JP2640164B2 - 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 a petroleum-based resin such as 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. Dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and added with a polarity controlling agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, and vinylpyrrolidone. .

In such a developer, the resin is dispersed in the form of particles having a diameter of several nm to several hundred nm as insoluble latex particles,
In the conventional liquid developer, the soluble dispersion stabilizing resin and the polarity controlling agent were easily diffused into the solution due to insufficient bonding between the soluble dispersion stabilizing resin and the polarity controlling agent and the insoluble latex particles. For this reason, there has been a drawback that the soluble dispersion stabilizing resin is detached from the insoluble latex particles due to long-term storage or repeated use, and the particles settle, aggregate, accumulate, and the polarity becomes unclear. Also, once aggregated,
The deposited particles are difficult to re-disperse, so that the particles remain attached to the developing device everywhere, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding pump.

Means for chemically binding the soluble dispersion stabilizing resin and the insoluble latex particles in order to improve these drawbacks have been considered and disclosed in U.S. Pat. No. 3,990,980 and the like.
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. Further, in the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle size 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. Further, there is a problem that the dispersion stabilizer to be used must be produced through a complicated and time-consuming production process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components. The method of improving the dispersibility of the particles, redispersibility, storage stability by the method described in JP-A-60-179751, 62-15
It is disclosed in 1868 and the like. Further, in the presence of a polymer utilizing a bifunctional monomer or a polymer utilizing a polymer reaction, an insoluble dispersion resin of a copolymer of a monomer insolubilized and a monomer containing two or more polar components Methods for improving the dispersibility, redispersibility, and storage stability of particles by making them into particles are disclosed in JP-A Nos. 62-166362 and 63-66567.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing a large number of 5,000 or more sheets using a master plate for offset printing by an electrophotographic method has been attempted. It has become possible to print 10,000 sheets or more in plate size. In addition, the operation time of the electrophotographic plate making system has been shortened, and the development-fixing process has been improved to be faster.

JP-A-60-179751, 62-151868, 62-16636
No. 2, the dispersed resin particles manufactured according to the means disclosed in the same 63-66567, when the development speed is increased,
In the case where the fixing time is shortened or in the case of a master plate of a large plate size (for example, A-3 size or more), the dispersibility and redispersibility of particles are still necessarily satisfied in terms of printing durability. It wasn't the performance it should have.

The present invention solves the problems of the conventional liquid developer as described above.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid developer which has a fast development-fixing process and has excellent dispersion stability, re-dispersibility and fixability even in an electrophotographic plate making system using a large-size master plate. That is.

Another object of the present invention is to provide a liquid developer capable of producing an offset printing master 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 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 problem) The above-mentioned objects are to achieve an electric resistance of at least 10 ⁹ Ωcm and a dielectric constant of 3.5
A liquid developer for electrostatography comprising at least resin particles dispersed in the following non-aqueous solvent, wherein the dispersed resin particles comprise a block A containing at least a polymer component represented by the following general formula (I): , Carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and (Q ₀ represents a —Q ₁ group or —OQ ₁ group, and Q ₁ represents a hydrocarbon group.) A polymer component and / or a monofunctional monomer containing at least one polar group selected from And a block B comprising a polymer component corresponding to (A), comprising an AB block copolymer having a weight average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁵ and soluble in the non-aqueous solvent. In the presence of a dispersion stabilizing resin, a monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and the following general formula (II)
Having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the following general formula (III) to only one end of the main chain of a polymer comprising a repeating unit represented by This is achieved by a liquid developer for electrophotography, which is a copolymer resin particle obtained by polymerizing a solution containing at least one functional macromonomer (M _A ).

General formula (I) In the formula (I), V ₀ represents —COO—, —OCO—, CH _{2 y} COO
-, CH _{2 y} OCO-, or -O- and represents (y is an integer of 1 to 3).

R ₀ represents an aliphatic group having 10 or more carbon atoms.

a ₁ and a _{2, which} may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₁ or -COO-Z ₁ via a hydrocarbon group (Z ₁ is hydrogen Atom or a hydrocarbon group which may be substituted).

General formula (II) Wherein (II), T ₁ is _{-COO -, - OCO, CH 2} l COO-, CH
_{2 l OCO -, - O -} , - SO 2 -, - CONHCOO -, - CONHCONH
−, Represents (D ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. 1 represents an integer of 1 to 3.) G ₀ represents a hydrocarbon group having 1 to 22 carbon atoms. Where G ₀
During the carbon chain -O -, - CO -, - CO 2 -, - OCO -, - SO 2
-, May be contained. Here, D ₂ represents the same content as D _1.

e ₁ and e _2, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ₃ or -COO-D ₃ (D ₃ through the hydrocarbon is a hydrogen atom Or a hydrocarbon group which may be substituted).

General formula (III) Wherein (III), T ₂ represents T ₁ same content as the formula (II). f ₁ and f ₂ may be the same or different from each other, and the formula (I
Represent e _1, e ₂ identical contents and I).

Furthermore, together with the monomer (A) to be used in the present invention, the copolymerization is monofunctional macromonomer (M _A) is preferably containing at least a repeating unit consisting of the following general formula (IIa).

General formula (IIa) In the formula (IIa), e ₁ , e ₂ and T ₁ represent the same symbols as in the formula (II).

G ₃ are a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

J ₁ and J ₂ may be the same or different from each other;
-, - CO -, - CO 2 -, - OCO -, - SO 2 -, Represents (D ₅ represents the same content as D ₁ of the formula (II)).

W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain. Here, J ₃ and J ₄ may be the same or different from each other, have the same contents as J ₁ and J ₂ above, and W ₃ is
It represents a C1-C18 hydrocarbon group which may be substituted.

m, n and p each independently represent an integer of 0-3. However, none of them is 0 at the same time.

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

The electric resistance used in the present invention is 10 ⁹ Ωcm or more, and the dielectric constant is 3.5.
As the following carrier liquid, a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen-substituted product thereof can be preferably used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E,
Isopar G, Isopar H, Isopar L (Isoper; trade name of Exxon), Cielsol 70, Cielsol 71 (Cielsol; trade name of Ciel Oil), AMSCO OMS, 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 method for preparing a monofunctional monomer (A) and a monofunctional macromonomer (M _A ) in a non-aqueous solvent in the presence of a dispersion stabilizing resin which is an AB block copolymer of the present invention. It is produced by copolymerization (so-called polymerization granulation method).

Here, as the non-aqueous solvent, basically, any solvent that is miscible with the carrier liquid of the liquid developer for electrostatography can be used.

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, nonane, dodecane, isododecane, isopaffin petroleum solvents such as Isopar E, Isopar G, Isopar H, Isopar L, Cielsol 70, Cielsol 71, Amsco OM
S, Amsco 460 solvent or the like is used alone or as a mixture.

