JPH087468B2 - Liquid developer for electrostatic photography - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid developer for electrostatography comprising at least a resin dispersed in a carrier liquid having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5. In particular, the present invention relates to a liquid developer having excellent redispersibility, storage stability, stability, image reproducibility, and fixability.

(Prior Art) A general liquid developer for electrophotography is an organic or inorganic pigment or dye such as carbon black, nigrosine or phthalocyanine blue and a natural or synthetic resin such as alkyd resin, acrylic resin, rosin or synthetic rubber, which are petroleum-based. A polar control agent such as a polymer which is dispersed in a liquid having a high insulating property and a low dielectric constant such as an aliphatic hydrocarbon and further contains a metal soap, lecithin, linseed oil, a higher fatty acid and a polymer containing vinylpyrrolidone. In such a developer, the resin is dispersed as insoluble latex particles in the form of particles having a diameter of several nm to several hundreds nm, but in a conventional liquid developer, a soluble dispersion stabilizing resin, a polarity control agent and insoluble latex particles are used. Due to insufficient bonding of the above, the soluble dispersion stabilizing resin and the polarity control agent were in a state of being easily diffused in the solution. For this reason, there has been a drawback that the soluble dispersion stabilizing resin is desorbed from the insoluble latex particles by long-term storage and repeated use, and the particles settle, aggregate, and accumulate, or the polarity becomes unclear. Further, since particles once aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to the failure of the developing machine such as dirt on the image area and clogging of the liquid feeding pump. In order to improve these drawbacks, means for chemically bonding the soluble dispersion stabilizing resin and the insoluble latex particles have been devised and disclosed in US Pat. No. 3,990,980. However, the dispersion stability of these liquid developers against spontaneous sedimentation of particles has been improved to some extent, but it is still insufficient, and when used in an actual developing device, the toner adhered to each part of the device becomes a coating film. In addition, it is difficult to re-disperse, and furthermore, it is not sufficient for re-dispersion stability which can be used practically, for example, it causes a failure of the apparatus, stains of a copied image, and the like. In the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle distribution, there is a remarkable restriction on the combination of a dispersion stabilizer to be used and a monomer to be insolubilized. The resulting particles were large in particle size distribution containing a large amount of coarse particles, or polydispersed particles having two or more average particle diameters. In addition, it was 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 were formed. Furthermore, the dispersion stabilizer used is
There is a problem in that it must be manufactured through a manufacturing process that is frequent and requires a long time.

Further, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of an insolubilizing monomer and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components, The method for improving the dispersity, redispersibility, and storage stability of the particles is disclosed in JP-A-60-179751 and JP-A-62-15.
It is disclosed in 1868 and the like.

(Problems to be Solved by the Invention) On the other hand, in recent years, using a master plate for offset printing by an electrophotographic method, a method of printing a large number of 5000 or more sheets has been attempted. It has become possible to print more than 10,000 sheets in plate size. Further, the operation time of the electrophotographic plate making system has been shortened, and the speeding up of the process of fixing the development has been improved.

Dispersed resin particles produced according to the means disclosed in JP-A-60-179951 and JP-A-62-151868, when the developing speed is increased, the dispersibility of the particles, in terms of redispersibility, also fixed. In the case where the time was shortened or in the case of a large plate size (for example, A-3 size or more) master plate, the performance was not always satisfactory in terms of printing durability.

The present invention improves the problems of the conventional liquid developers described above.

An object of the present invention is to provide a liquid developer which has a stable development fixing step and is excellent in dispersion stability, redispersibility and fixing property even in an electrophotographic plate making system using a large plate size master plate. That is.

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

Another object of the present invention is to provide a liquid developer suitable for various kinds of electrophotography and various kinds of transfer 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 ink jet recording, cathode ray tube recording, and recording of various change processes such as pressure change or electrostatic change. That is.

(Means for Solving the Problems) An object of the present invention is to have an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant.
In a non-aqueous solvent of 3.5 or less, in a liquid developer for electrophotography comprising at least a resin dispersed, the dispersed resin particles,
At least one polar group selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group and a phospho group is bonded to only one end of the main chain of a polymer containing a repeating unit represented by the following general formula (I). In the presence of a dispersing resin having a weight average molecular weight of 1 × 10 ⁴ or more, which is soluble in a non-aqueous solvent but is insolubilized by polymerization, and a monofunctional monomer (A) The polymer having a repeating unit represented by the formula (II) has a number average molecular weight of 1 × 10 ^{4 which} is obtained by bonding the polymerizable double bond group represented by the following general formula (III) to only one end of the main chain. The following is achieved by a liquid developer for electrostatic photography, which is a copolymer resin particle obtained by polymerizing a solution containing at least one monofunctional macromonomer (B) below. Is found .

General formula (I) In the formula (I), X is -COO -, - OCO -, - CH 2 OCO -, -
CH ₂ COO -, - O- or -SO ₂ - represent.

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

a ₁ and a ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Z or a hydrocarbon group having 1 to 8 carbon atoms. Through -COO-Z (Z represents a hydrocarbon group having 1 to 22 carbon atoms).

