group, 2-N-methylcarboxyaminoethyl group, cyclopentyl group, chlorocyclohexyl group, diamide group, etc.).

el and C2 may be the same or different, and each represents the same content as dl or R2 in the general formula (I).

Specific monofunctional monomers (A) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.) or allyl esters, optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (as an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-fluoroX
thyl group, trifluoroethyl group, 2hydroxoethyl group,
2-cyanoethyl group, 2nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group. 2-(N,N-dimethylamino)ethyl group, 2-(N,N-diethylamino)ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-
Carboxybutyl group, 3-sulfopropy JL, jf5,
4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group,
trimethoxysilylpropyl group, 2-carboxyamidoethyl S, etc.), styrene gM i form (e.g. Eva, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, promostyrene, vinylhenzenecarboxylic acid) , vinylhenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N.

N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylhenzenesulfamide, etc.), unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, or cyclic anhydrides of maleic acid and itaconic acid , acrylonitrile, methacrylonitrile, heterocyclic compounds with polymerizable double bond foundations (specifically, for example, "Polymer Data Handbook Basic Edition" edited by the Society of Polymer Science, p. 175-184, Baifukan) (I986
For example, N-vinylpyridine,
N-vinylimidazole, N-vinylpyrrone, vinylthiophene, vinyltetrahydrofuran, vinylmorpholine, vinylthiophene, N-vinylmorpholine, etc.).

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

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

In general formula (II), R3 preferably 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, Y is -COO-1CON
II-8-CON- (However, R4 preferably has 1 carbon number
~32 aliphatic groups (for example, aliphatic groups include alkyl groups, alkenyl groups, or aralkyl groups)]
, -0CO--CII□0CO- or -0-.

bl and bZ may be the same or different, preferably a hydrogen atom, a methyl group, -COOR5 or -CIl□C0O
R' (provided that R5 preferably represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 1 to 32 carbon atoms).

Furthermore, more preferably, in formula (II), Y is COO--
CONII- or -Colt-, bl and b2
may be the same or different and represent a hydrogen atom or a methyl group, and R'' represents the same content as described above.

Specific examples of the monomer (B) represented by the above general formula (II) include aliphatic groups having a total carbon number of 10 to 32 (aliphatic groups include halogen atoms, hydroxyl groups, amine groups, alkoxy groups, etc.). acrylic acid, which may contain a substituent group of
Esters of unsaturated carboxylic acids such as methacrylic acid, crotonic acid, maleic acid, itaconic acid (aliphatic groups such as decyl group, dodecyl group, tridecyl group, tetrazotyl group, hexadecyl group, octadecyl group, docosanyl group, dodecenyl group, (hexadecenyl group, oleyl group, lylyl group, tocosenyl group, etc.), amides of the aforementioned unsaturated carboxylic acids (aliphatic groups are the same as those shown for esters), vinyl esters or allyl esters of higher fatty acids (As higher fatty acids, for example, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc.), or vinyl ethers substituted with aliphatic groups having a total number of carbon atoms of 10 to 32 (the aliphatic groups are as described above). (representing the same range as the aliphatic group of unsaturated carboxylic acid), etc.

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 the monomer (B) represented by general II (II) in an amount of 0.1 to 20% by weight, more preferably 0.3 to 20% by weight, based on the monomer (A) that contains It is 8% by weight. Further, the molecular weight of the dispersion resin of the present invention is preferably 101 to
106, more preferably 10' to 10b.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and monomer (B) are mixed in 1M and 1L hendyl in a non-aqueous solvent. The polymerization may be carried out by heating in the presence of a polymerization initiator such as , abbisisobutyronitrile, butyllithium, or the like.

Specifically, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, monomer (A), and monomer (B), a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, A method in which the compound (A) and the monomer (F3) are dropped together with a polymerization initiator, or a method in which the entire amount of the dispersion stabilizing resin is mixed with a part of the mixture of the monomer (A) and the monomer CB) A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a solution, and a method of optionally adding a mixture of a dispersion stabilizing resin and a monomer to a non-aqueous solvent 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) and monomer (B) is 10% of the nonaqueous solvent.
The proportion is approximately 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 5 to 50 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of polymerization initiator is 0.1 to 5% (weight) of the total monomer amount
is appropriate.

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 the above-mentioned alcohols, ketones, ethers, esters, etc. are used in combination with the non-aqueous solvent used in the reaction, or when the monomer (A) or monomer CB is polymerized and granulated. ) If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than the boiling point or distilling it off, or by distilling it off under residual pressure.