Solvents that can be used by mixing with these organic solvents include alcohols (eg, methyl alcohol,
Ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc., ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propionate) Ethyl ether, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, methylene dichloride, chloroform, carbon tetrachloride, cigloloethane,
Methyl chloroform, etc.).

The non-aqueous solvent used by mixing these, after 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.

Monomers used in producing the non-aqueous dispersion resin,
A monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and a monofunctional macromonomer (M _A ) which is copolymerized with the monomer ( _A ). can do.

The monomer (A) in the present invention may be any monofunctional monomer which is soluble in a non-aqueous solvent but insolubilized by polymerization. Specifically, for example,
Examples include a monomer represented by the following general formula (IV).

General formula (IV) In the formula (IV), V ₁ represents —COO—, —OCO—, —CH ₂ OCO—, —CH ₂
COO -, - O -, - CONHCOO -, - CONHOCO -, - SO 2 -, Represents Here, Z ₂ represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl A 3-methoxypropyl group).

R ₁ is a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2,2-dichloroethyl group, 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.).

b ₁ and b ₂ may be the same or different, each represent the same contents as a ₁ or a ₂ in the general formula (I).

Specific monomers (A) include, for example, those having 1 to 1 carbon atoms.
6 vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid Alkyl esters or amides of a carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group as the alkyl 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-carboxyamidoethyl group, etc .; styrene derivatives (eg, styrene, vinyltoluene, α-methyl) Styrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid;
Maleic acid, itaconic acid cyclic acid anhydride; acrylonitrile; methacrylonitrile; polymerizable double bond group-containing heterocyclic compound (specifically, for example, "Polymer Data Handbook-Basic Edition-" edited by The Society of Polymer Science, Japan , P175-184, compounds described in Baifukan (1986), for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran,
Vinyloxazoline, vinylthiazole, N-vinylmorpholine and the like).

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

Next, the monofunctional macromonomer (M _A ) used in the present invention will be further described.

The monofunctional macromonomer (M _A ) can be copolymerized with the monomer (A) only at one end of the main chain of the polymer comprising the repeating unit represented by the general formula (II), It is a macromonomer having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by III).

In the general formulas (II) and (III), e ₁ , e ₂ , T ₁ , G ₀ , f
_1, the hydrocarbon group contained in f ₂ and T ₂ have each indicated number of carbon atoms (as unsubstituted hydrocarbon group), these hydrocarbon groups may be substituted.

In the formula (II), D ₁ in the substituent represented by T ₁ is not only a hydrogen atom, but also a preferred hydrocarbon group has 1 to 1 carbon atoms.
22 optionally substituted alkyl groups (for example, methyl group,
Ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl,
Tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl An alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, a 2-methyl-1-propenyl group, a 2-butenyl group, a 2-pentenyl group, a 3-methyl-2-pentenyl group, A 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linolel group, or the like; An aralkyl group which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naph A methyl group, a 2-naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), and may have 5 to 8 carbon atoms. An alicyclic group (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, or the like), or an optionally substituted aromatic group having 6 to 12 carbon atoms (for example, a phenyl group, a 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, propioamidophenyl group, dodecylylamidophenyl group,
Etc.).

T ₁ In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a chloromethyl group, a methoxymethyl group, and the like).

G ₀ preferably represents a hydrocarbon group having 1 to 22 carbon atoms,
Specifically, representing the same contents as those described for D ₁ described above. However, in the carbon chain of G _0, -O -, - CO
-, -CO _2- , -OCO-, -SO _2- , May be contained. Here, D ₂ represents the same content as D _1.

e ₁ and e ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -COO
-D ₃ or -CH ₂ COOD ₃ (D ₃ represents 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, represent represent) the same contents as those described above D _1.

Further, in the macromonomer (M _A ) provided in the present invention, G ₀ in the general formula (II) as a constituent repeating unit includes at least one specific polar group, and a repeating unit component in the molecule Preferably contains a component of the general formula (IIa) characterized in that it contains at least two or more specific polar groups.

General formula (IIa) In the formula (IIa), e ₁ , e ₂ and T ₁ are as described above.

J ₁ and J ₂ may be the same or different from each other;
-, - CO -, - CO 2 -, - OCO -, - SO 2 -, The representative (D ₅ represents the same content as D ₁ of the formula (II)).

W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms (as the hydrocarbon group, an alkyl group, an alkenyl group, an aralkyl group or an alicyclic group) which may be interposed in the bond of the main chain. Specific examples of preferable these aliphatic groups may include the same content as the preferred aliphatic groups D ₁ of the formula (II).

However, J ₃ and J _4, which may be the same or different, said J ₁
And J ₂ represent the same content and, W ₃ is the same content as W ₁ or W _2, represents a substituted also good C1-18 hydrocarbon group.

Further, for W ₁ and W ₂ , specific examples include: (D ₇ and D ₈ represent a hydrogen atom, an alkyl group, a halogen atom, etc.), CH ＝ CH, (J ₃ , J ₄ , W ₃ , G ₃ and p represent the same symbols as described above).

m, n and p may each be the same or different;
Represents the numbers 1, 2, and 3. However, none of them will be 0 at the same time.

G ₃ are a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. Preferably, it represents a aliphatic which may be substituted having 1 to 22 carbon atoms, specifically, represent the same contents as D ₁ of the formula (II).

Furthermore, in the formula (IIa), it is preferable that the total number of atoms of each atomic group of T ₁ , W ₁ , J ₁ , W ₂ , J ₂ and G ₃ is composed of 8 or more.

The repeating unit represented by the general formula (IIa) as described above will be more specifically described below. However, the content of the present invention is not limited to these.

In the following, a is -H or -CH _3; an alkyl group R 'is a hydrogen atom or a C _1-18; R an alkyl group of C _1-18 is;
k ₁ and k ₂ each represent an integer of 1 to 12; and l ₁ represents an integer of ₁ to 100.

The macromonomer (M _A ) used in the present invention is represented by the general formula (III) only at one end of the main chain of the polymer comprising the repeating unit represented by the general formula (II) as described above. The polymerizable double bond group has a chemical structure in which it is directly bonded or bonded via an arbitrary linking group.

In the formula (III), T ₂ has the same meaning as T ₁ in the formula (II), f ₁ and f ₂ may be the same or different from each other, and e ₁ or e _{2 in the} above formula (II) Is synonymous with The preferred ranges of T ₂ , f ₁ and f ₂ are the same as those described for T ₁ , e ₁ and e ₂ , respectively.

More preferably, _one of e ₁ and e _{2 in} the formula (II) or f ₁ and f _{2 in} the formula (III) is a hydrogen atom.

The group linking the components of formula (II) and formula (III) includes a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen Atoms, silicon atoms, etc.), and any combination of heteroatom-heteroatom bond atomic groups.

Preferred among the macromonomers (M _A ) of the present invention are those represented by formulas (V) and (Va).

General formula (V) General formula (Va) In the formulas (V) and (Va), the symbols other than A represent the same symbols as those in the formulas (II), (IIa) and (III).

A is a single bond or [D ₉ and D ₁₀ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (eg, a methyl group,
Ethyl group, propyl group, etc.), CH = CH, -O-, -S-, -COO-, -SO _2- , -NHCOO-, -NHCONH-, (D ₁₁ and D ₁₂ each independently represent a hydrogen atom, a hydrocarbon group having the same content as D ₁ , etc.) or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

In the general formula (III), (V) or (Va),
Particularly preferred examples of each of e ₁ , e ₂ , f ₁ , f ₂ , T ₁ , and T ₂ are shown below.

The _{T 1, -COO -, - OCO} -, - O -, - CH 2 COO-,
Or -CH ₂ OCO-, as T ₂ , all of the above (where D ₁ is a hydrogen atom), and e ₁ , e ₂ , f ₁ , and f ₂ are each a hydrogen atom or a methyl group. Can be

Below, it is shown in the general formulas (V) and (Va). A specific example will be described. However, the content of the present invention is not limited to these.

In the following, b is -H or -CH _3; m ₁ is an integer of 1 to 12; n ₁ is an integer of 2 to 12.

Further, the macromonomer (M _A ) used in the present invention may contain, as a copolymerization component, another repeating unit together with the repeating unit represented by the general formula (II) or (IIa). As the other copolymer component, any compound may be used as long as it is a monomer copolymerized with a monomer corresponding to the repeating unit of the general formula (II). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4-pentenoic acid and esters or amides of these unsaturated carboxylic acids, having 1 to 1 carbon atoms
22 fatty acid vinyl esters or allyl esters, vinyl ethers, styrene and styrene derivatives,
Heterocyclic compounds containing an unsaturated bond group are exemplified. Specifically, for example, the compounds exemplified for the above-mentioned monomer (A) and the like can be mentioned, but it should not be construed that the invention is limited thereto.

In the sum of the repeating units of the macromonomer (M _A ),
The repeating unit component represented by the formula (II) or (IIa) is preferably contained in an amount of at least 40% by weight, more preferably 60 to 100% by weight.

When the content of the component represented by the general formula (II) is less than 40% by weight, the mechanical strength of the image area formed by the dispersed resin particles is not sufficiently maintained, and therefore, the printing durability when used as an offset master. The effect of improvement cannot be seen.

The above-mentioned macromonomer (M _A ) of the present invention preferably has a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ and preferably 2 × 10 ^{3 to} 9
× 10 ³ is more preferred.

The upper limit of the number average molecular weight of macromonomer (M _A ) is 1 × 10
^If it exceeds ⁴ , printing durability will decrease. On the other hand, if the molecular weight is too small, soiling tends to occur, so it is preferably 1 × 10 ³ or more.

The macromonomer (M _A ) of the present invention can be produced by a conventionally known synthesis method. For example, a method using an ionic polymerization method in which various reagents are reacted with the terminal of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer, a reactive group such as a carboxyl group, a hydroxy group, or an amino group in a molecule. By reacting an oligomer having a terminal reactive group bond obtained by radical polymerization with various reagents using a polymerization initiator and / or a chain transfer agent containing A method by a polyaddition condensation method in which a polymerizable double bond group is introduced into the oligomer obtained by the polycondensation reaction in the same manner as in the above-mentioned radical polymerization method.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp & E.Franta, Ad
v.Polym.Sci., 58 , 1 (1984), V.Percec, Appl.Polym.Sc
i., 285 , 95 (1984), R. Asami & M. TakaRi, Makvamol. Ch
em. Suppl., 12 , 163 (1985), P. Rempp et al, Makvamol. C
hem. Suppl., 8 , 3 (1984), Yusuke Kawakami "Chemical Industry" 38 , 56
(1987), Yuya Yamashita "Polymer" 31 , 988 (1982), Shiro Kobayashi "Polymer" 30 , 625 (1981), Toshinobu Higashimura "Journal of the Adhesion Society of Japan" 18 , 536 (1982), Koichi Ito "High molecular processing "35, 262
(1986), Takashiro Higashi, Takashi Tsuda "Functional Materials" 1987 , No.10,5
And can be synthesized according to the methods described in the literatures and patents cited therein.

The dispersion resin of the present invention comprises at least one of each of a monomer (A) and a macromonomer (M _A ). What is important is that a resin synthesized from these monomers is insoluble in the non-aqueous solvent. If so, a desired dispersion resin can be obtained.

More specifically, for the monomer (A) to be insolubilized,
It is preferred to use macromonomer (M _A) 0.05 to 10 wt%, more preferably from 0.1 to 5 wt%. Still more preferably, it is 0.3 to 3% by weight.

The molecular weight of the dispersion resin of the present invention is from 1 × 10 ³ to 1 × 10 ⁶ , preferably from 1 × 10 ^{4 to} 5 × 10 ⁵ .

The dispersion stabilizing resin used in the present invention is an AB block copolymer, and one block (referred to as block A) is composed of a polymer component comprising a repeating unit represented by the general formula (I). The other one block (referred to as block B) is a polymer component containing at least one kind of polar group selected from the above-mentioned specific polar groups and / or
Or a polymer component corresponding to the above-mentioned monofunctional monomer (A), and having a weight average molecular weight of 1 × 10 ^{4 to} 5 × 1
It is characterized by being 0 ⁵ .

The proportion of the blocks A and B in the AB block copolymer is preferably 99/1 to 50/50 (weight ratio).

The specific polar group-containing polymer component contained in the block B is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the dispersion stabilizing resin. When no specific polar group-containing polymer component is present in the block B, the polymer component corresponding to the monofunctional monomer (A) is preferably used in an amount of 5 to 5 parts by weight in 100 parts by weight of the resin.
0 parts by weight, more preferably 10 to 40 parts by weight.

The weight average molecular weight of the AB block copolymer is preferably 2 × 10 ⁴ to 1 × 10 ⁵ .

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

In the general formula (I), V ₀ is preferably -COO-, -O
Represents CO- or -O-.

R ₀ represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc. .

a ₁ and a ₂ may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a chlorine atom,
Bromine atom, etc.), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -COO
-Z ₁ or -CH ₂ COO-Z ₁ [Z ₁ is a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (for example, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, An aryl group).