General formula (II) Wherein (II), V is -COO -, - OCO -, - CH 2 OCO -, -
_{CH 2 COO -, - O -} , - SO 2 -, (R ₁₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

 W represents a hydrocarbon group having 1 to 22 carbon atoms.

b ₁ and b ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Q or a hydrocarbon group having 1 to 8 carbon atoms. Represents -COO-Q (wherein Q represents a hydrocarbon group having 1 to 18 carbon atoms).

General formula (III) In the formula (III), V ′ has the same meaning as V in the formula (II).

c ₁ and c ₂ may be the same or different from each other, and each is b ₁
Or synonymous with b ₂ .

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

As the carrier liquid having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less used in the present invention, linear or branched resin group hydrocarbons, alicyclic hydrocarbons or aromatic hydrocarbons and these are preferable. Halogen substitutes can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; a product of Exxon) Name), Shersol 70, Shersol 71 (Shersol; trade name of Shell Oil Company), AMSCO OM
S, Amsco 460 solvent (Amsco; trade name of Spirits), etc. are used alone or in combination.

Non-aqueous dispersion resin particles, which are the most important components in the present invention (hereinafter sometimes referred to as latex particles)
Is a monomer (A) and a non-aqueous solvent in the presence of a dispersion stabilizing resin having a weight average molecular weight of 1 × 10 ⁴ or more, which is formed by bonding a polar group only to one end of the polymer main chain. It is produced by polymerizing and granulating by copolymerizing the macromonomer (B).

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

That is, the solvent used for producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. Hydrogen and halogen-substituted products thereof are exemplified. For example, hexane, octane, isooctane, decane, isodecane, decalin, inane, dodecane, isododecane, Isopar E, Isopar G, Isopar H, Isopar L, Cielsol 70, Cielsol 71, Amsco OMS, Amsco 460 solvent, etc., alone or in combination. To use.

Solvents that can be used in combination with these organic solvents include alcohols (eg, methyl alcohol,
Ethyl alcohol, propyl alcohol, butyl alcohol, fluoroalcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), carboxylic acid esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate) ,
Ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg,
Methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methylchloroform, etc.) and the like.

The non-aqueous solvent used as a mixture of these, after the polymerization granulation,
It is desirable to evaporate under heating or under reduced pressure.However, as a latex particle dispersion, even if brought into the liquid developer, there is a problem if the liquid resistance of the developer can satisfy the condition of 10 ⁹ Ωcm or more. No.

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

The dispersion-stabilizing resin of the present invention used for forming a stable resin dispersion of the solvent-insoluble copolymer produced by copolymerizing the monomer in a non-aqueous solvent, is polymerized with the monomer. It is a resin not containing a graft group, and has a carboxy group, a sulfo group, a phospho group, a hydroxyl group and an amino group only at one end of a polymer main chain containing at least one repeating unit represented by the general formula (I). It is a polymer formed by bonding at least one polar group selected.

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

In the general formula (I), X is preferably -COO-, -O.
_{CO -, - CH 2 OCO -} , - CH 2 COO- or represents -O-, more preferably -COO -, - represents a CH ₂ COO- or -O-.

Y preferably represents an optionally substituted alkyl group, alkenyl group or aralkyl group having 8 to 22 carbon atoms. The substituent may be any substituent other than a polar group bonded to one end of the polymer main chain, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), -O-Z _{1, -COO-Z 2, -OCO} -Z 2 (Z 1, Z 2 represents an alkyl group having 6 to 22 carbon atoms, e.g., hexyl, octyl, decyl, dodecyl, hexadecyl group, octadecyl Group) and the like. More preferably, Y represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. Examples thereof include an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and a docosanyl group.

a ₁ and a ₂ may be the same or different from each other, and preferably a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms, —COO. -Z or -CH ₂ COO-Z (Z is an aliphatic group of carbon number 1 to 22) represent. More preferably, a ₁ and a ₂
May be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -COO-Z or -CH ₂ COO-Z (Z is more It preferably represents an alkyl group or an alkenyl group having 1 to 18 carbon atoms, for example, a methyl group, an ethyl group, a propyl group,
Butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, pentenyl group, hexenyl group, octenyl group, decenyl group and the like, these alkyl groups, alkenyl groups It may have the same substituents as those shown for Y).

Further, the polar group bonded only to one end of the polymer main chain has a chemical structure directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

As the bonding group, a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom bond It is composed of any combination of atomic groups. For example, [R ₁ and R ₂ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) ], CH = CH, -O-, -S-, −COO−, −SO ₂ −, -NHCOO-, -NHCONH-, [R ₃ represents a hydrogen atom, or a hydrocarbon group having the same meaning as Z represented by the general formula (I), etc.] or a single linking group selected from atomic groups or any combination thereof. Examples of the bonding group are as follows.

The polymer component of the resin for dispersion of the present invention corresponds to the homopolymer component or copolymer component selected from the repeating units represented by the general formula (I) or the repeating unit represented by the general formula (I). It is composed of a copolymer component obtained by polymerizing the above monomer with another monomer that can be copolymerized. Examples of the other monomer serving as the copolymer component together with the polymer component of general formula (I) include compounds represented by general formula (IV) described later.

The repeating unit represented by the general formula (I) is 30% by weight to 100% by weight in the resin polymer for dispersion used in the present invention.
Wt% is suitable, preferably 50-100 wt%
Is.