The non-aqueous latex particles produced as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, especially after repeated use over a long period of time in a developing device. It has good dispersibility and is easy to redisperse even when the development speed is increased, and no stains are observed at all on various parts of the device.

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

Furthermore, the liquid developer of the present invention 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.

If necessary, a coloring agent may be used in the liquid developer of the present invention.

The coloring agent is not particularly limited; various conventionally known pigments or dyes can be used.

When coloring the dispersed resin itself, for example, one method of coloring is to physically disperse molecules into the resin using pigments or dyes. very much known. Examples include n-type iron oxide powder, powdered lead iodide, carbon blank, nigrosine, alkali blue, Hanzaiero, quinacridonelend, phthalocyanine fillet, and the like.

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-53-54029, or as described in JP-B No. 44-22955, etc.
When producing by a polymerization granulation method, there is a method of using a monomer containing a dye in advance to form a dye-containing copolymer.

Various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics, etc., as necessary. Those specifically described in No. 2, page 44 are used.

Examples include di-2-ethylhexyl sulfosuccinic acid metal salts, naphthenic acid metal salts, higher fatty acid metal salts, lenotin, 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.

It is preferable that the L-ner particles mainly composed of a resin and, if necessary, a colorant, be in an amount of 0.5 parts by weight to 501 parts by weight based on too many parts by weight of the carrier liquid. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, capri will likely occur in non-image areas. Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization is also used as necessary, and the carrier liquid 1000
It can be added in an amount of about 0.5 parts by weight to 100 parts by weight. The charge control agent as described above can be added to the carrier liquid 10.
It is preferably 0.001 parts by weight to 1.0 parts by weight per 00 parts by weight. Furthermore, various additives may be added as necessary, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. In other words, if the electrical resistance of the liquid developer with toner particles removed is lower than 109 Ωcm, it will be difficult to obtain a high-quality continuous tone image, so the amount of each additive added must be controlled within this limit. It is necessary to.

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

Octadecyl methacrylate 100g, toluene 15
A mixed solution of 0 g of isopropanol and 50 g of isopropanol was heated to 75° C. with stirring under a nitrogen stream. 2゜2'-Azobis(4-cyanovaleric acid) (abbreviation A, C, V) 30
g was added and reacted for 8 hours. After cooling, it was reprecipitated into methanol 22, and the white powder was filtered and dried. The resulting white color)
50g, vinyl acetate 3.3g, acetic acid water il 0.02
5 g, hydroquinone 0.2 g and toluene 100
The mixture of g was heated to a temperature of 40°C and reacted for 2 hours. Next, the temperature was raised to 70°C, and 100% sulfuric acid 3.8
Added Xl0-"d and reacted for 10 hours. Temperature: 25°C
Cool to 3.0 and add 0.02g of sodium acetate trihydrate
After stirring for 0 minutes, it was re-precipitated in methanol 11, and 21 tons of slightly discolored powder was collected and dried. The yield was 41 g and the weight average molecular 'fk (Mw) was 38,000.

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

Table 1 1 10: ″″ 1 A polymerization reaction was carried out in the same manner as in Production Example 1, except that a mixture of 100 g of dodesol methacrylate, 150 g of toluene, and 50 g of isopropanol was used.

After cooling, it was reprecipitated in methanol 21, and a colorless and transparent viscous substance was obtained by decantation, and then dried.

50 g of the resulting viscous material, glycidyl methacrylate
1.5 g, 2.2'-methylenebis-(6-L-butyl-
A mixture of 1.0 g of p-cresol), 0.5 g of N,N-dimethyldodecylamine, and ioog of toluene was heated to 100°C and stirred for 12 hours. This reaction mixture was reprecipitated in methanol 1j2 to obtain a pale yellow viscous substance by decantation, which was then dried. Yield: 139g, Mw3
7. It was OOO.

100g of octadecyl methacrylate and 30g of toluene
0 g of the mixed solution was heated to 70° C. while stirring under a nitrogen stream. 5 g of 4,4'-azobis(4-cy7/pentanol) was added and reacted for 8 hours.

Next, after cooling this reaction product, methacrylic anhydride 6.2
g, 0.8 g of t-butylhydroquinone and 1 drop of concentrated sulfuric acid were added, stirred at a temperature of 30°C for 1 hour, and further heated to a temperature of 5°C.
The mixture was stirred at 0°C for 3 hours. After cooling, it was reprecipitated in methanol 22, and the white powder was filtered and dried. Yield 88g Mw
It was 38,000.