Specifically, Z ₁ is, in addition to a hydrogen atom, a preferred hydrocarbon group such as an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group). Group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 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, decenyl group,
A dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, a linolel group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2 -Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (For example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.), and an aromatic group which may be substituted having 6 to 12 carbon atoms (for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, meth Xyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group,
Chlorophenyl, dichlorophenyl, bromophenyl, cyanophenyl, acetylphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, butoxycarbonylphenyl, acetamidophenyl, propioamidophenyl, dodecyloylamidophenyl, etc. ).

Further, in the block A of the dispersion stabilizing resin provided in the present invention, together with the repeating unit represented by the general formula (I),
Other repeating units may be contained as a copolymer component.
The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (I).

However, it is preferable that other components are not contained, and it is used in an amount not exceeding 20 parts by weight in the block A at most. If it exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles will be deteriorated.

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

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

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

Examples of the polymer component corresponding to the monofunctional monomer (A) include the same contents as described above for the insoluble monomer (A).

Preferably, it is composed of the same monomer as the monofunctional monomer (A) to be the dispersed resin particles.

Also, among specific polar groups, In the formula, Q ₀ represents a —Q ₁ group or —OQ ₁ group, and Q ₁ represents a C 1-10 hydrocarbon group. As the hydrocarbon group for Q ₁ , preferably an aliphatic group which may be substituted and has 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group, butenyl group, pentenyl group,
A hexenyl group, a 2-chloroethyl group, a 2-cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group or the like, or an aromatic group which may be substituted (for example, a phenyl group, a tolyl group) Group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Further, in a polar group of the present invention, the amino group, -NH _2, -NHZ ₃ or Represents Z ₃ and Z ₄ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms,
Specifically, the same meaning as the hydrocarbon group for Q ₁ described above.

Even more preferably, the hydrocarbon groups of Q ₁ , Z ₃ and Z ₄ are
Examples thereof include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, and an optionally substituted phenyl group.

As the monomer corresponding to the polymer component containing the specific polar group, any monofunctional monomer containing at least one specific polar group may be used. For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by the Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2
-Amino) methyl form, α-chloro form, α-bromo form, α
-Fluoro form, α-tributylsilyl form, α-cyano form,
β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, -Alkenylcarboxylic acids (e.g., 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-
2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzene carboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-esters of vinyl or allyl groups of dicarboxylic acids Derivatives, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituents of the amide derivatives, and the like.

The following are specific examples of these compounds. However, in each of the following examples, e is -H, -C
H _3, shows -Cl, -Br, -CN, a -CH ₂ COOCH ₃ or -CH ₂ COOH, f represents -H or -CH _3, n ₁ represents an integer of 2 to 10, m ₁ is An integer of 1 to 10 is shown, and l ₁ is an integer of ₁ to 4. X ₁ is -COOH, -SO ₃ H, -OH, -CHO or (R _a and R _{b each} represent a C _1-4 alkyl group). X ₁ is −
Represents COOH or -OH.

The AB block copolymer of the present invention can be produced by a conventionally known polymerization reaction method. In particular,
In the monomer corresponding to the polymer component containing the specific polar group, the polar group is previously protected as a functional group, and an organometallic compound (eg, alkyl lithiums, lithium diisopropylamide, alkyl magnesium halides, etc.) or Ion polymerization reaction by hydrogen iodide / iodine system, photopolymerization reaction using porphyrin metal complex as catalyst,
Alternatively, after synthesizing an AB block copolymer by a known so-called living polymerization reaction such as a group transfer polymerization reaction, a functional group having a protected polar group is subjected to a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction or A deprotection reaction is performed by a decomposition reaction or the like to form a polar group. One example is shown in the following reaction scheme (1).

For example, P. Lutz, P. Masson et al, Polym. Bull., 12 , 79
(1984), BCAnderson, GDAndrews et al, Macromole
cules, 14 , 1601 (1981), K. Hatada, K. Ute, et al, Polym.
J., 17, 977 (1985) , the same 18, 1037 (1986), the right hand Koichi, Koichi Hatada "Polymer Processing" 36, 366 (1987), Higashimura Satoshinobe, Mitsuo Sawamoto "polymer Collected Papers" 46, 189 (1989), M. Kuroki, T. Aid
a, J. Am. Chem. Soc., 109 , 4737 (1987), Takuzo Aida, Shohei Inoue "Synthetic Organic Chemistry" 43 , 300 (1985), DYSogah, WRH
It is easily synthesized according to the synthesis method described in ertler et al, Macromolecules, 20 , 1473 (1987).

As another method for synthesizing the AB block copolymer, it can also be synthesized by a photoiniferter polymerization method using a monomer having a polar group unprotected and using a disiocarbamate compound as an initiator. . For example, Takayuki Otsu "polymer" 37, 248 (1988), Shunichi Hinokimori, Ryuichi Otsu, Polym.Rep.
Jap., 37 , 3508 (1988), JP-A-64-111, JP-A 1-2661
It is synthesized according to the synthesis method described in No. 9, etc.

Further, the protective group for protecting the specific polar group of the present invention and the elimination of the protective group (deprotection reaction) can be easily carried out using conventionally known knowledge. For example, various descriptions are given in the above cited references, and furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977)
TWGreene, "Protective Groups in Organic Sy
nthesis ", John Wiley & Sons (1981), JFWMoOm
ie, `` Protective Groups in Organic Chemistry '', Plen
um Press, (1973) and the like can be carried out by appropriately selecting a method described in detail.

In order to produce the dispersing resin used in the present invention as described above, generally, the resin for stabilizing the dispersion of the AB block copolymer of the present invention, the monofunctional monomer (A) and the functional macromonomer (M _a) and benzoyl peroxide in a non-aqueous solvent, azobisisobutyronitrile, it is sufficient to heat polymerization in the presence of a polymerization initiator such as butyl lithium. Specifically, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (A) and a macromonomer (M _A ), mETHOD slide into dropwise body of (a) and the macromonomer (M _a) together with the polymerization initiator or includes a portion of the mixture of the dispersion stabilizing resin total amount and the monomer (a) and the macromonomer (M _a) A method of optionally adding the remaining monomer mixture together with the polymerization initiator to the mixed solution, and furthermore, dispersing the dispersion stabilizing resin and the monomer (A) and the macromonomer (M _A ) in a non-aqueous solvent. There is a method of arbitrarily adding the mixed solution together with the polymerization initiator, and any method can be used for the production.

The total amount of the monomer (A) and the macromonomer (M _A ) 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 suitably from 0.1 to 5% by weight based on the total amount of the monomers.

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

In the non-aqueous solvent used for the reaction, the alcohols described above,
When polar solvents such as ketones, ethers and esters are used in combination, or when the unreacted product of the monomer (A) to be polymerized and granulated remains, the boiling point of the solvent or monomer is increased. It is preferable to remove by heating or distilling off under reduced pressure.