In the polymer main chain, a carboxyl group, a sulfo group,
Those which do not contain a copolymerization component containing polar groups such as hydroxyl group, amino group and sulfo group are preferred.

The dispersion stabilizing resin of the present invention in which a specific polar group is bonded only to one end of the polymer main chain is a method of reacting various reagents with the end of a living polymer obtained by conventionally known anionic polymerization or cationic polymerization. (Method by ionic polymerization method), method of radical polymerization using polymerization initiator and / or chain transfer agent containing specific polar group in molecule (method by radical polymerization method), or ionic polymerization method as described above or It can be easily produced by a synthetic method such as a method of converting a polymer having a reactive group at a terminal obtained by a radical polymerization method into a specific polar group of the present invention by a polymer reaction.

Specifically, P.Dreyfuss, RPQuirk, Encycl.Polym.Sc
Review articles such as i.Eng, 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986), etc. It can be produced by the method described in the cited document or the like.

The dispersion stabilizing resin of the present invention has a weight average molecular weight of 1 × 10 ⁴ to
1 × 10 ⁵ is preferable, and more preferably 1.5 × 10 ⁴ to 8 × 10 ⁴
Is. If the weight average molecular weight is less than 1 × 10 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, 0.5
(beyond μm) and the particle size distribution becomes wider. Also,
If it exceeds 1 × 10 ⁵ , the average particle size of the resin particles obtained by polymerization granulation becomes large, and it may be difficult to make the average particle size within the preferable range of 0.2 to 0.4 μm.

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

Monomers used in producing the non-aqueous dispersion resin,
It is possible to distinguish between a monofunctional monomer (A) that is soluble in the solvent but is insolubilized by polymerization, and a monofunctional macromonomer (B) that causes copolymerization with the monomer (A). it can.

The monomer (A) in the present invention may be any monofunctional monomer which is soluble in a non-aqueous solvent but insolubilized by polymerization. Specific examples include a monomer represented by the general formula (IV).

General formula (IV) Wherein, T is -COO -, - OCO -, - CH 2 OCO -, - CH 2 COO
-, -O-, Or [U represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group). 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.) R is A hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group, 2,2,2 -Trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
-Cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group , Trimethoxysilylpropyl group, 3-bromopropyl group, 4-
Hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl Group, 3-sulfopropyl group, 4-sulfobutyl group, 2
-Carboxyamidoethyl group, 3-sulfamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

d ₁ and d ₂ may be the same as or different from each other, and each has the same content as a ₁ or a ₂ in the general formula (I).

Specific examples of the monomer (A) include, for example, 1 to 1 carbon atoms.
Unsaturation of vinyl esters or allyl esters of aliphatic carboxylic acids of 6 (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.), acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Alkyl esters or amides of carboxylic acid having 1 to 4 carbon atoms which may be substituted (eg, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group) Group, trifluoroethyl group, 2-hydroxyethyl group, 2
-Cyanoethyl group, 2-nitroethyl 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-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
Chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxamidoethyl group, etc.), styrene derivative (eg, styrene, vinyltoluene, α-methyl) Styrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylethylene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, Vinylbenzenesulfoamide), unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or maleic acid, cyclic anhydrides of itaconic acid, acrylonitrile, methacrylonitrile, Heterocyclic compounds containing a compatible double bond group (specifically, for example, compounds described in "Polymer Data Handbook-Basic Edition", edited by The Polymer Society of Japan, p175-184, Baifukan (1986), N-vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone, vinyl thiophene, vinyl tetrahydrofuran, vinyl oxazoline, vinyl thiazole, N-vinyl morpholine and the like).

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

The monofunctional macromonomer (B) can be copolymerized with the monomer (A) only at one terminal of the main chain of the polymer comprising the repeating unit represented by the general formula (II). ) Is a macromonomer having a number average molecular weight of 10 ⁴ or less formed by bonding a polymerizable double bond group.

In the general formulas (II) and (III), b ₁ , b ₂ , V, W and c
_The hydrocarbon groups contained in ₁ , c ₂ and V ′ each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted, formula (II) In the above, R ₁₁ in the substituent represented by V is a hydrogen atom,
The preferred hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group,
2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc., alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group) , 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7
To 12 optionally substituted aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group) , A methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), and an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.),
Or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, 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, butoxycarbonylphenyl group, acetamidophenyl group , A propioamidophenyl group, a dodecyloylamidophenyl group, etc.).

V is When represented by, the benzene ring may have a substituent.
Examples of the substituent include a herogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.) and the like.

W preferably represents a hydrocarbon group having 1 to 18 carbon atoms,
Specifically, the same contents as those described for R ₁₁ above are represented.

b ₁ and b ₂ may be the same or different from each other, and are preferably each a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (eg, methyl Group, ethyl group, propyl group, etc.),-
COO-Q or -CH ₂ COOQ (Z is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, Specifically, it represents the same contents as those described for R ₁₁ ).

In the formula (III), V ′ has the same meaning as V in the formula (II), and c ₁ and c ₂ may be the same or different from each other,
It has the same meaning as b ₁ or b ₂ in the above formula (II). V ', c ₁ and
The preferred range of c ₂ is the same as that described for V, b ₁ and b ₂ above.

More preferably, either one of b ₁ and b _{2 in} formula (II) or c ₁ and c ₂ in formula (III) is a hydrogen atom.

The macromonomer used in the present invention is, as described above, a polymerizable double bond represented by the general formula (III) only at one end of the polymer main chain composed of the repeating unit represented by the general formula (II) The groups have a chemical structure that is directly bonded or bonded by an arbitrary linking group. Examples of the group connecting the component of the formula (II) and the component of the formula (III) include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (for example, an oxygen atom,
Sulfur atom, nitrogen atom, silicon atom, etc.), hetero atom-
It is composed of any combination of heteroatom-bonded atomic groups.

Preferred among the macromonomers (B) of the present invention are those represented by the formula (V).

Equation (V) In the formula (V), b ₁ , b ₂ , c ₁ , c ₂ , V, W and V'represent the same contents as those described in the formula (II) and the formula (III), respectively.

T is a simple bond or [R ₂₁ and R ₂₂ represent a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (eg, methyl group, ethyl group, propyl group, etc.), etc. ], CH = CH, -O-, -S-, −COO−, −SO ₂ −, -NHCOO-, -NHCONH-, [R ₂₃ represents a hydrogen atom or a hydrocarbon group having the same content as R ₁₁ ] or the like, and represents a single linking group selected from atomic groups or a linking group composed of any combination.

The upper limit of the number average molecular weight of macromonomer (B) is 1 x 10
_If it exceeds ₄ , printing durability will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so 1 × 10 ₃ or more is preferable.

In the general formula (II), (III) or (V), particularly preferable examples of V, W, U, b ₁ , b ₂ , d ₁ and d ₂ are shown below.

The V e -COO -, - OCO -, - O -, - CH 2 COO-
Or —CH ₂ OCO—, W is an alkyl group or an alkenyl group having a carbon number of 18 or less, and V ′ is all of the above (provided that R ₁₁ is a hydrogen atom), b ₁ , b ₂ ,
Examples of c ₁ and c ₂ include a hydrogen atom and a methyl group.

The macromonomer (B) of the present invention can be produced by a conventionally known synthesis method. For example, by reacting various reagents with the ends of a living polymer obtained by anionic polymerization or cationic polymerization, a macromer, a method by an ionic polymerization method, a caboxyl group,
Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a hydroxy group and an amino group, various reagents are reacted with an oligomer having a terminal reactive group bond obtained by radical polymerization to form a macromer. Examples of the method include a radical polymerization method, a polyaddition condensation method of introducing a polymerizable double bond group into a trigomer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method.

Specifically, P.Dreyfuss & RPQuirk, Encycl, Poly
m.Sci.Eng. , 7,551 (1987), PFRempp, E.Franta, Adu.,
Polym.Sci. 58, 1 (1984), V.Percec, Appl., Polym.Sci.
285, 95 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Sup
pl. 12 , 163 (1985), P.Rempp, etal, Makvamol.Chem.Supp
l. 8, 3 (1984), Kawakami press, chemical industry, 38, 56 (1987),
Yuya Yamashita, polymer, 31,988 (1982), Shiro Kobayashi, polymer, 30, 625 (1981), Higashimura Satoshinobe, Journal of the Adhesion Society of Japan, 18, 536
(1982), Koichi Ito, polymer processing, 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda, functional materials, according to the method described in the review, such as 1987 Nanba10,5 and it references the literature, patents, etc. Can be synthesized.

Specific examples of the macromonomer (B) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

The dispersion resin of the present invention comprises at least one of each of the monomer (A) and the macromonomer (B). What is important is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. Thus, a desired dispersion resin can be obtained. More specifically, the macromonomer (B) is preferably used in an amount of 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight, based on the insoluble monomer (A). Still more preferably, it is 0.3 to 3% by weight. The molecular weight of the dispersion resin of the present invention is 10 ³ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersion resin used in the present invention as described above, generally, the dispersion stabilizing resin and the monomer (A) as described above are used.
The macromonomer (B) may be heat-polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and bityl lithium. Specifically, a method for adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (A) and a macromonomer (B),
A method of dropping the monomer (A) and the macromonomer (B) together with a polymerization initiator into a solution in which the dispersion stabilizing resin is dissolved, or the total amount of the dispersion stabilizing resin, the monomer (A) and the macromonomer. A method of optionally adding the remaining monomer mixture together with the polymerization initiator to a mixed solution containing a part of the mixture of (B), and further, adding the dispersion stabilizing resin and the monomer to a non-aqueous solvent. There is a method of optionally adding the mixed solution together with the polymerization initiator, and any method can be used for production.

The total amount of the monomer (A) and the macromonomer (B) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous solvent.

The amount of the soluble resin serving as 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 amount of the polymerization initiator is 0.1 to 5% (weight) of the total amount of the monomers.
Is appropriate.

The weight temperature is about 50 to 180 ° C, preferably 60.
~ 120 ° C. The reaction time is preferably 1 to 15 hours.

In the non-aqueous solvent used in the reaction, the alcohols described above,
When a polar solvent such as ketones, ethers and esters is used in combination, or when unreacted monomers (A) and macromonomers (B) to be polymerized and granulated remain, the solvent or a single amount thereof It is preferably removed by heating at a temperature higher than the boiling point of the body and distilling off, or by distilling under reduced pressure.