A mixed solution of 100 g of octadecyl methacrylate and 200 g of te]-rahydrofuran was heated to a temperature of 70"C while stirring under a nitrogen stream. 4.4'-Azobis(4-
4 g of Soanobentasol) was added and reacted for 5 hours. Furthermore, 1.0 g of the above azobis compound was added and reacted for 5 hours. The reaction mixture was cooled to a humidity of 20°C in a water bath and added with 3.2 g of pyridine and 2.2'methylenebis-(6-L-
butyl-p-cresol)1. og was added and stirred. To this mixed solution, 4.2 g of methacrylic acid chloride was added dropwise over 30 minutes while keeping the reaction temperature from exceeding 25°C.

The mixture was stirred for 4 hours at a temperature of 20°C to 25°C. Next, this reaction product was reprecipitated in a mixed solution of 1.52 parts of methanol and 0.5 parts of water, and a white powder was collected and dried. M with a yield of 86g
w33. It was OOO.

In Production Example 12, each dispersion stabilizing resin was produced in exactly the same manner as in Production Example 12, except that the acid chloride shown in Table 2 below was used instead of methacrylic acid chloride.

A mixed solution of 98.5 g of dodecyl methacrylate, 1.5 g of thioglycolic acid and 200 g of toluene was heated to 70°C under a nitrogen stream. 1. Beazobis (cyclohexane) Add 0.5 g of -1-carbonitrile) 5
After reacting for an hour, 0.5 g of the above azobis compound was added and the reaction was further continued for 5 hours. This reaction product contained 3.0 g of glycidyl methacrylate I and 1.0 g of L-butylhydroquinone.
g and 0.6 g of N,N-dimenalaniline were added to the temperature t.
The reaction was carried out at +o'c for 8 hours. After cooling, the mixture was reprecipitated with methanol 2 and a pale yellow viscous substance was obtained by decantation, followed by drying. The total weight was 80 g, and the Mw was 33.000.

98.5 g of hexadecyl methacrylate, 1.5 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran
The mixed solution of g was heated to a temperature of 80°C under a nitrogen stream.

1. 0.3 g of 1'-azobis(nclohexane)-carbonitrile was added and reacted for 5 hours 1-1 Furthermore, 0.3 g of the above azobis compound was added and reacted for 5 hours. To this reaction mixture were added 2.5 g of acrylic anhydride and 2゜2'-methylenebis-(
6-butyl-p-cresol)1. og was added and stirred at a temperature of 40°C for 5 hours.

After cooling, the reaction product was reprecipitated into methanol 21 to obtain a colorless viscous substance. The weight was 82g and the Mw was 20,000.

A mixed solution of 100 g of dodecyl methacrylate and 200 g of tetrahydrofuran was heated to 65° C. under a nitrogen stream. 6 g of 2.2'-azobis(4-cyanovaleric acid chloride) was added and stirred for 10 hours.

This reaction i8 liquid was cooled to a temperature of 25°C or less in a water bath,
2.4 g of allyl alcohol was added. 2.5g pyridine
was added dropwise without exceeding the reaction temperature of 25°C, and the mixture was stirred for 1 hour. After further stirring for 2 hours at a temperature of 40°C, the mixture was reprecipitated into methanol 2P. A pale yellow viscous substance was obtained by decantation and then dried. Yield 80 and Mw 38
,000.

Table-3 12g of dispersion stabilizing resin P-1, 100g of vinyl acetate,
A mixture of 1.0g of Octadene Methacrylate and 384g of Isopar H? 8 (& was heated to a temperature of 70'C while stirring under a nitrogen stream. 2.2'-azobis(isovaleronitrile) (abbreviation ^, 1.V, N,) 0.8 g
was added and reacted for 6 hours. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88°C. temperature to 100
The temperature was raised to °C and stirred for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex with a polymerization rate of 90% and an average particle size of 0.24.

In Production Example 1 of Latex Particles, latex particles D-
2 to D-12 were manufactured.

In the production example of 13 to 18 knee latex particles D-1, each latex particle was prepared in the same manner as in Production Example 1, except that 1 g of each of the monomers in Table 4 was used instead of octadecyl methacrylate Ig. was manufactured.

- One batch of 19 Nilatecus 0 was a latex with an average particle size of 0.25μ.

A mixed i8 solution of 6 g of dispersion stabilizing resin P-10, 8 g of poly(octadecyl methacrylate), ?FM Vinyl 1008, 0.8 g of dodecyl methacrylate, and 400 g of Isopar H was heated to 75°C while stirring under a nitrogen stream.2. Add 0.7 g of 2'-azobis(isobutylnitrile) (abbreviation A, 1.B, N,) and react for 4 hours.
Furthermore, A.1. 0.5 g of B and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.17 mm.

A mixed solution of 20 g of dispersion stabilizing resin P-1, 94 g of vinyl acetate, 6 g of crotonic acid, 2 g of hexadecyl methacrylate, and Isopar G was heated to a temperature of 6 while stirring under a nitrogen stream.
Warmed to 0°C. Let A,[,V,N,become 1. og addition 2
Time reacted. Furthermore, A.1. 0.5 g of V, lJ was added and reacted for 2 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex with an average particle size of 0.28-.

Log of dispersion stabilizing resin P-11, 90 g of vinyl acetate,
A mixed solution of 10 g of N-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. 1.5 g of B and N were added and reacted for 4 hours. After cooling, a mixed solution of 25 g of the obtained white dispersion stabilizing resin P-16, 100 g of methyl methacrylate, 2 g of decyl methacrylate, and Isopar H was heated to a temperature of 60' while stirring under a nitrogen stream.
It was heated to C. 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 0.38/I11.

-Tex U's! l-23;--Nox particles - 25g of leaf dispersion stabilizing resin P-15, 100g of styrene, 2g of octadecyl vinyl ether, and Isopar H380
The mixed solution of g was heated to 45° C. with stirring under a nitrogen stream. A hexane solution of n-butyllithium was added in an amount to give a solid amount of n-butyllithium of 1.0 g, and the mixture was reacted for 4 hours. After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was a latex with an average particle size of 0.35.

-Tex's 124 = "A poly(octadecyl methacrylate-1-)<dispersion stabilizing resin (R)-1
The process was carried out in the same manner as in Production Example 1 of Latex Particles, except that a mixed solution of 20 g of 20 g of 100 g of vinyl acetate, 1-1 g of octadecyl methacrylate, and 380 g of Isopar H was used to obtain a polymer with a polymerization rate of 88% and a plane particle size of 0.27. A white dispersion of latex particles was obtained.

M-X's ``'257 B octadecyl methacrylate 97g, acrylic acid 3g and toluene 2
Add 00g of the mixed solution to a temperature of 75°C with a nitrogen stream.
FA L/ta. A.1. B, N, @1.0g was added and reacted for 8 hours. Next, 12 g of glycodyl methacrylate,
1.0 g of t-butylhydroquinone and 1.2 g of N,N dimethyldodecylamine were added and stirred at a temperature of 100°C for 40 hours. After cooling, it was reprecipitated into 2 liters of methanol, and the white powder was dried on a filter. Dispersion stabilizing resin (R)-2 with the following structure
I got it. The yield is 84g7? Mw was 35.000.

Dispersion stabilizing resin [R) -2 -(C11□-C--'j-i-'' CII□-CII
l-r CIf xCOOC+5lht
C00CII□CII CH□0OC-C,C
112 10 g of this dispersion stabilizing resin (R)-2, ffi
Bivinyl acid 100, octadecyl methacrylate
A white dispersion of latex particles with a polymerization rate of 89% and an average particle size of 0.15 nm was obtained by processing in the same manner as in Production Example 1 of Latex Particles except for using a mixed solution of 8384 g of log and Isopar.

M-X's "26: C JP-A-61-6
12 g of dispersion stabilizing resin (R)-3 having the following structure manufactured by the method described in No. 3855 and 100 g of vinyl acetate.
, Octadecyl methacrylate-1-1-1,0g, and Isopar H 382g were treated in the same manner as in Production Example 1 of latex particles, with a polymerization rate of 87% and an average particle size of 0.
．． A white dispersion of latex particles of 23 Vm was obtained.

Dispersion stabilizing resin (R)-3: C00C+Jat Coo (CI□). C00
CR, CI+□Mw: 46.000 (weight composition ratio) Example 1 Dodecyl methacrylate/acrylic acid copolymer (copolymerization ratio (95/5) weight ratio) is Log, Nigrosine 10
30 g of Isopar G and glass beads were placed in a paint shaker (Tokyo Seiki ■) and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

For electrostatic photography, 30 g of the resin dispersion of Production Example 1 of latex particles, 2.5 g of the above nigrosine fraction, and 0.07 g of octadecene/decomaleic acid octadenylamide copolymer were diluted to 12 of Isopar G. A liquid developer was prepared.

(Comparative Liquid Developers A-C) Three types of comparative liquid developers A, B, and C were prepared by replacing the resin dispersion with the following resin particles in the above production example.

Comparative liquid developer A Resin dispersion of latex particle production example 24 Comparative liquid developer B: Resin dispersion of latex particle production example 25 Comparative liquid developer C Resin dispersion of latex particle production example 26 Using these liquid developers as a developer in a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film ■), an electrophotographic light-sensitive material, ELP Master ■ type (manufactured by Fuji Photo Film ■), was exposed and developed. The plate making speed was 7 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ type, the presence or absence of toner adhesion stains on the developing device was observed.

The W conversion rate (image area) of the copied image was determined using a 40% original. The results are shown in Table-5.

Table 5 When plate making was performed using each developer under the plate making conditions described above, as is clear from the results in Table 5, the developing device was not contaminated and the image on the 2000th plate making plate was clear. One developer was the only developer of the present invention.

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 at the edges, etc. place, the present invention, comparative example A,
In the master plates obtained using the developers of Comparative Example B and Comparative Example C, no problem occurred even after 10,000 sheets or more.

As shown in the above results, only the developer made using the resin particles of the present invention does not cause any staining of the developing device, and
The number of printed master plates was also good, 5.

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

Although the staining of the developing devices in Comparative Examples B and C was dramatically improved compared to Comparative Example A, satisfactory performance was still not achieved when the developing conditions were severe.

That is, the known dispersion stabilizing resins of Comparative Examples B and C contain a polymerizable double bond group that copolymerizes with the monomer (A) [vinyl acetate in this example] contained in the polymer. It is characterized by a chemical structure in which components that perform the following steps are randomly copolymerized in the polymer, and therefore it is thought that the redispersibility of latex particles is inferior to that of the dispersion stabilizing resin of the present invention.

Example 2 White dispersion 100 obtained in latex particle production example 2
A mixture of 1.5 g and Sumikaron blank was heated to temperature 1.
The mixture was heated to 00°C and stirred at 730°C for 4 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mm nylon cloth to obtain a black resin dispersion with an average diameter of 0.20 mm.

32g of the above black resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05 g of Shell Silua J IP.

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.

Furthermore, the image quality of the obtained master plate for offset printing was clear, and the image quality of the stamped IC (1) after printing 10,000 sheets was also clear and inauthentic.

Example 3 White dispersion 10 obtained in latex particle production example 21
A mixture of 0g and 3g of Victoria Blue B was heated to a temperature of 70'C to go'c and stirred for 6 hours.

After cooling in a chamber, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.16.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 0.05 g of Isopar I to 11.

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.6 Also, the image quality of the obtained offset printing master plate was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear. .

Example 4 White dispersion 3 obtained in Production Example 12 of Latte Z-kus particles
A liquid developer was prepared by diluting 2.5 g of the nigrosine dispersion obtained in Example 1 and 0.02 g of a semi-docosanylamidated product of a copolymer of diisobutylene and maleic anhydride 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 to the device was observed. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after printing 10,000 sheets were both clear.

After this developer was left to stand for 3 months, the same treatment as above was carried out, but there was no difference in the overall performance from before aging.

Example 5 Poly(decyl methacrylate) log, isopar 8
30 g of alkali blue and 8 g of alkali blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

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

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 printing 10,000 sheets were very clear.

Examples 6 to 21 In Example 5, the solid amount of latex particles shown in Table 6 was used in place of the white resin dispersion in Production Example 1 of latex particles, except that the amount was 6.0 g. A liquid developer was prepared in the same manner as in 5.

When the front surface was developed using the same apparatus as in Example 1, no toner adhesion was observed on the apparatus even after 2000 sheets were developed. Furthermore, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were very clear.

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device did not become contaminated, and both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were very clear. Ta.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: A monofunctional monomer (
A monofunctional monomer that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization in the presence of a dispersion stabilizing resin that has a polymerizable double bond group that can be copolymerized with A). body (A), 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 the general formula (I), X is -COO-, -OCO-, -C
H_2OCO-, CH_2COO-, -O-, or -S
Represents O_2-. R^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-R^2, or a carbonized group having 1 to 8 carbon atoms. -COO-R^2 (R^2 has 1 or more carbon atoms) via a hydrogen group
22) represents a hydrocarbon group. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In general formula (II), R^3 represents an aliphatic group having 8 or more carbon atoms. Y is -COO-, -CONH-, ▲Mathematical formula, chemical formula, table, etc.▼(R^4 represents an aliphatic group), -OCO
-, -CH_2COO-, or -O-. b^1 and b^2 may be the same or different, and each represents a hydrogen atom, an alkyl group, -COOR^5 or -CH_2
-COOR^5 (R^5 represents an aliphatic group).