As described above, the non-aqueous dispersion resin produced according to the present invention exhibits very stable dispersibility at the same time as being present as fine particles having uniform particle size distribution, and can be used repeatedly for a long time especially in a developing device. However, even if the dispersibility is good and the developing speed is improved, re-dispersion is easy, and it is not recognized at all that any contamination occurs on each part of the apparatus.

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

Further, the liquid developer of the present invention has a rapid development-fixing process and is excellent in dispersion stability, re-dispersibility and fixability even when a large-size master plate is used.

In particular, in the non-aqueous dispersion resin described in JP-A-62-166362 or JP-A-63-66567, an ester bond or the like that can be copolymerized with a monomer that is polymerized and insolubilized, is contained in the molecule. A random copolymer soluble in the non-aqueous solvent containing a copolymer component having a polymerizable double bond group at a site separated from the polymer main chain by at least 8 atoms, together with at least two or more monomers. Using the polymer as a dispersion stabilizing resin,
Polymerized and granulated resin particles (latex particles). The dispersibility and printing durability of these particles have been greatly improved compared to conventional particles. Plate making machine (eg, Fuji Photo Film Co., Ltd., ELP-560, ELP-820, etc.), or if the processing speed of the plate making machine is increased, there is still a problem in the dispersibility of the particles. Dirt (especially dirt on the developing device) was generated, particles were aggregated and settled, or when the master plate was printed, the strength of the image portion was not yet sufficient, and the printing durability was reduced. When the resin particles used in the present invention are used, no problem occurs even under such severe conditions.

As described above, the high redispersibility of the latex particles of the present invention is due to the insolubilizable monomer (A) and macromonomer (M _A )
It depends on the soluble AB type block copolymer used together.

That is, the dispersion stabilizing resin of the present invention has a block A composed of a polymer component containing a long-chain aliphatic group having a high affinity for the non-aqueous solvent, and a small affinity for the non-aqueous solvent,
It is an AB block copolymer in which a block B composed of a polymer component having an affinity for the monomer (A) to be insolubilized is bonded.

Thereby, the block B portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation,
In addition, the block A portion having a high affinity for the non-aqueous dispersion medium can sufficiently solvate the solvent and sufficiently exert a steric repulsion effect (so-called tail-like adsorption). It is estimated that the effects of the present invention have been achieved.

On the other hand, in a conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, in the polymer chain in which the component serving as the adsorbed portion is composed of a solvating component. Randomly bonded to the resin particles, the adsorption to the dispersed resin particles was not sufficient, and further, the adsorption pattern became loop-shaped, so that the steric repulsion effect was also alienated, and the dispersion stability was not sufficient. .

Moreover, it high printing durability, good compatibility with the monomer copolymerized with the macromonomer (M _A) to be insolubilized is also under mild fixing conditions, which sufficiently compatibilized to form a uniform film It is estimated that this is achieved.

If desired, a colorant may be used in the liquid developer of the present invention. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used.

In the case of coloring the dispersion resin itself, for example, as one of the coloring methods, there is a method of physically dispersing the dispersion resin in a dispersion resin using a pigment or a dye. I have. 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 of chemically bonding a dispersing resin and a dye as disclosed in JP-A-53-54029, or
As described in, for example, No. 2955, 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, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol.
And those specifically described on page 44 are used.

For example, di-2-ethylhexylsulfosuccinic 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 amounts of the main components of the liquid developer of the present invention will be described below.

The toner particles mainly composed of a resin (and a coloring agent optionally used) are used in an amount of 0.1 parts by weight per 1000 parts by weight of the carrier liquid.
5 parts by weight to 50 parts by weight are preferred. When the amount is less than 0.5 part by weight, the image density is insufficient, and when the amount is more than 50 parts by weight, fogging to a non-image portion is liable to occur. Further, the carrier liquid soluble resin for stabilizing the dispersion is also used as desired, and about 0.5 to 100 parts by weight can be added to 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated 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 Ωc
If it is lower than m, it becomes difficult to obtain a good quality continuous tone image, so it is necessary to control the amount of each additive within this limit.

(Examples) Hereinafter, a synthesis example of the dispersion stabilizing resin according to the present invention, a production example of latex particles and an example will be described, but the content of the present invention is not limited thereto.

Synthesis Example 1 of dispersion stabilizing resin 1: P-1 95 g of dodecyl methacrylate and tetrahydrofuran 2
00 g of the mixed solution was sufficiently degassed under a nitrogen stream, and cooled to -78 ° C. 1.0 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Further, 5 g of triphenylmethyl methacrylate and 25 g of tetrahydrofuran were added to this mixed solution.
Was sufficiently degassed under a nitrogen stream, and added, followed by further reaction for 8 hours. After the mixture was cooled to 0 ° C., 10 ml of methanol was added and reacted for 30 minutes to terminate the polymerization. The obtained polymer solution was brought to a temperature of 30 ° C. with stirring, and 30%
15 ml of a hydrogen chloride ethanol solution was added, and the mixture was stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount became half, and then the reaction mixture was reprecipitated in methanol 1. The polymer obtained by collecting the precipitate and drying under reduced pressure had a weight average molecular weight of 4.5 × 10 ⁴ and a yield of 70 g.

b indicates block connection (the same applies hereinafter).

Synthesis Example 2 of Dispersion Stabilizing Resin: P-2 A mixed solution of 46 g of octadecyl methacrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to 30 ° C. under a nitrogen stream. This was irradiated with light from a 300 W-xenon lamp through a glass filter from a distance of 25 cm, and reacted for 12 hours. 4 g of benzyl methacrylate was further added to the mixture, and the mixture was irradiated with light for 8 hours in the same manner. Then, 3 g of methanol was added to the reaction mixture, and the mixture was stirred for 30 minutes to stop the reaction. Next, Pd—C was added to the reaction mixture, and a catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, reprecipitate in 500 ml of methanol,
The precipitate was collected and dried. The obtained polymer had a yield of 33 g and a weight average molecular weight of 3 × 10 ³ .

Synthesis Example 3 of dispersion stabilizing resin: P-3 A mixed solution of 90 g of tridecyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream,
Cooled to ° C. 0.8 g of lithium 1,1-diphenyl-3-methylpentyl was added and stirred for 6 hours. Further, 10 g of 4-vinylphenyloxytrimethylsilane was added to this mixture, and the mixture was stirred for 5 hours. Then, 3 g of methanol was added, and the mixture was stirred for 30 minutes.

The reaction mixture is then added to a 10% 30% hydrogen chloride ethanol solution.
g, and the mixture was stirred at 25 ° C. for 1 hour, and then reprecipitated in methanol 1 to collect a precipitate. 300m of methanol in the precipitate
Washed twice with l and dried. The obtained polymer had a weight average molecular weight of 3.5 × 10 ⁴ in a yield of 58 g.

Synthesis Example 4: Dispersion Stabilizing Resin: P-4 A mixture of 95 g of hexadecyl methacrylate and 2.0 g of benzyl N, N-diethyldithiocarbamate was sealed in a container under a nitrogen stream, and heated to a temperature of 60 ° C. This is passed through a glass filter from a distance of 10 cm with a 400 W high-pressure mercury lamp,
Light irradiation was carried out for a time to carry out photopolymerization. After 5 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen and light irradiation was performed again for 10 hours.

The obtained reaction mixture was reprecipitated in 1.5 l of methanol, collected, and dried. The obtained polymer had a weight average molecular weight of 4 × 10 ⁴ in a yield of 68 g.

Synthesis Example 5 of dispersion stabilizing resin: P-5 A mixed solution of 80 g of stearyl methacrylate and 200 g of tetrahydrofuran was sufficiently degassed under a nitrogen gas flow, and was subjected to -78 ° C.
And cooled. 1.0 g of potassium 1,1-diphenyl-3-methylpentyl was added, and the mixture was stirred for 10 hours. Further, 20 g of styrene was added to this mixture, and the mixture was stirred for 8 hours. Then, the temperature of the reaction mixture was adjusted to 0 ° C., and 10 ml of methanol was added. Next, this was reprecipitated in 1.5 l of methanol, and the precipitate was collected by filtration and dried. The obtained polymer had a yield of 68 g and a weight average molecular weight of 3 × 10 ⁴ .

Preparation of Macromonomer M _A 1: M _A -1 methyl methacrylate 100 g, a 3-mercapto mixed solution of propionic acid 5g and toluene 200 g, while stirring under a nitrogen gas stream, was heated to a temperature of 75 ° C.. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviated AIBN) was added and reacted for 4 hours, and 0.5 g of AIBN was added for 3 hours.
Was added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate and N, N-dimethyldodecylamine were added to the reaction solution.
1.0 g and t-butyl hydroquinone 0.5 g were added, and the temperature was 10
The mixture was stirred at 0 ° C for 12 hours. After cooling, this reaction solution was reprecipitated in 2 l of methanol to obtain 82 g of a white powder. The number average molecular weight of the polymer was 6,500.

Preparation of Macromonomer M _A two to thirty-nine: Production Example 1 of M _A -2~M _A -39 macromonomer M _A, except that in addition to the compound corresponding only methyl methacrylate in the following Table-1, Preparation Macromonomer M _A -2 to M _A
-39 was synthesized. The number average molecular weight of each obtained macromonomer was in the range of 5,000 to 7,000.

Preparation of Macromonomer M _A 40: M _A -40 2,3- dipropylcarbamoylmethyl propyl methacrylate 96 g, while the mixed solution of thioethanol 4g and toluene 200g stirring under nitrogen gas stream, was heated to a temperature of 70 ° C.. 1.0 g of AIBN
The reaction was performed for 4 hours. Add 0.5g of AIBN and 3 hours,
Thereafter, 0.3 g of AIBN was further added and reacted for 3 hours. The reaction solution was cooled to room temperature, 16.2 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 60 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred for 4 hours.

The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 l of methanol.

The precipitated oil was collected by decantation, dissolved in 150 ml of methylene chloride and reprecipitated in methanol 1. The oil was collected and dried under reduced pressure to yield 54 g.
Thus, a polymer having a number average molecular weight of 6.30 × 10 ³ was obtained.

Preparation of Macromonomer M _A 41 to 46: Production Example of M _A -41~M _A -46 macromonomer M _A -40, (corresponding to 2,3-propylene oxy propyl methacrylate) methacrylate monomer and an unsaturated carboxylic acid (2-carboxyethyl corresponding ethyl methacrylate) instead respectively, in the same manner as production example M _a -40, we were prepared each macromonomer in the following table 2. The number average molecular weight of each of the obtained macromonomers was in the range of 5 × 10 ³ to 8 × 10 ³ .

Production Example 48 of Macromonomer: M _A -48 _A mixed solution of 90 g of dodecyl methacrylate, 10 g of methacrylic acid, 5 g of thioethanol and 200 g of toluene was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of AIBN was added and reacted for 4 hours. Furthermore, 0.5g of AIBN is added and 3 hours,
Thereafter, 0.3 g of AIBN was further added and reacted for 3 hours. The reaction solution was cooled to room temperature, 20.2 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 10.2 g of DCC and 60 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butylhydroquinone was added, and the mixture was stirred for 4 hours. The precipitated crystals were separated by filtration, and the obtained filtrate was reprecipitated in 2 l of methanol. The precipitated oil is collected by decantation,
This was dissolved in 150 ml of methylene chloride and reprecipitated in methanol 1 again. The oil was collected and dried under reduced pressure to yield
A polymer having a number average molecular weight of 5,800 was obtained with 54 g.

Production Example 49 of Macromonomer: M _A -49 _A mixed solution of 70 g of n-dodecyl methacrylate, 30 g of t-butyl methacrylate, 4 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran was heated to 70 ° C. under a nitrogen stream. Add 1.0g of AIBN and react for 4 hours.
0.5 g of BN was added and reacted for 4 hours. Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C., 7.9 g of triethylamine was added, and 6.3 g of acrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C. or lower. After the addition, the mixture was further stirred for 1 hour. Thereafter, 0.5 g of t-butylhydroquinone was added, the mixture was heated to a temperature of 60 ° C, and stirred for 4 hours. After cooling, reprecipitation in 2 l of methanol was performed twice to obtain 63 g of a pale yellow viscous substance.
The number average molecular weight was 6,600.

Production Example 50 of Macromonomer: _A mixed solution of 100 g of MA-50 octadecyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated to a temperature of 75 ° C. under a nitrogen stream. 4.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) was added and 5
After reacting for 1.0 hour, 1.0 g of ACV was further added and reacted for 4 hours.
After cooling, the reaction solution was reprecipitated in 1.5 l of methanol, and the oil was collected by decantation and dried under reduced pressure. Yield 85
g.

50 g of this oil, 15 g of glycidyl methacrylate,
1.0 g of N, N-dimethyldodecylamine and 1.0 g of 2,2′-methylenebis (6-t-butyl-p-cresol) were added,
The mixture was stirred at a temperature of 100 ° C. for 15 hours. After cooling, the reaction solution was reprecipitated in petroleum ether 1 to obtain a white powder. The number average molecular weight was 7,500.

Production Example 1 of Latex Particles: D-1 _A mixed solution of 10 g of dispersion stabilizing resin P-5, 100 g of vinyl acetate, 1.0 g of macromonomer M-28 and 380 g of Isopar H was stirred under a nitrogen stream while stirring. Heated to a temperature of 75 ° C. 2,2'-azobis (valeronitrile) (abbreviation: ABV
N.) was added and reacted for 4 hours. Further, 0.4 g of ABVN was added and reacted for 2 hours. Twenty minutes after the initiator addition, cloudiness occurred,
The reaction temperature rose to 88 ° C. The temperature was raised to 100 ° C. and the mixture was stirred for 1 hour to distill off unreacted vinyl acetate. 200 after cooling
Through a mesh nylon cloth, the resulting white dispersion is
It was a latex having a polymerization rate of 86% and an average particle size of 0.20 μm.

Production Example 2: Latex Particles: D-2 _A mixed solution of 10 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1.0 g of macromonomer M _A- 30 and 380 g of Isopar H was stirred at 70 ° C. under a nitrogen stream. Was heated. 2,
2'-azobis (isovaleronitrile) (abbreviation AIV
N.) was added and reacted for 2 hours, and 0.6 g of AIVN was further added and reacted for 2 hours. Twenty minutes after the addition of the initiator, cloudiness 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, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a conversion of 86% and an average particle size of 0.21 μm.

Latex Particle Production Examples 3 to 5: D-3 to D-5 Same as Production Example 2 except that the dispersion stabilizing resin P-1 was replaced with each resin shown in Table 3 below in Latex Particle Production Example 2. Thus, each latex particle D-3 to D-5 was produced.

Latex Particle Production Example 6 to 16: D-6 to D-16 Same as Production Example 2 except that the dispersion stabilizing resin P-1 was replaced with each resin shown in Table 4 below in Production Example 2 of latex particles. Thus, each latex particle D-6 to D-16 was produced. The conversion was 83-88% for each latex.

Preparation of latex particles 17~40: D-17~D-40 in Preparation Example 1 of latex grains D-1, a dispersion stabilizing resin P-5 and macromonomer M _A -28 in the compounds of Table -5 Except for the substitution, each latex particle was produced under the same conditions as in Production Example 1. The polymerization rate of each latex particle is 85
~ 90%.

The average particle size of the obtained particles was in the range of 0.18 to 0.25 μm, and the particle size distribution was sharp and the monodispersity was good.

Preparation of latex particle 41: D-41 vinyl acetate 90 g, N-vinylpyrrolidone 10 g, the macromonomer M _A -40 1.0 g, the dispersion stabilizing resin P-17 of the following structure 2
A mixed solution of 0 g and 380 g of n-decane was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.7 g of AIBN was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 2 hours.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.26 μm.

Production Example 42 of Latex Particles: D-42 A mixed solution of 25 g of dispersion stabilizing resin P-7 and 680 g of n-dodecane was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. To this solution, methyl methacrylate 100 g, macromonomer M _A- 28 1.0 g, n-dodecyl mercaptan 1.0 g
And a mixed solution of 0.8 g of ABVN was added dropwise over 2 hours.
After reacting for 2 hours, 0.3 g of ABVN was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion had an average particle size of 0.25 μm.
Latex.

Production Example 43 of Latex Particles: 18 g of D-43 dispersion stabilizing resin P-16, 95 g of vinyl acetate, 5 g of crotonic acid, 1.5 g of macromonomer M _A- 33 and 1.5 g of Isopar E
While stirring 68 g of the mixed solution under a nitrogen stream, the temperature is 70 ° C.
Was heated. After adding 0.8 g of ABVN and reacting for 6 hours,
The temperature was raised to 0 ° C., and the mixture was stirred for 1 hour, and the remaining vinyl acetate was distilled off. After cooling, the mixture was passed through a 200-mesh nylon cloth. The resulting white dispersion had a conversion of 85% and an average particle size of 0.25.
μm latex.

Production Example 44 of latex particles: D-44 18 g of dispersion stabilizing resin P-18 having the following structure, vinyl acetate 94
g, 4-pentenoic acid 6.0 g, a mixed solution of 380g of a macromonomer M _A -26 1.5 g of Isopar G, a flow of nitrogen under stirring, was heated to a temperature of 75 ° C.. 0.7 g of ABVN was added and reacted for 4 hours, and further 0.5 g of ABVN was added and reacted for 2 hours.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 45 of latex particles: D-45 While stirring a mixed solution of 20 g of dispersion stabilizing resin P-19 having the following structure and 680 g of n-dodecane under a nitrogen stream, a temperature of 60
Warmed to ° C. In this solution, add the macromonomer M _A- 27
A mixed solution of 1.2 g, 100 g of methyl methacrylate, 1.0 g of n-dodecyl mercaptan and 0.8 g of ABVN was added dropwise over 2 hours. After reacting for 2 hours, 0.3 g of ABVN was added and reacted for 2 hours. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 46 of latex particles: D-46 _A mixed solution of 20 g of dispersion stabilizing resin P-5, 100 g of styrene, 1.0 g of macromonomer MA 43 and 380 g of Isopar H was added to a temperature of 45 ° C. while stirring under a nitrogen stream. Warmed. A hexane solution of n-butyllithium was added in an amount of 1.0 g as a solid amount of n-butyllithium, and reacted for 4 hours. After cooling
The white dispersion obtained by passing through a 200-mesh nylon cloth was latex having an average particle size of 0.26 μm.

Production Example 47 of Latex Particles: (Comparative Example A) In Production Example 1 of latex particles D-1, 20 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 1.0 g of monomer (I) having the following structure and Isopar H were used. The same operation as in Production Example 1 was carried out except that 385 g of the mixed solution was used.

The resulting white dispersion had a conversion of 85% and an average particle size of 0.20 μm.
Latex. (Latex particles described in JP-A-60-179751) Production Example 48 of Latex Particles: (Comparative Example B) In Production Example 1 of latex particles D-1, 10 g of dispersion stabilizing resin R-1 having the following structure, The same operation as in Production Example 1 was carried out except that a mixed solution of 100 g of vinyl, 1 g of monomer (I) having the following chemical structure and 385 g of Isopar H was used.

The resulting white dispersion had a conversion of 86% and an average particle size of 0.24 μm.
Latex. (Latex particles described in JP-A-63-66567) Example 1 Dodecyl methacrylate / acrylic acid (copolymerization ratio: 95 /
(5 weight ratio) 10 g of the copolymer, 10 g of nigrosine and 30 g of Shellsol 71 were placed in a paint shaker (Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

The resin dispersion D-1 of Production Example 1 of latex particles was added to 30
g, 2.5 g of the above nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol), and 0.1 g of [octadecene-half-maleic acid octadecylamide copolymer].
08 g was diluted in 1 of Shellsol 71 to prepare a liquid developer for electrostatography.

(Comparative Developers A and B) Two kinds of liquid developers A and B for comparison were prepared by replacing the resin dispersion in the above Production Example with the following resin particles.

Comparative Liquid Developer A: Resin Dispersion of Production Example 47 of Latex Particles Comparative Liquid Developer B: Resin Dispersion of Production Example 48 of Latex Particles These liquid developers were fully automated plate making machine ELP-560 (Fuji Photo Using ELP Master II type (manufactured by Fuji Photo Film Co., Ltd.), which is an electrophotographic photosensitive material, was used as a developer for a film (manufactured by Fuji Photo Film Co., Ltd.) and exposed and developed. The plate making speed was 5 plates / min. Further, after the 2,000 sheets of ELP Master II type were processed, it was observed whether or not the toner adhered to the developing device. The blackening rate (image area) of the copied image was determined using a 30% original.

 The results are shown in Table-6.

When plate making was performed using each developer under the above-described plate making conditions, the developer which did not cause staining of the developing device and had a clear image on the 2000th plate making plate was only in the case of the present invention.

On the other hand, a master plate for offset printing (ELP master) obtained by making a plate on the tenth plate from each developer is printed by a conventional method until characters on the printed image are missing, and solid portions are blurred. When the number of printed sheets was compared, no master plate was obtained using any of the developers of the present invention and Comparative Examples A and B, even at 10,000 sheets or more.

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 also significantly improved the number of printed master plates.

On the other hand, Comparative Examples A and B are used under severe plate making conditions (conventionally, the blackening rate of a copied image is about 8 to 10% at a plate making speed of 2 to 3 sheets / min). And the developing device (especially on the back electrode plate) becomes stained,
After 2,000 sheets, the quality of the copied image on the plate was affected (Dmax was reduced, fine lines were blurred, etc.). Therefore, with these master plates, when printed, the image quality of the printed matter is degraded from the start of printing and is no longer practical.

Example 2 100 g of the white dispersion obtained in Production Example 2 of latex particles
And 1.5 g of Sumicaron Black were 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 0.24 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 FOC-1600 (hexadecyl alcohol, manufactured by Nissan Chemical Industries, Ltd.) into 1 of Shellsol 71.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains occurred on the apparatus.

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 the white dispersion obtained in Production Example 44 of latex particles
And a mixture of 3 g of Victoria Blue B at a temperature of 70 ° C. to 80 ° C.
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 25 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 to 1 of Isopar H.

This was developed with the same apparatus as in Example 1, and
Even after the development of 00 sheets, no toner adhesion stains were observed on the apparatus. 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 32 obtained in Production Example 6 of latex particles
g, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-1400
A liquid developer was prepared by diluting 20 g of a tetradecyl alcohol (manufactured by Nissan Chemical Industries, Ltd.) and 0.02 g of a semi-docosanil amidated copolymer of diisobutylene and maleic anhydride into 1 of Isopar G.

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

After the developer was allowed to stand for three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

Example 5 10 g of poly (decyl methacrylate) and 3 parts of Isopar H
0 g and 8 g of alkali blue were put into a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

30 g of the white resin dispersion D-5 obtained in Production Example 5 of latex particles, 4.2 g of the above-mentioned alkali blue dispersion, 15 g of isostearyl alcohol and 0.06 g of a semi-docosanyl amidated copolymer of diisobutylene and maleic anhydride Was diluted to 1 of Isopar G to prepare a liquid developer.

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

Examples 6 to 29 Liquid developers were prepared in the same manner as in Example 5, except that latex particles D-5 were replaced with the respective latexes shown in Table 7 below.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains occurred on the apparatus.

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.

After the developer was allowed to stand for three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

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

Claims (2)

(57) [Claims] An electrophotographic liquid developer comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5, wherein the dispersed resin particles have the following general formula: A block A containing at least the polymer component represented by (I), a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and (Q ₀ represents a —Q ₁ group or —OQ ₁ group, and Q ₁ represents a hydrocarbon group.) A polymer component and / or a monofunctional monomer containing at least one polar group selected from And a block B comprising a polymer component corresponding to (A), comprising an AB block copolymer having a weight average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁵ and soluble in the non-aqueous solvent. In the presence of a dispersion stabilizing resin, a polymer comprising a monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and a repeating unit represented by the following formula (II): _A monofunctional macromonomer (M _A ) having a number average molecular weight of 1 × 10 ⁴ or less formed by bonding a polymerizable double bond group represented by the following general formula (III) to only one end of the main chain of the united polymer Are copolymer resin particles obtained by polymerizing a solution containing at least one kind of each. Liquid developer for electrostatic photography wherein the Rukoto. General formula (I) In the formula (I), V ₀ represents —COO—, —OCO—, CH _{2 y} COO—,
CH _{2 y} OCO-, or -O- and represents (y is an integer of 1 to 3). R ₀ represents an aliphatic group having 10 or more carbon atoms. a ₁ and a _{2, which} may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ₁ or -COO-Z ₁ via a hydrocarbon group (Z ₁ is hydrogen Atom or a hydrocarbon group which may be substituted). General formula (II) Wherein (II), T ₁ is _{-COO -, - OCO, CH 2} l COO-, CH
_{2 l OCO -, - O -} , - SO 2 -, - CONHCOO -, - CONHCONH
−, Represents (D ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. 1 represents an integer of 1 to 3.) G ₀ represents a hydrocarbon group having 1 to 22 carbon atoms. However, in the carbon chain of the _{G 0 -O -, - CO -} , - CO 2 -, - OCO -, - SO
_2- , May be contained. Here, D ₂ represents the same content as D _1. e ₁ and e _2, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ₃ or -COO-D ₃ (D ₃ through the hydrocarbon is a hydrogen atom Or a hydrocarbon group which may be substituted). General formula (III) Wherein (III), T ₂ represents T ₁ same content as the formula (II). f ₁ and f ₂ may be the same or different from each other, and the formula (I
Represent e _1, e ₂ identical contents and I). (2) The monofunctional macromonomer (M _A ) contains at least a repeating unit represented by the following general formula (IIa) as a repeating unit thereof.
6. The liquid developer for electrostatography according to the above item. General formula (IIa) In the formula (IIa), e ₁ , e ₂ and T ₁ represent the same symbols as in the formula (II). G ₃ are a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. J ₁ and J ₂ may be the same or different from each other, -O-,
_{-CO -, - CO 2 -,} - OCO -, - SO 2 -, The representative (D ₅ represents the same content as D ₁ of the formula (II)). W ₁ and W ₂ may be the same or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain. Here, J ₃ and J ₄ may be the same or different from each other, have the same contents as J ₁ and J ₂ above, and W ₃ is
It represents a C1-C18 hydrocarbon group which may be substituted. m, n and p each independently represent an integer of 0-3.
However, none of them is 0 at the same time.