JP2609152B2 - 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) In general, a liquid developer for electrophotography is an organic or inorganic pigment or dye such as carbon black, nigrosine or phthalocyanine blue, a natural or synthetic resin such as an alkyd resin, acrylic resin, rosin or synthetic rubber, and a petroleum-based fat. It is dispersed in a liquid having a high insulating property and a low dielectric constant such as an aromatic hydrocarbon, and further added with a polarity restricting 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 defect 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, coagulate, accumulate or the polarity becomes unclear. Further, since the particles once aggregated and deposited are difficult to re-disperse, the particles remain adhered to various parts of the developing device, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised, and is disclosed in US Pat. No. 3,990,980.
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. 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 for improving the degree of dispersion, redispersibility and storage stability of particles by the method described in JP-A-60-179951 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, 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. Further, the operation time of the electrophotographic plate making system has been shortened, and improvement in speeding up the development-fixing process has been performed.

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 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 Problems) An object of the present invention is to provide a liquid developer for electrostatography 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 substantially dispersed resin particles have the following general formula (I) only at one end of a polymer main chain containing at least one polymer component represented by the following general formula (IIa) or (IIb): A) a monofunctional macromonomer (M) having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ^{4 formed} by bonding a polymerizable double bond group represented by the following general formula (III):
In the presence of a dispersion-stabilizing resin soluble in the non-aqueous solvent, a monofunctional monofunctional monomer which is at least soluble in the non-aqueous solvent but is insolubilized by polymerization This is achieved by a liquid developer for electrostatography, which is a polymer resin particle obtained by polymerizing a solution containing at least one of the monomers (A).

General formula (I) In the formula (I), V represents —COO—, —OCO—, CH _{2 m} OCO
_{-, CH 2 m COO -,} - O -, - CONHCOO -, - CONHCO
_{-, - SO 2 -, -} CO-, Represents Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 to 3.

a ₁ and a ₂ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O—Z ₂ or —COO—Z ₂ via a hydrocarbon (Z ₂ represents a hydrogen atom or a hydrocarbon group which may be substituted).

General formula (IIa) General formula (IIb) In formula (IIa) or (IIb), X ₀ represents the same content as V in formula (I).

Q ₀ represents an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

Q is -CN or Represents Here, Y represents a hydrogen atom, a halogen atom, an alkoxy group or —COOZ ₃ (Z ₃ represents an alkyl group, an aralkyl group or an aryl group).

b ₁ and b ₂ may be the same or different from each other, and have the formula (I)
It represents the same contents as a ₁ and a ₂ in the table.

General formula (III) In formula (III), X ₁ has the same content as X ₀ in formula (IIa), and Q ₁ has the same content as Q ₀ in formula (II a). d ₁ and d ₂ may be the same or different from each other and represent the same contents as a ₁ and a ₂ in the formula (I).

However, the macromonomer (M) represented by the general formula (II)
In the component and the monomer component represented by the general formula (III), at least _one of Q ₀ and Q ₁ has a carbon number
Represents 10 to 22 aliphatic groups.

The resin for stabilizing the dispersion of the comb-type copolymer provided in the present invention has a weight average molecular weight of 2 × 10 ⁴ to 2 × 10 ⁵ , and a —PO ₃ H ₂ group at one end of the polymer main chain. , -SO ₃ H group, -COOH
Group, -OH group, -SH group, (Here, Z ₀ represents a -Z ₁₀ group or -OZ ₁₀ group, and Z ₁₀ represents a hydrocarbon group), a formyl group, and a comb-type copolymer formed by bonding polar groups selected from amino groups. Preferably, there is.

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

As a carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less used in the present invention, preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon, and a halogen thereof. Substitutes can be used. For example, octane, isooctane, decane, isodecane, decalin, inane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; a product of Exxon) Name), Dierzol 70, Dierzol 71 (Dierzol; trade name of Ciel Oil Co., Ltd.), AMSCO OM
S, Amsco 460 solvent (Amsco; trade name of Spirits) or the like is 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 produced by polymerizing the monomer (A) in a non-aqueous solvent in the presence of the dispersion stabilizing resin which is the comb-type copolymer (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. And their halogen-substituted products. For example, hexane, octane, isooctane,
Decane, Isodecane, Decalin, Nonane, Dodecane, Isododecane, Isopar E, Isopar G, Isopar H, Isopar L, Cielsol 70, Cielsol 71,
AMSCO OMS, AMSCO 460 solvent or the like is used alone or in combination.

Solvents that can be used in combination 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, dichloroethane,
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.

In general, it is preferable to use the same solvent as the carrier liquid in the step of producing the resin dispersion, and as described above, a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a halogen. And the like.

The dispersion stabilizing resin used in the present invention is a comb-type copolymer obtained by polymerizing a monofunctional macromonomer (M) and a monomer represented by the general formula (III) each containing at least one or more kinds. And is characterized by being soluble in the non-aqueous solvent. Further, a comb-type copolymer obtained by bonding the above-mentioned specific polar group to one end of the polymer main chain of the comb-type copolymer is more preferable.

The weight-average molecular weight of the comb copolymer is 2 × 10 ⁴ to 2 × 1.
0 is ^5, and preferably from ^{3 × 10 4 ~1 × 10 5} . When the weight average molecular weight is less than 2 × 10 ⁴ or more than 2 × 10 ⁵ , any of them is used. The average particle size of the resin particles obtained by polymerization granulation becomes coarse or the particle size distribution is widened, so that the monodispersibility is impaired, and further, the resin particles become aggregates instead of dispersions.

The proportion of the monofunctional macromonomer (M) as a copolymer component of the comb copolymer is 1% by weight to 70% by weight, preferably 5% by weight to 50% by weight. If the ratio is less than 1% by weight, the number of comb portions is significantly reduced, resulting in a chemical structure similar to that of a conventional random copolymer. I will not be able to. On the other hand, if the proportion exceeds 70% by weight,
The copolymerizability with the monomer represented by the general formula (III) becomes insufficient.

The proportion of the other copolymer component represented by the general formula (III) in the comb-type copolymer is 30 to
It is 99% by weight, preferably 50-95% by weight.

On the other hand, the macromonomer (M) of the present invention, which is the comb portion of the comb copolymer, has a weight average molecular weight of 1 × 10 ³ to
It is 2 × 10 ⁴ , preferably 2 × 10 ³ to 1 × 10 ⁴ .
When the weight average molecular weight is less than 1 × 10 ³ , the redispersibility of the obtained dispersed resin particles is reduced. ^{On the other hand} , when it exceeds 2 × 10 ⁴ , the copolymerizability with the monomer represented by the general formula (III) is reduced, and a comb copolymer cannot be obtained.

Since the comb-type copolymer of the present invention as described above is soluble in the non-aqueous solvent, it contains a repeating unit which becomes soluble in one or both of the polymer main chain and the comb. Therefore, in the macromonomer (M) component represented by the general formula (II) and the monomer component represented by the general formula (III), at least _one of Q ₀ and Q 1
One represents an aliphatic group having 10 to 22 carbon atoms.

That is, when Q ₀ in the general formula (IIa) represents an aliphatic group or an aromatic group having less than 10 carbon atoms as a repeating unit of the macromonomer (M), which is a comb part, and the general formula (II
In the case of the repeating unit represented by b), in the monomer represented by the general formula (III) constituting the polymer main chain, Q ₁
Represents an aliphatic group having 10 to 22 carbon atoms. The general formula (II
When to Q ₁ I) is an aliphatic group or an aromatic group of less than 10 carbon atoms, as the repeating units of the macromonomer (M) to be combined, Q ₀ is a carbon number of at least the general formula (II a) 10 ~ 22 aliphatic group repeating units.

Hereinafter, the content of the comb copolymer will be further described.

The monofunctional macromonomer (M) comprises a monomer represented by the general formula (III) only in one of the main chains of the polymer comprising the repeating unit represented by the general formula (IIa) or (IIb). Having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ^{4 formed} by bonding a polymerizable double bond group represented by the general formula (I) which can be copolymerized with a polymer.
Is a macromonomer.

In the general formulas (I) and (IIa) and (IIb), a ₁ ,
The hydrocarbon groups contained in a ₂ , V, b ₁ , b ₂ , X ₀ , Q ₀ and Q each have the indicated carbon number (as an unsubstituted hydrocarbon group). It may be substituted.

In the formula (I), Z ₁ in the substituent represented by V is a hydrogen atom, and a preferred hydrocarbon group is a group having 1 to 1 carbon atoms.
22 optionally substituted alkyl groups (for example, methyl group,
Ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl , 2-methoxycarbonylethyl group, 2-
A methoxyethyl group, a 3-bromopropyl group and the like), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, a 2-methyl-1-propenyl group, a 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.), having 7 to 7 carbon atoms.
12 aralkyl groups which may be substituted (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.), an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, Cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
Or, 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, 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, dodecyloylamidophenyl group, etc.).

V is In the case where is represented, the benzene ring may have a substituent.
Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom, etc.) and an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl 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), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -CO
O-Z ₂ or -CH ₂ COOZ ₂ (Z ₂ 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 is substituted even if well, specifically, represent represent) the same contents as those described above Z _1.

In the formulas (IIa) and (IIb), X ₀ has the same meaning as V in the formula (I), and b ₁ and b ₂ may be the same or different from each other. it is synonymous with a ₁ or a _2.

Q ₀ preferably represents an aliphatic group having 1 to 22 carbon atoms, and specifically, has the same content as the alkyl group described for Z ₁ described above.

The alkyl residue in the case where Y is an alkoxy group, specifically, those similar to the examples shown in the Q ₀ can be mentioned. Z ₃ represents an alkyl group, an aralkyl group or an aryl group, and specific examples thereof include the same examples as those described for Q ₀ .

Preferred ranges of X ₀ , b ₁ and b ₂ are each V,
The same contents as those described for a ₁ and a _2.

A ₁ and a ₂ of the formula (I) or b _{1 of the} formulas (II a) and (II b)
And more preferably one of b ₂ is a hydrogen atom.

The macromonomer (M) repeating unit of the present invention contains at least one unit represented by the general formula (IIa) or (IIb), and specific examples will be described below. However, the scope of the present invention is not limited to this.

In the following, Q ₀ : −C _p H _{2p + 1} (p: an integer from 1 to 18) or b: H or —CH ₃ l: an integer of 2 to 12 R ₁ : H or —C _r H _{2r + 1} (r: an integer of 1 to 8).

_{X: -OH, -OR 2 (R} 2: -C r H 2r + 1), - F, -Cl, -Br,
Or -CN The macromonomer (M) used in the present invention is, as described above, only at one end of a polymer main chain containing at least one repeating unit represented by the general formula (IIa) or (IIb). Having a chemical structure in which the polymerizable double bond group represented by the general formula (I) is directly bonded or bonded by an arbitrary linking group. Formula (I) component and formula (II
Examples of the group connecting the component (a) or (IIb) include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, carbon atom, sulfur atom, nitrogen atom, silicon Atoms) and any combination of heteroatom-heteroatom bond atomic groups.

Preferred among the macromonomers (M) of the present invention are those represented by the formula (IV).

Formula (IV) In the formula, a ₁ , a ₂ , b ₁ , b ₂ , and V represent the same contents as those described in Formula (I), Formula (IIa), and (IIb), respectively.

T represents -Q represented by the general formula (II a) -X ₀ -Q ₀ or general formula represented by (II b), respectively formula (II a), the same as described in Formula (II b) Indicates the content.

W ₁ is a simple bond or [Z ₄ and Z _{5 each} represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, etc.], CH ＝ CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [Z ₆ and Z ₇ represent a hydrogen atom, a hydrocarbon group or the like having the same content as Z ₁ above] or a single linking group selected from an atomic group such as Express.

Formula (I), (IIa), (IIb) or (I
In V), particularly preferable examples of each of X ₀ , Y, V, a ₁ , a ₂ , b ₁ , and b ₂ are shown below.

The _{X 0 -COO -, - OCO -} , - O -, - CH 2 COO- or -CH ₂ OCO- is, Y is an alkyl or alkenyl group having 18 or less carbon atoms, as the V those of the (Wherein Z ₁ is a hydrogen atom), but a ₁ , a ₂ , b ₁ , and b ₂ include a hydrogen atom or a methyl group.

Hereinafter, in the general formula (IV) Specific examples of the group represented by are shown below. However, the content of the present invention is not limited to these.

In the following, m ₁ represents an integer of _{1 to} 12, n ₁ represents an integer of 2 to 12, a: H or —CH ₃ .

(B) -20 CH ₂ = CH-OCO (CH _{2 m1} S- (B) -26 CH ₂ = CH-CH ₂ OCO (CH _{2 m1} S- The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, a method by 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. Using the contained polymerization initiator and / or chain transfer agent, an oligomer having a terminal reactive group bond obtained by radical polymerization is reacted with various reagents to obtain a macromer by a radical polymerization method, polyaddition or polymerization. A method by a polyaddition condensation method in which a polymerizable double bond group is introduced into the oligomer obtained by the condensation reaction in the same manner as in the radical polymerization method, may be mentioned.

Specifically, P. Dreyfuss & RPQuirk, Eucycl.Poly
m.Sci.Eng., 7 , 551 (1987), PFRempp & E.Franta, A
dv.Polym.Sci., 58 , 1 (1984), V.Percec, Appl.Polym.Sc
i., 285, 95 (1984), R. Asami, M. TakaRi, Makvamol. Chem.
Suppl., 12 , 163 (1985), P. Rempp, et al., Makvamol. Chem.
Suppl., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (19
87), 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, Polymer Processing, 35 , 262 (198
6), can be synthesized according to the methods described in the reviews of Kishiro Higashi, Takashi Tsuda, Functional Materials, 1987 , No. 10, 5, etc. and references and patents cited therein.

Next, together with the macromonomer (M) described above, a monomer represented by the general formula (III) which is a copolymer component of the comb-type copolymer will be described.

In the formula (III), X ₁ has the same content as X ₀ in the formula (IIa), and preferably represents —COO—, —OCO—, —CH ₂ O
_{CO -, - CH 2 COO -} , - O-, or Is mentioned.

Q ₁ has the same contents as Q ₀ in the formula (IIa), and preferably represents an aliphatic group having 1 to 22 carbon atoms. Specifically, the aliphatic group of Z _{1 in} the above formula (I) Represents the same content as the group.

d ₁ and d ₂ may be the same or different from each other, and specifically represent the same contents as a ₁ and a _{2 in} the formula (I). Preferably
One of d ₁ and d ₂ represents a hydrogen atom.

The comb-type copolymer may contain, in addition to the monomer represented by the general formula (III), which is a copolymerization component, another monomer copolymerizable with this monomer. For example, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, styrene, chlorostyrene, bromostyrene, vinylnaphthalene, a heterocyclic compound containing a polymerizable double bond group (for example, vinylpyridine, vinylimidazoline, vinylthiophene, vinyldioxane, Vinylpyrrolidone, etc.), unsaturated carboxylic acids (eg, acrylic acid,
Methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc.), itaconic anhydride, maleic anhydride and the like.

The monomer other than the general formula (III) may be any monomer as long as it is a copolymerizable monomer, but preferably, the proportion of these other monomers in all the polymerization components of the comb-type copolymer Is preferably 30% by weight or less.

Further, the comb-type copolymer of the present invention may have the following specific polar group bonded only to one terminal of the polymer main chain.

That, -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, -S
H group, (Here, Z ₀ represents a —Z ₁₀ group or —OZ ₁₀ group, and Z ₁₀ represents a hydrocarbon group), a formyl group, and an amino group.

In polar groups, In showed Z ₀ -Z ₁₀ radical or -OZ ₁₀ group, Z ₁₀ preferably represents a hydrocarbon group having 1 to 18 carbon atoms. It is more preferably Z ₁₀ hydrocarbon group, an optionally substituted aliphatic group (e.g., methyl group having 1 to 8 carbon atoms, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a butenyl group,
Pentenyl group, hexenyl group, 2-chloroethyl group, 2
A cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, etc., or an optionally substituted aromatic group (for example, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a chlorophenyl group) Group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Further, in a polar group of the present invention, the amino group, -NH _2, -NHZ ₁₁
Or Represents Z ₁₁ and Z ₁₂ each independently represent a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, the hydrocarbon group of Z ₁ described above. Represents the same content as.

Still more preferably, the hydrocarbon group of Z ₁₀ , Z ₁₁ and Z ₁₂ is an alkyl group having 1 to 4 carbon atoms which may be substituted, a benzyl group which may be substituted, or a phenyl group which may be substituted. No.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group. Examples of the group linking the comb-type copolymer component and the polar group include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, Silicon atoms), and any combination of heteroatom-heteroatom bond atomic groups.

Among the comb-type copolymers having a specific polar group bonded to one terminal of the polymer main chain of the present invention, preferred are those represented by the formula (Va) or (Vb).

Equation (V a) Equation (V b) Wherein (V a) and _{(V b), a 1,} a 2, b 1, b 2, d 1, d 2,
X ₁ , Q ₁ , V, W ₁ , and T represent the same contents as the symbols in the formulas (I) to (IV).

A represents the above-mentioned polar group bonded to one end of the comb-type copolymer.

W ₂ represents a mere bond or a group linking the specific polar group A and the polymer main chain, and specifically has the same contents as described for W ₁ .

As described above, in the case of a comb-type copolymer having a specific polar group bonded to the terminal of the polymer main chain, a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, Group, amino group, mercapto group, Those which do not contain a copolymer component containing a polar group are preferred.

In order to produce a comb-type copolymer in which a specific polar group is bonded only to one terminal of these polymer main chains, various reagents are reacted with the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization. (Method by ionic polymerization), radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific polar group in the molecule (radical polymerization), or ionic weight as described above. It can be easily produced by a synthesis method such as a method of converting a polymer having a terminal reactive group obtained by a synthetic method or a radical polymerization method into a specific polar group of the present invention by a polymer reaction.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita,
"Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai,
It can be produced by a method described in a review such as "Science and Industry", 60 , 57 (1986) and references cited therein.

Examples of the polymerization initiator containing a specific polar group in the above-mentioned molecule include 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric chloride), 2,2 '-Azobis (2-cyanopropanol),
2,2'-azobis (2-cyanopentanol), 2,2'-
Azobis [2-methyl-N- (2-hydroxyethyl)
-Propioamide], 2,2'-azobis {2-methyl-
N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis {2-methyl-N- [1,1
-Bis (hydroxymethyl) -2-hydroxyethyl]
Propioamide｝, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2 '
-Azobis [2- (4,5,6,7-tetrahydro-1H-1,3-
Diazepin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis [2- (5-hydroxy -3,4,5,6-tetrapyrimidin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane},
2,2'-azobis [N- (2-hydroxyethyl) -2
-Methyl-propionamidine] and 2,2'-azobis [N- (4-aminophenyl) -2-methylpropionamidine].

As a chain transfer agent containing a specific polar group in the molecule, for example, a mercapto compound containing the polar group or a substituent derivable to the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [ N
-(2-Mercaptoethyl) amino] propionic acid, N
-(3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto -2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-
Mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol or the like, or an iodoalkyl compound containing the above polar group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethane) Sulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

These chain transfer agents or polymerization initiators are each used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total monomers.

In the comb-type copolymer having a polar group bonded to one end of the polymer main chain of the present invention, the above-mentioned general formula (V
a) or (Vb), where A-
Further specific examples of the site represented by W _2- will be shown below. However, the scope of the present invention is not limited to these.

In the following, k ₁ represents an integer of 1 or 2, k ₂ represents an integer of _{2 to} 16, and k ₃ represents an integer of 1 or 3.

(B-1) HOOCCH _{2 k1} S- (B) -3 HOOC (CH _{2 k2} OOC (CH _{2 k1} S− (B) -4 HOOC (CH _{2 k2} NHCO (CH _{2 k1} S− (B) -7 HO (CH _{2 k1} S- (B) -8 H ₂ N (CH _{2 k1} S- _{(B) -12 HO 3 S (} CH 2) 2 S- (B) -29 HOOC (CH ₂ ) ₂ NH (CH _{2 k1} S− (B) −30 HOOCCH _{2 k2} CONH (CH _{2 k2} S−) The monomer (A) in the present invention can be used in a non-aqueous solvent. Any monofunctional monomer which is soluble but insolubilized by polymerization may be used, and specific examples include a monomer represented by the general formula (VI).

General formula (VI) Wherein (VI), alpha is -COO -, - OCO -, - CH 2 OCO -, -
CH ₂ COO−, −O−, Represents Here, R ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms (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).

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

e ₁ and e ₂ may be the same or different from each other, and each represents the same content 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-ethoxyethyl 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, cyclic anhydride of itaconic acid; acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable bibond group (specifically, for example, "Polymer Data Handbook-Basic Edition", edited by The Society of Polymer Science, p. 175- 184, Baifukan (1
986), 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.

In order to produce the dispersion resin used in the present invention as described above, generally, the dispersion stabilizing resin as described above and the monomer (A) are mixed with benzoyl peroxide, azobisisobutyroyl in a non-aqueous solvent. Heat polymerization may be performed in the presence of a polymerization initiator such as nitrile and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin and a monomer (A), and a method of adding a monomer (A) together with a polymerization initiator to a solution in which a dispersion stabilizing resin is dissolved The remaining monomer (A) is added together with the polymerization initiator to a method of dropping, or in a mixed solution containing the whole amount of the dispersion stabilizing resin and a part of the monomer (A).
And a method of optionally adding a mixed solution of the dispersion stabilizing resin and the monomer (A) together with the polymerization initiator in a non-aqueous solvent, and the like. Can also be manufactured.

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

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

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 decomposition stability, re-dispersibility and fixability even when a large-size master plate is used.

If desired, a colorant may be used in the liquid developer of the present invention. The colorant is not particularly specified, 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 described in JP-A-44-22955. As described above, 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.

Hereinafter, embodiments of the present invention will be exemplified, but the contents of the present invention are not limited thereto.

Production example 1 of macromonomer 1: M-1 methyl methacrylate 100 g, mercaptopropionic acid
A mixed solution of 5 g and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added and reacted for 4 hours.
Further, 0.5 g of AIBN was added and reacted for 3 hours, and 0.3 g of AIBN was further added and reacted for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to the reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in methanol 2 to obtain 82 g of a white powder. The weight average molecular weight of the polymer was 6,500.

Macromonomer M-1: Macromonomer Preparation Examples 2 to 27: M-2 to M-27 The reaction was carried out in the same manner as in Preparation Example 1 except that in Example 1 of macromonomer, only the methacrylate was replaced with a compound corresponding to Table 1 below. Macro-monomers M-2 to M-
27 was synthesized. The weight average molecular weight of each obtained macromonomer was in the range of 5,000 to 7,000.

Production Example 28 of Macromonomer: M-28 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
In addition, the reaction was performed for 4 hours. Further, 0.5 g of AIBN was added, and the reaction was performed for 3 hours, and then 0.3 g of AIBN was further added, and the reaction was performed for 3 hours.
The reaction solution was cooled to room temperature, 18.2 g of 2-carboxyethyl methacrylate was added, and 24 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 1 g of methylene chloride were added.
50 g of the mixed solution 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 out the precipitated crystals was separated into methanol 2
Re-sinked inside. 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 obtain a polymer having a weight average molecular weight of 5,800 in a yield of 54 g.

Macromonomer M-28: Macromonomer Production Examples 29-35: M-29-35 In the macromonomer M-28 production examples, the methacrylate monomer (corresponding to dodecyl methacrylate) and the unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) were respectively replaced. , M-28 in the same manner as in the production example
Each of the macromonomers shown in Table 2 below was produced. The weight average molecular weight of each obtained macromonomer was 5,000 to 7,000.

Production Example 36 of Macromonomer: M-36 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., 6.5 g of triethylamine was added, and 5.6 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 methanol 2 was performed twice to obtain 63 g of a pale yellow viscous substance.
The weight average molecular weight was 6,600.

Macromonomer M-36: Production Example 37 of Macromonomer: M-37 A mixed solution of 100 g of 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 reacted for 5 hours, and 1.0 g of ACV was further added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 of methanol, and the oil was collected by decantation and dried under reduced pressure. