JPS61172158A - Liquid developer for electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain an electric charge controller and additive having a wide permissible addition range by using the metallic salt of a specific compd. and specific copolymer resin as well as chlorine-contg. resin in combination. CONSTITUTION:This liquid developer contains at least >=1 kinds of the metallic salt of the compd. expressed by formula (I) or (II) and further the copolymer resin expressed by formula (III) and chlorine-contg. resin. The terminal groups R<1>, R<2> of a carboxylic acid or sulfonic acid have a hydrogen atom, alkyl group, substd. alkyl group, etc. and the bond A is an alkylene group or substd. alkylene group. The copolymer side chains R<3>, R<4> are a hydrogen atom and methyl group and the terminal group R<5> is an alkyl group and subtd. alkyl group. The more particularly preferable example is the copolymer of an acrylic acid and lauryl methacrylate. The more particularly preferable example of the metallic salt is the metallic salt of the metal selected from nickel, titanium, zirconium and cobalt.

Description

DETAILED DESCRIPTION OF THE INVENTION ``Industrial Application Field'' The present invention relates to charge control agents and additives for liquid developers used for developing electrostatic charges.

``Prior art'' Liquid developers conventionally used for this purpose have high electrical resistance (
A colorant such as carbon black or nigrosine is adsorbed or coated in a carrier liquid having a resistance of 709 to 7 o 15Ω・CIK) to adjust the charge of toner particles, promote dispersion, and improve image quality after development. It is prepared by dispersing a toner particle forming resin that contributes to improving the fixing properties of toner particles, a substance that dissolves or swells in a carrier liquid and increases the dispersion stability of toner particles, and a substance that strengthens and stabilizes the charge of toner particles. There is.

Since the charge of toner particles has a large effect on the image after processing, a great deal of effort has been made to stably adjust it, but at present there are roughly two known methods. . The first method is to coat the surface of toner particles with a substance that can ionize or adsorb ions. Materials used for this purpose include fats and oils such as linseed oil and soybean oil, alkyd resins, and halogenated Polymers, Aromatic polycarboxylic acids shown in JP-B 1974-J 4A4A, Acidic group-containing water-soluble dyes shown in JP-B 74-/Cort, JP-A-Sho! Oxidized condensates of aromatic polyamines shown in 0-/koo4kota are known. In this method, since the toner particles themselves have polar groups, it is possible to reduce the ionic components contained in the carrier liquid.
Although it is possible to create a lubricant with excellent current characteristics, there are problems such as it is somewhat difficult to finely adjust the amount of charge, and depending on the material used, the amount of charge may deteriorate significantly over time.

In general, such particles containing many polar groups have a large cohesive force and are difficult to disperse in a concentrated manner, requiring special measures as shown in JP-A-Sho, ts-J17J.

The second method is to coexist with a substance that is dissolved in the carrier liquid and can exchange ions with the toner particles.
Metal soaps such as cobalt naphthenate, nickel naphthenate, and cobalt coethylhexanoate, sulfonic acid metal salts such as calcium dodecylbenzenesulfonate, petroleum-based sulfonic acid metal salts, and metal salts of sulfocoba/fl ester, lecithin, and polyvinylpyrrolidone. Resin, polyamide resin, Tokkosho! ≦-24A sulfonic acid-containing resins described in Reference μ, hydroxybenzoic acid derivatives described in JP-A-77/J-711, and the like are known.

The second method is easy to add a charge control substance, and is the most widely used method that allows fine adjustment of the amount of charge.
In general, since substances that are easily ionized are added, there is a tendency to lower the electrical resistance of the current irrigation agent. As a result, the optimum amount of addition is severely limited, and if it is exceeded, adverse effects such as blurred images and decreased copy density may occur. Furthermore, when a large number of copies are made in succession, so-called fatigue of the developer occurs due to the accumulation of the charge control agent, resulting in a decrease in perceptual density and resolution. Some carrier materials change in quality due to oxidation, etc. during storage, and some even lose their charge control function. By developing an ionic substance that changes little over time and combining several types of additives, we have succeeded in improving the charge control effect and improving the above-mentioned problems.

[Problems to be Solved by the Invention] The first object of the present invention is to provide charge control substances and additives that have a wide range of permissible addition. A second object of the present invention is to provide a liquid developer in which the charge on toner particles has better stability over time and is less tiring due to repeated use.

A third object of the present invention is to provide charge control substances and additives that do not impair the dispersion stability and fixing properties of toners.

"Friendly Means to Solve Problems" In other words, the present inventors have conducted extensive research and found that a metal salt of a compound represented by the following general formula CI) or CH3, a copolymer resin represented by [■], and a chlorine-containing resin It has been discovered that by using a combination of the following, an excellent liquid fixing agent for electrostatic charge friction which eliminates the above-mentioned disadvantages can be obtained.

In the formula, R1 and R2 are a hydrogen atom, an alkyl group having up to 7-2 carbon atoms, a substituted alkyl group (substituents include dialkylamino group, alkyloxy group, and alkylthio group), and an alkyl group having up to 7 to 2 carbon atoms; aryl group, substituted aryl group (substituents include dialkylamino group, alkyloxy group, alkylthio group, chlorine group, bromine group, cyano group, nitro group, hydroxyl group), aralkyl group, carbon number 1 to here Acyl group, alkylsulfonyl group or carbon number 4-
4ct represents a sulfonyl group. RζR3 may be the same or different, and R1-R2
may form a ring, but it cannot become a hydrogen atom at the same time.

A represents an alkylene group having up to 1.10 carbon atoms or a substituent alkylene group.

R3 and Ha represent a hydrogen atom and a methyl group, and R5 represents an alkyl group having a carbon number of .mu. to 2 or a substituted alkyl group (an alkyl group having a carbon number/up to 10 as a substituent). X
The molar ratio of and y is 00O7:0. Tata~o, r:o,
It is Ko.

In the liquid developer of the present invention, fatigue of the developer due to repeated use is significantly improved. Also, the ryotsu property has been improved,
In particular, "fogging" and "image blurring" are slightly reduced.

In the compound of the general formula [Engine] or [■] used in the present invention, it is preferable that the total number of carbon atoms of R1 and R2 shown in the general formula is within the range of r to 3, and which one of R1 and R2 is Preferably, this is an acyl group. Metal salts include calcium, barium, manganese, copper,
Preferred are metal salts of metals selected from lithium, titanium, zinc, lead, zirconium, cobalt, nickel, aluminum, cerium, lanthanum, chromium 1, X)07-) rum, vanadium, tin, magnesium, iron, and cadmium.

Particularly preferred are nickel, titanium, zirconium,
Cobalt) is a metal salt of the selected metal.

As the titanium salt, it is preferable to use a reaction mixture obtained by reacting a compound of the general formula CI] [■] with an organic titanium compound. Examples of organic titanium compounds include compounds represented by the following general formula CM).

RnTtX(4n) (W) where R
6 represents an alkyl group or an aralkyl group, 1t represents an aryl group, X represents a halogen atom or an alkoxy group, and n
represents an integer from 0 to 3.

When n is 0, at least one X is an alkoxy group.

Specific examples include φ tantetrine propoxylate, titanium tetrabutoxide, titanium tetrastearylofoside, diisopropoxytitanium dichloride, triisopropoxytitanium monochloride, diethyltitanium diisopropoxide, diethyltitanium dichloride, titanium diiso dioleate. Examples include propoxide.

From the viewpoint of ease of handling, alkoxides are preferred among these compounds, and titanium tetraisopropoxide is most preferred.

These metal salts are special! I-/-1227, special request! It can be synthesized by the method described in Patent No./7-Ta J'j.

Next, specific examples of metal salts of the compound of general formula (I) or [■] will be given, but the present invention is not limited thereto.

Compound-No Compound-2 Compound-3 zas Compound-4 Compound-! Compound-t 2Hs Compound-7 Various copolymer resins can be used as the copolymer resin represented by the general formula (III), but a particularly preferred one is a copolymer of acrylic acid and lauryl methacrylate with a copolymerization molar ratio of 0. Examples include those where .05=0.2!~o, u:o, t.

Further, the number average molecular weight is desirably 1,000 or 100,000. Examples include the following, but the present invention is not limited thereto.

x/y=0. 10. r copolymer-cox/y=0, co10. l copolymer-3 x/y=o, alo, copolymer-μ x/y=0. 10. f Copolymer - CH3) T 2H5 X / y = 0, / / 0, Ri! As the fC chlorine-containing resin, the following can be preferably used.

Vinyl chloride resin, vinylidene chloride resin, chlorinated polyether resin, chlorinated polyethylene resin, chlorinated polypropylene resin, vinyl chloride propylene copolymer resin, ethylene-vinyl chloride copolymer resin, chlorinated rubber, chlorinated paraffin, etc. Particularly preferred are chlorinated polyethylene and chlorinated polypropylene.

As the coloring agent used in the present invention, it is possible to use pigments and dyes, or both, which have been conventionally used for liquid preservatives and are well known. For example, hen f i x mouth (C1
I, /1410), benzidine yellow G (C, 1, 100), benzidine orange (C, 1, 110)
), First Red (C0 engineering, J70rJr), Brilliant Carmy yJB (c, I, /60/j-Lake
), Phthalocyanine Blue CC, 1, yai≦O), Phthalocyanine Green (C, I, ya2≦O), Victoria Blue (C, i, gcoj P! Lake
), Spirit Black (C,1,!Dulj), Oil Blue (C1■, 74c3jo), Alkali Blue (
C, I, 4ca770 people), 7th Scarlet (
C4,/coJ/Z), rhodamine tf3 (C11,44
! l O), First Skives, -(C11,7
gkooO-Lake), Niproshiy (C0I, 704c
/j), car a; infrastructure 1, etc. Surface treatment, dyeing with pigments such as nigrosine, nine carbon black, graft polymerization with polymers, and then grafting carbon, etc. can also be used to kill the surface. Others include Tokko Akira! 7-795/! A bisarylazo derivative of J-naphthalenediol described in 7-4 AagoK, a formazan dyeing pigment described in Tokko Sho! Also useful are the lake pigments disclosed in Japanese Patent Publication No. 74-4C 1-/$3i, Japanese Patent Publication No. 74-4C 1/2010, and JP-B-J Buri 1/.

Various types of carrier liquids known in the art can be used as the carrier liquid used in the present invention; It is desirable to select a non-aqueous solvent with a molecular weight of 3 or less.For example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, polysiloxanes, etc. can be used, but they are generally volatile.・From the viewpoint of safety, toxicity, odor, etc., Isono (rough-in petroleum solvent) is preferred.Isoparaffin petroleum solvents include Esso's Iso, R-G1 Aituno e H, Isono L, and Isopar with 1 liter petroleum. Examples include Scherzol 7) manufactured by the company.

The developer of the present invention may contain a resin that is insoluble or swellable in the carrier liquid as a resin for forming toner particles. These resins have the effect of being resistant to adhesion to the colorant or forming a coating film around it to promote the dispersion of the colorant,
It has the effect of improving the fixability of the developer by acting as a binder for the colorant after the development process.

As the resin, many types of known resins can be used, including rubbers such as butadiene rubber, styrene-butadiene rubber, cyclized rubber, and natural rubber, styrene resins,
Synthetic resins such as vinyltoluene resin, acrylic resin, methacrylic resin, polyester resin, polycarbonates, polyvinyl acetate, rosin resin, hydrogenated rosin resin, alkyd containing modified alkyd such as linseed oil modified alkyd Examples include natural resins such as resins and polyterpenes. Other phenolic resins including modified phenolic resins such as phenol-formalin resins, natural resin-modified maleic acid resins, pentaerythritol phthalate, chroman-indene resins, ester gum resins,
Vegetable oil polyamides and the like are also useful.

Known dispersants can be used to enhance the dispersibility of the present preparation. The dispersant is a resin that dissolves or swells in the high electrical resistance non-aqueous solvent used in the developer of the present invention and improves the dispersibility of the toner, such as styrene-butadiene rubber, vinyltoluene-butadiene, butadiene-butadiene rubber, etc. Synthetic rubbers such as isoprene, polymers of acrylic monomers with long chain alkyl groups such as coethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, lauryl acrylate, octyl acrylate, or combinations thereof with other polymerizable monomers. Copolymers (for example, styrene-lauryl methacrylate copolymer, vinyltoluene-lauryl methacrylate copolymer, etc.), polyolefins such as polyethylene, polyterpenes, etc. can be used. Other Tokukai Sho Jr4A-J/7
Polymers containing primary ammonium salt monomers as disclosed in No. 3 are also useful.

Although not necessarily required, a known charge control agent can be used in combination with the developer of the present invention. Suitable examples include metal salts of fatty acids such as naphthenic acid, octenoic acid, oleic acid, stearic acid, isostearic acid or lauric acid; metal salts of sulfosuccinic acid esters;
rr5 Tokukai Sho! Co374t31. Tokukai Akira! λ-370
Oil-soluble sulfonic acid metal salts shown in 4t, etc., Tokko Showl! -Metal salts of phosphoric acid esters shown in Buddha from Ta, Tokko Show φr-Jjbut≦ Metal salts of abietic acid or hydrogenated abietic acid, Tokko Show! j
- Alkylbenzenesulfonic acid Ca salts shown in
JIr? J7, JP-A-37-206+! , Japanese Patent Application Publication No. 77-
The aromatic carboxylic acids shown in 7J-J, etc. are metal salts of sulfonic acids, nonionic surfactants such as polyoxyethylated alkylamines, oils and fats such as lecithin and linseed oil, Polyvinylpyrrolidone, organic acid ester of polyhydric alcohol, oil-soluble phenol resin shown in Japanese Patent Publication No. 5f97--IOJ
The phosphate ester surfactant shown in gj, Tokukosho! Examples include sulfonic acid resins shown in 4-2μ2aa.

The developer of the present invention can be produced by a conventionally known method. An example of the manufacturing method is shown below.

First, a coloring agent consisting of a pigment or a dye, or both, and the above-mentioned resin for forming toner particles are kneaded in a parent solvent of the resin using a mixing machine such as a ball mill, a roll mill, or an int shaker, and then heated, etc. The processing solvent is removed to obtain a blend.

Alternatively, the mixture is poured into a liquid that does not dissolve the resin, and a mixture is obtained by reprecipitation.

Alternatively, the coloring agent and the resin are kneaded using a mixing machine such as a kneader-1 three-roll mill while heating to a temperature higher than the melting point of the resin, and the mixture is cooled to obtain an Eri mixture.

The thus obtained mixture is dry pulverized or wet pulverized together with a dispersant to obtain a toner concentrate. The solvent during wet grinding may be a carrier liquid or
Add l- to the parent solvent of the above resin such as toluene or acetone.
It may be added in an amount of 20% by weight.

The toner concentrate thus obtained is dispersed in a nonaqueous solvent solution containing the charge control agent of the present invention to prepare a liquid developer for electrostatic images. The concentration of toner particles in the developer is not particularly limited, but is usually 0.0/l to carrier liquid/l.
f, 100f, preferably 0. /f, 10f. Note that the charge control agent of the present invention may be added by an addition method other than the above-mentioned method. That is, it may be added during cross-mixing or wet pulverization, or they may be used in combination. The concentration of the charge control agent of the present invention is determined in the final usage form in the developer l! It is desirable to adjust the range to include o, ooiy, and toy, and more preferably in the range of 0° oty to /f. Further, b of the general formula CI) of the charge control agent of the present invention is [I
] The metal salts of the compounds represented by these may be used alone or in combination.

The compound represented by the general formula (m) can be added in the same manner as the charge control agent, but if it is insoluble in the Φ Yarya liquid, it can also be added by dissolving it in toluene or the like and then adding it downward.

The concentration of the compound represented by general formula (III) is developer/l
It is desirable that 0.0001-co is included.

More preferably, the range is o, oat, iy.

Examples of methods for adding the chlorine-containing resin include the following methods.

(1) A method of mixing and kneading the colorant, the fixing resin, and the chlorine-containing resin in a mixer such as a T-ball mill, a roll mill, or a pamper.

(2) A method in which the toner is dissolved in a carrier liquid or a suitable solvent such as toluene and added during or after the preparation of the toner concentrate.

(3) Method of adding to the working solution after dilution in the same manner as in (2).

The concentration of chlorine-containing resin added is 0.00 per liter of developer.
It is desirable to adjust it so that it contains 0/~zy.

More preferably, it is in the range of 0.0/~3t.

The developing agent of the present invention can be used for photoconductors using well-known organic photoconductors and inorganic photoconductors. (9) The developer of the present invention can also be used to develop a static latent image produced by a means other than photosensitivity, such as by charging a dielectric material with a charging needle.

Organic photoconductors include a wide variety of well-known organic photoconductors. A specific example is rResearchDisclosure
ej magazine #1OriJ! (Article entitled "Electrophotographic Elements, Materials and Processes," published on page 4 of the 1973 J issue).

Examples of those in practical use include electrophotographic photoreceptors made of poly-N-vinylcarbashield'v''*7-dolinitrofluorene-?-one (U.S. Patent J, 4t14A, 2Jf); -N-vinylcarbazole sensitized with all pyrylium salt dye (Tokuko Sho μ
l-coz4zt), an electrophotographic photoreceptor whose main component is an organic pigment (Japanese Patent Application Laid-open No. 2003-110012), an electrophotographic photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (Japanese Patent Application Laid-open No. 4
17-1073 etc.

The inorganic photoconductor used in the present invention is “Elect
rophotographyJ R,M.

5chaffert, Focal Press (L
ondon) Publication (1970) Coto page ~ 37μ
Representative examples include various inorganic compounds disclosed in, for example, p. Specific examples include zinc oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium alloy, selenium-arsenic alloy, selenium-tellurium-arsenic alloy, and the like.

"Example" Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these examples.Example-1 The above composition g was dispersed in a ball mill for 7 days and nights, and the mixture was (manufactured by Esso) and the precipitate was separated.

This was mixed with a solution in which parts by weight of Turprene 1201 (styrene-butadiene copolymer manufactured by Asahi Kasei ■) was dissolved in parts by weight of Isopar HuO, and dispersed day and night in a ball mill to obtain a toner concentrate. The average particle diameter was measured with a Nanosizer (manufactured by Coulter) and was found to be 0.31μ.

Next, dilute the developer (liquid used) to the following concentration.
-I got it.

Developer A Developer B for comparison Developer A has exactly the same composition except that chlorinated polyethylene was removed.

Developer C for comparison A developer obtained by removing the copolymer resin -λ from developer A.

Comparative developer: Developer A obtained by removing copolymer-2 and chlorinated polyethylene.

Next, poly-N-vinylcarbazole (PVCz) 10
0 parts by weight, 3 parts by weight of vinylidene chloride-acrylonitrile copolymer, 3 parts by weight of styrene-butadiene copolymer, λ
, 6-di-t-butyl≠-C≠-(N,N-dichloroethylamino)styryl]thiapyryliumtetrafluorobole)i/.

Dissolve the solution in λ-dichloroethane 2000- to a thickness of z
100 μm thick with onm I n 203 deposited layer
polyethylene terephthalate (PET) film (I
After coating (N203 conductive PET film), drying to remove the solvent, thickness! An electrophotographic film was prepared by providing a .mu.m photoconductive layer.

+J on the surface of this film! OV! /c was charged and Ryotsu exposure was applied through the positive original to produce an electrostatic latent image.

This electrostatic latent image was developed using the developer A, B, C, In-.

Images A, B, and D gave clear images with no image blurring, but image color C had low image density and image blurring occurred.

Next, use A%B and D developers! After forced aging at 0°C/week, a similar test was carried out.

Developer D caused image blurring, and developer B produced clear images that were almost the same as before forced aging.

Next, each of these developers A and BE is l! An original pattern with an image area t and a tucyt "blackening" 4λ0% is continuously printed on / 000 sheets so that Dmax /, j is used (running test).

In the case of developer A, the decrease in Dmax is determined by setting the initial value t-1oo to 3. On the other hand, in the case of B, the number has dropped to 7.

It was found that the developer A of the present invention has good electrophotographic image characteristics, shows little change in forced aging characteristics, and satisfies running properties, and is a good developer.

Example 2 A concentrated toner solution having the following composition was prepared in the same manner as in Example 1.

Next, use the above toner concentrated solution to re-in the following concentration.
When the image was developed in the same manner as in Example 1 of Gupto/1, a clear image was obtained with no image drift or double images occurring around lines or characters.

A running test was carried out in the same manner as in Example 1, and it was found that the decrease in Dmax started from 100 at the initial stage and remained at yoVc, whereas when chlorinated polypropylene was added to the developer, it decreased to Aj.

Example 3 The above composition was subjected to a dispersion treatment for 100 hours in a ball mill, and then the solvent was distilled off to obtain a lump consisting of a colorant and a resin.

Next, after coarsely pulverizing this, Turprene/201 was dissolved in 7 parts by weight of Inpar Hioo, mixed with a diluted solution, and subjected to IZO time dispersion treatment in a ball mill to obtain a toner concentrated solution.

Next, prepare the developer (liquid used) to the following concentration.
I got it.

Using this developer, the electrophotographic photosensitive film shown in Example 1 was developed in the same manner as in Example 1, and a clear and pure black image was obtained in nine areas.

When this developer was left at room temperature for a month and then processed, no deterioration in image quality was observed.

Further, as an evaluation of dispersion stability, the sedimentation property of the toner was observed at the same time, and a trace amount of sediment was observed in some places.

Next, a running test was carried out using the method of Example 1, and it was found that there was almost no decrease in density and the running properties were excellent (rl after running when the initial image density was t-100).

On the other hand, the LM developer that does not contain chlorinated paraffin shows almost the same image staining and toner sedimentation properties other than running properties, but its running properties are inferior (lower to 72 compared to the initial image density of ioo). .

Example 4 The above composition solution was dispersed in a ball mill for 3 days and nights, and then toluene was distilled off. This was coarsely ground, mixed with a solution of 2 parts by weight of Nluprene/205 (5t-Bu copolymer manufactured by Asahi Kasei ■) dissolved in 4 parts by weight of Isopar 0, and dispersed in a ball mill for 110 hours to obtain a toner concentrate. The average particle diameter was measured with a Nanosizer (manufactured by Coulter) and was found to be 0. It was Hirojmu.

Next, using the above toner concentrated solution, make BS of the following concentration.
Paper) was charged with a corona discharge of -6 KV, and after image exposure, a reversal development operation was performed using the developer described above, and a clear reversal image was obtained. As in the other examples, the developer of the present invention has superior running performance compared to the developer containing no chlorinated polypropylene.90 In similar experiments, chlorinated polypropylene and copolymer -j-AFI+! -Volume 14 Tax Fake Power Electricity - Needle Powder Soso I Pregnancy Confirmed that pregnancy was inferior.

As is clear from the above examples, charge control agents such as Compounds -1 to -7 alone have a problem in aging properties, but by combining them with copolymer resins -/ and j, the aging properties can be improved. A good friend. However, there is a problem with running performance.

The solution to this problem is the combination of the three with a chlorine-containing resin.

On the other hand, when a charge control agent is used in combination with a chlorine-containing resin, the image properties are significantly inferior (image slag running, low image density).

Normal image quality can only be achieved by the combination of the three,
This makes it possible to improve practicality such as stability over time and running performance.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment λ month d day, 1985

Claims (5)

[Claims] (1) It is characterized by containing at least one kind of metal salt of a compound represented by the following general formula [I] or [II], and further comprising a copolymer resin represented by the general formula [III] and a chlorine-containing resin. Liquid developer for electrostatic images. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1, R^ 2 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a substituted alkyl group (as a substituent, a dialkylamino group, an alkyloxy group, an alkylthio group)
, an aryl group having 6 to 24 carbon atoms, a substituted aryl group (
Substituents include dialkylamino group, alkyloxy group, alkylthio group, chloro group, bromo group, cyano group, nitro group, hydroxyl group), aralkyl group, and carbon number 1 to
It represents an acyl group of up to 22, an alkylsulfonyl group or an arylsulfonyl group having from 6 to 24 carbon atoms. R^1R
^2 may be the same or different, R^
1-R^2 may form a ring, but it cannot become a hydrogen atom at the same time. A represents an alkylene group or substituted alkylene group having 1 to 10 carbon atoms. R^3 and R^4 represent a hydrogen atom or a methyl group, and R^5 represents an alkyl group having 4 to 22 carbon atoms or a substituted alkyl group (an alkyl group having 1 to 10 carbon atoms as a substituent). The molar ratio of x and y is 0.01:0.99 to 0.8:0
．． It is 2. (2) The electrostatic charge according to claim 1, wherein the metal is a metal salt of a compound of general formula [I] or [II] and a metal selected from Ni, Ti, Zr, and Co. Liquid image developer. (3) The electrostatic charge image according to claim (1), wherein the metal salt is a reaction mixture obtained by reacting the compound of general formula [I] or [II] with an organic titanium compound. liquid developer. (4) The copolymer resin of general formula [III] is a copolymer of acrylic acid or methacrylic acid and lauryl methacrylate, and the copolymerization molar ratio x:y is 0.05:
The liquid developer for electrostatic images according to claim (1), characterized in that the ratio is in the range of 0.95 to 0.4:0.6. (5) The liquid developer for electrostatic images according to claim (1), wherein the chlorine-containing resin is chlorinated polyethylene or chlorinated polypropylene.