The non-aqueous dispersion resin produced according to the present invention as described above exists as fine particles having a uniform particle size distribution and, at the same time, exhibits very stable dispersibility, and is particularly repeatedly used for a long time in a developing device. However, even if the dispersibility is good and the developing speed is improved, re-dispersion is easy, and no adhesion stain is found on each part of the apparatus.

Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited.

Furthermore, the liquid developer of the present invention is excellent in dispersion stability, redispersibility, and fixability even when the constant development process is accelerated and a master plate having a large plate size is used.

A colorant may be used if necessary in the liquid developer of the present invention.

The colorant is not particularly specified, and various conventionally known pigments or dyes can be used.

When the dispersed resin itself is colored, for example, as one of coloring methods, there is a method of physically dispersing it in a dispersed resin by using a pigment or a dye, and many pigments or dyes to be used are known. There is. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red, phthalocyanine blue and the like can be mentioned.

As another method of coloring, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, there is a method in which a dispersing resin and a dye are chemically bonded as disclosed in JP-A-53-54029.
As described in JP-A-44-22955 and the like, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Various additives may be added to the liquid developer of the present invention as needed in order to enhance charging characteristics or improve image characteristics. For example, Yuji Harazaki "Electrophotography" Vol. 16, Vol. No. 4, p.44 is used.

For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin,
Examples include poly (vinylpyrrolidone) and a copolymer containing a semi-maleic acid amide component.

The amount of each main component of the liquid developer of the present invention will be described below. Toner particles mainly composed of a resin and optionally a colorant are 0.5 parts by weight with respect to 1000 parts by weight of a carrier liquid. Part to 50
Parts by weight are preferred. If the amount is less than 0.5 parts by weight, the image density is insufficient, and if it exceeds 50 parts by weight, fog is easily generated in the non-image part. Further, the carrier liquid soluble resin for stabilizing the dispersion is also used if necessary. 0.5 for 1000 parts by weight
About 100 to 100 parts by weight can be added. The charge control agent as described above is preferably 0.001 to 1.0 parts by weight per 1000 parts by weight of the carrier liquid. Further, various additives may be added if necessary, and the upper limit of the total amount of these additives is restricted by the electric resistance of the developer. That is, the electric resistance of the liquid developer from which the toner particles have been removed is 10 ⁹ Ωcm.
If the value is lower, it is difficult to obtain a high quality continuous tone image. Therefore, it is necessary to control the amount of each additive within this limit.

(Examples) Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto.

Production Example 1 of Dispersion Stabilizing Resin A mixed solution of 100 g of octadecyl methacrylate, 150 g of toluene and 50 g of isopropanol was heated to 70 ° C. while stirring under a nitrogen stream. 5.0 g of 2,2'-azobis (cyanovaleric acid) (abbreviation ACV) was added and reacted for 8 hours. After cooling, it was reprecipitated in 2 l of methanol, and the white powder was collected by filtration and dried to give a weight average molecular weight (hereinafter referred to as w) of 26,00 with a yield of 85 g.
0 powder was obtained.

Production Example 2 of dispersion stabilizing resin A polymerization reaction was carried out in the same manner as in Production Example 1 except that a mixed solution of 100 g of dodecyl methacrylate, 150 g of toluene and 50 g of isopropanol was used. After cooling, reprecipitation in 2 l of methanol gave 83 g of a colorless and transparent viscous product. w is 27,000
Met.

Production Example 3 of Resin for Dispersion Stabilization A mixed solution of 100 g of octadecyl methacrylate and 300 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 6 g of 4,4-azobis (4-cyanopentanol) was added and reacted for 8 hours. After cooling, reprecipitation in 2 l of methanol,
86 g of white powder was obtained. w was 28,000.

Dispersion Stabilization Resin Production Example 4 Dodecyl Methacrylate 70g, Butyl Methacrylate 3
A mixed solution of 0 g, 150 g of toluene and 50 g of isopropanol was heated to 70 ° C. with stirring under a nitrogen stream. ACV
6 g was added and reacted for 8 hours. The w of the copolymer was 23,000.

Production Example 5 of dispersion stabilizing resin Tridecyl methacrylate 98.5 g, thioglycolic acid
A mixed solution of 1.5 g and 200 g of toluene was heated to a temperature of 65 ° C. 2,2'-azobis (isobutyronitrile) (abbreviation A.
After adding 1.0 g of IBN) and stirring for 5 hours, 0.3 g of AIBN was added and further stirring for 4 hours. The w of the obtained copolymer is 2
It was 4,000.

Production Example 6 of dispersion stabilizing resin Octadecyl methacrylate 98.0 g, 2-mercaptoethanesulfonic acid 2.0 g, toluene 200 g and methanol 10
0 g of the mixed solution was heated to a temperature of 65 ° C. under a nitrogen stream. A.
After adding IBN 0.8g and reacting for 5 hours, AIBN 0.3g
Was added and reacted for 2.5 hours. The reaction solution was reprecipitated in 2 l of acetonitrile to obtain 88 g of white powder. w was 25,000.

Production Example 7 of Resin for Stabilizing Dispersion A mixed solution of 90 g of hexadecyl methacrylate, 8 g of 2-chloroethyl methacrylate, 2.0 g of thiomalic acid, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75 ° C. 1.0g of 1,1'-azobis (cyclohexane-1-carbonitrile) was added and reacted for 6 hours.
Was added and reacted for 6 hours. After cooling, reprecipitation in 2 l of methanol gave 86 g of a colorless and transparent viscous product. It was Mw23,000.

Production Example 8 of Dispersion Stabilizing Resin A mixed solution of 100 g of tetradecyl methacrylate, 100 g of tetrahydrofuran and 100 g of methanol was heated to 70 ° C. while stirring under a nitrogen stream. 2,2'-azobis {2-
Methyl-N- [1,1-bis (hydroxymethyl) -2-
Hydroxyethyl] propioamide} 5g was added and reacted for 8 hours. After cooling, reprecipitation was performed in 2 l of a mixed solution of methanol / water (7/3 volume ratio) to obtain 80 g of a colorless viscous substance. w is 28,00
It was 0.

Production Example 9 of Dispersion Stabilizing Resin A mixed solution of 95 g of dodecyl methacrylate and 200 g of toluene was heated to 70 ° C. under a nitrogen stream. 5 g of 4,4-azobis (4-cyanopentanol) was added and reacted for 8 hours.
Next, 1.0 g of N, N-dimethylaniline and 10 g of glutaconic anhydride were added to this reaction solution, and the mixture was stirred at a temperature of 90 ° C. for 12 hours. After cooling, reprecipitation in 2 l of methanol gave a pale yellow viscous product 88
got g. w was 28,000.

Production Examples 10 to 17 of Dispersion Stabilizing Resin In place of octadecyl methacrylate and ACV which was the initiator in Production Example 1, each of the compounds shown in Table A below was produced to be a dispersion stabilizing resin.

The repeating units of the terminal portion and the main chain containing the polar group of the resins obtained in Production Examples 1 to 17 of the above dispersion stabilizing resins are shown below.

Dispersion stabilizing resin production example 1: Production Example 1 of Latex Particles 20 g of resin obtained in Production Example 1 of resin for dispersion stabilization, 100 g of vinyl acetate, compound example II- (8) of macromonomer (M) 1.
A mixed solution of 0 g and Isopar H380 g was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. AIBN 0.8g was added and reacted for 6 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88 ° C. The temperature was raised to 100 ° C., and the mixture was stirred for 2 hours to remove unreacted vinyl acetate. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion had a polymerization rate of 90.
% Was a latex having an average particle size of 0.24 μm.

Production Example 2 of Latex Particles 20 g of resin obtained in Production Example 2 of resin for dispersion stabilization, 100 g of vinyl acetate, compound example II- (3) of macromonomer (M) 1.
A mixed solution of 2 g and 380 g of Isopar H was heated to a temperature of 70 ° C. with stirring under a nitrogen stream. 0.9 g of benzoyl peroxide was added and reacted for 6 hours. 40 minutes after the addition of the initiator, the homogeneous solution became cloudy and the reaction temperature rose to 85 ° C. After cooling, the white dispersion obtained by passing it through a 200-mesh nylon cloth has a polymerization rate of
The latex was 88% and had an average particle size of 0.27 μm.

Production Example 3 of Latex Particles 12 g of the resin obtained in Production Example 1 of dispersion stabilizing resin, 8 g of poly [octadecyl methacrylate], 100 g of vinyl acetate, 1.5 g of compound II- (9) of macromonomer (M) and 450 g of Isopar H. The temperature of the mixed solution is 75 with stirring under a nitrogen stream.
Warmed to ° C. AIBN 0.7 g was added and reacted for 4 hours, and further AIBN 0.5 g was added and reacted for 2 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having an average particle size of 0.20 μm.

Production Example 4 of Latex Particles 25 g of resin obtained in Production Example 3 of resin for dispersion stabilization, 100 g of vinyl acetate, and compound example II- (10) of macromonomer (M) 1.
A mixed solution of 5 g and 380 g of isodecane was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. AIBN 1.0 g was added and reacted for 4 hours, and AIBN 0.5 g was further added and reacted for 2 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having an average particle size of 0.23 μm.

Production Example 5 of Latex Particles 18 g of the resin obtained in Production Example 10 of dispersion stabilizing resin (as solid content), 100 g of vinyl acetate, 1.2 g of Compound II- (15) of macromonomer (M) and 380 g of n-decane The mixed solution was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. AIBN
After adding 1.0 g and reacting for 4 hours, 0.5 g of AIBN was added and reacted for 2 hours. The temperature was raised to 110 ° C. and the mixture was stirred for 2 hours, and the low boiling point solvent and residual vinyl acetate were distilled off. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having an average particle size of 0.23 μm.

Production Example 6 of Latex Particles 20 g (as solid content) of the resin obtained in Production Example 12 of dispersion stabilizing resin, 100 g of vinyl acetate, 1.5 g of compound II- (18) of macromonomer (M) and 380 g of shell sol 71 The mixed solution was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.5 g of benzoyl peroxide was added and reacted for 6 hours. After adding the initiator
After 10 minutes, cloudiness occurred and the reaction temperature was raised to 90 ° C. The temperature was raised to 100 ° C. and the mixture was stirred for 1 hour as it was, and the residual vinyl acetate was distilled off. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 90% and an average particle size of 0.
It was a 25 μm latex.

Production Example 7 of Latex Particles A mixed solution of 18 g of the resin obtained in Production Example 6 of a resin for dispersion stabilization and 200 g of shell sol 71 was stirred under a nitrogen stream at a temperature of 70.
Warmed to ° C. Vinyl acetate 100g, macromonomer (M)
Compound Example II- (11) 2.0 g, Shell Sol 71 180 g and 2,
2'-azobis (isovaleronitrile) (abbreviation AIV
The mixed solution of N.) 1.0 was added dropwise over 2 hours, and the mixture was stirred as it was for 4 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a weight percentage of 85% and an average particle size of 0.20.
It was a μm latex.

Production Example 8 of Latex Particles 20 g of the resin obtained in Production Example 7 of dispersion stabilizing resin, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 2.0 g of compound II- (32) of macromonomer (M) and 400 g of isododecane.
The mixed solution of (1) was heated to a temperature of 65 ° C with stirring under a nitrogen stream. After adding AIBN (1.5 g) and reacting for 4 hours, the mixture was cooled, passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having an average particle size of 0.28 μm.

Production Example 9 of Latex Particles Mixing 20 g of the resin obtained in Production Example 1 of dispersion stabilizing resin, 100 g of vinyl acetate, 5 g of 4-pentenoic acid, 1.5 g of compound II- (21) of macromonomer (M) and Isopar G The solution was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. AIVN1.
0 g was added and reacted for 2 hours. Further, 0.5 g of AIVN was added and reacted for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having an average particle size of 0.28 μm.

Production Example 10 of Latex Particles 25 g of the resin obtained in Production Example 2 of dispersion stabilizing resin, 100 g of isopropyl methacrylate, 1.2 g of Compound Example II- (1) of macromonomer (M) and Isopar H were stirred under a nitrogen stream. While warming to a temperature of 70 ° C. AIVN 1.2g
Was added and reacted for 4 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having an average particle size of 0.45 μm.

Production Example 11 of latex particles 25 g of resin obtained in Production Example 1 of dispersion stabilizing resin, styrene 1
00g, Example of macromonomer (M) compound II- (23) 1.0g
And a mixed solution of 380 g of Isopar H were heated to a temperature of 50 ° C. while stirring under a nitrogen stream. An n-butyllithium hexane solution was added in an amount of 1.0 g as a solid content, and the mixture was reacted for 4 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having an average particle size of 0.36 μm.

Latex Particle Production Examples 12 to 17 Latex Particle Production Example 1 was repeated in the same manner as in Production Example 1 except that the dispersion stabilizing resin was added to the resin in Table B instead of the weight of Production Example 1 as a latex. Particles were produced.

Production Example 18 of Latex Particles (Comparative Example A) Treated in the same manner as in Production Example 1 of latex particles except that a mixed solution of 20 g of poly [octadecyl methacrylate], 100 g of vinyl acetate and 380 g of Isopar H was used, and the weight ratio was 88.
%, A white dispersion of latex particles with an average particle size of 0.23 μm was obtained.

Production Example 19 of Latex Particles (Comparative Example B) Except for using a mixed solution of 20 g of octadecyl methacrylate / acrylic acid (copolymerization ratio (95/5) weight ratio) copolymer, 100 g of vinyl acetate and 380 g of Isopar H, latex particles are prepared. The same treatment as in Production Example 1 was performed to obtain a white dispersion which was latex particles having a weight ratio of 90% and an average particle diameter of 0.25 μm.

Example 1 [Dodecylmethacrylate-acrylic acid (copolymerization ratio (95/5) weight ratio)] 10 g of copolymer, 10 g of nigrosine and 30 g of shell sol 71 were added together with glass beads to a paint shaker (Tokyo Seiki Co., Ltd.). The mixture was placed in a flask and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30 g of the resin dispersion of Production Example 1 of latex particles, 2.5 g of the above nigrosine dispersion, and 0.08 g of [octadecene-half-maleic acid octadecylamide copolymer] were added to 1 of Shell Sol 71.
To obtain a liquid developer for electrostatography.

(Comparative Developers A to 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 Latex Particle Production Example 18 Comparative Liquid Developer B: Resin Dispersion of Latex Particle Production Example 19 These liquid developers were fully automated plate-making machine ELP404V (Fuji Photo Film ( ELP Master II type (manufactured by Fuji Photo Film Co., Ltd.), which is an electrophotographic photosensitive material, was exposed and developed. The plate making speed was 5 plates / minute. In addition, the ELP Master II type is 2000
After the sheet processing, it was observed whether or not the toner adhered to the developing device. The blackening ratio (image area) of the copied image was 20%. The results are shown in Table 1.

As described above, a plate made using each developer under the plate making conditions,
As is clear from the results shown in Table 1, the developer of the present invention was the only developer that did not stain the developing device and had a clear image on the 2000th plate.

On the other hand, the master plate for offset printing (ELP-master) obtained by plate-making from each developer is printed by a conventional method, and the number of printed sheets until the occurrence of missing characters and blurring of solid parts in the image of printed matter is compared. The present invention, Comparative Example A
The master plate obtained by using the developer of Comparative Example B did not occur even after 10,000 sheets.

As described above, only the developer using the resin particles of the present invention as a developer did not cause any stain on the developing device, and the number of printed master plates was good.

That is, in the case of Comparative Examples A and B, there was no problem in the number of printed sheets, but the developing device was extremely dirty and could not withstand continuous use.

In particular, the dispersion stabilizing resin used in Comparative Example B uses acrylic acid as a copolymerization component and contains a carboxy group in the middle of the polymer main chain, which is the polymer main chain according to the present invention. The redispersibility was remarkably inferior to the polymer containing a carboxy group only at one end.

These results show that the resin particles of the present invention are clearly superior.

Example 2 100 g of white background dispersion obtained in Production Example 2 of latex particles
And a mixture of Sumicaron Black (1.5 g) was heated to a temperature of 100 ° C., and heated and stirred for 4 hours. By cooling to room temperature and passing through a 200 mesh nylon cloth to remove the remaining dye,
A black resin dispersion having an average particle size of 0.20 μm was obtained.

32 g of the above black resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g of shell sol 71 to 1.

When this was developed by the same apparatus as in Example 1, 2000
After the development of one sheet, the toner adhered to the device did not stain at all.

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

Example 3 100 g of white dispersion obtained in Production Example 9 of latex particles
And a mixture of Victoria Blue B3g at a temperature of 70 ℃ -80 ℃.
And stirred for 6 hours. After cooling to room temperature, it was passed through a 200-mesh nylon cloth to remove the remaining dye, and the average particle size was 0.2.
A 16 μm blue resin dispersion was obtained.

32 g of the above blue resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g in Isopar H1.

When this was developed by the same apparatus as in Example 1, 2000
No toner adhesion stains on the apparatus were observed even after the sheet development. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 4 White Resin Dispersion Liquid 32 Obtained in Production Example 2 of Latex 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 half-docosanilamide compound of a copolymer of diisobutylene and maleic anhydride into Isopar G1.

When this was developed by the same apparatus as in Example 1, 2000
No toner adhesion stains on the apparatus were observed even after the sheet development. 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 also clear.

Further, this developer was allowed to stand for 3 months and then subjected to the same treatment as above, but there was no difference from that before the passage of time.

Example 5 10 g of poly [decyl methacrylate], 30 g of Isopar H
Then, 8 g of alkali blue and glass beads were put into a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

White resin dispersion obtained in Production Example 3 of latex particles
A liquid developer was prepared by diluting 30 g, the above-mentioned alkali blue dispersion 4.2 g, and 0.06 g of a half-docosanilamide compound of a copolymer of diisobutylene and maleic anhydride to Isopar G1.

When this was developed by the same apparatus as in Example 1, 2000
No toner adhesion stains on the apparatus were observed even after the sheet development. Further, 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 9 As Example 5, except that the latex particles shown in Table 2 were used in an amount of 6.0 g as a solid content instead of the white resin dispersion of Production Example 3 of latex particles. A liquid developer was prepared in the same manner.

When this was developed by the same apparatus as in Example 1, 2000
No toner adhesion stains on the apparatus were observed even after the sheet development. Further, 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.

Claims (1)

[Claims] 1. A liquid developer for electrostatic photography comprising at least a resin dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles have the following general formula ( Weight average obtained by bonding at least one polar group selected from a carboxyl group, a sulfo group, a hydroxyl group, an amino group and a phospho group to only one end of the main chain of the polymer containing the repeating unit represented by I). Molecular weight is 1 × 10
^In the presence of a dispersing resin of ⁴ or more, a monofunctional monomer (A) soluble in a non-aqueous solvent but insolubilized by polymerization and a repeating unit represented by the following general formula (II) A monofunctional macromonomer having a number average molecular weight of 1 × 10 ⁴ or less, in which a polymerizable double bond group represented by the following general formula (III) is bonded to only one end of the main chain of a polymer consisting of A liquid developer for electrostatic photography, which is a copolymer resin particle obtained by polymerizing a solution containing at least one of B). General formula (I) In the formula (I), X is -COO -, - OCO -, - CH 2 OCO -, - CH
₂ COO -, - O- or -SO ₂ - represent. Y represents an aliphatic group having 6 to 32 carbon atoms. a ₁ and a ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Z or a hydrocarbon group having 1 to 8 carbon atoms. Through -COO-Z (Z represents a hydrocarbon group having 1 to 22 carbon atoms). General formula (II) Wherein (II), V is -COO -, - OCO -, - CH 2 OCO -, - CH
_{2 COO -, - O -,} - SO 2 -, (R ₁₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). W represents a hydrocarbon group having 1 to 22 carbon atoms. b ₁ and b ₂ may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Q or a hydrocarbon group having 1 to 8 carbon atoms. Represents -COO-Q (wherein Q represents a hydrocarbon group having 1 to 18 carbon atoms). General formula (III) In the formula (III), V ′ has the same meaning as V in the formula (II). c ₁ and c ₂ may be the same as or different from each other and are synonymous with b ₁ or b ₂ .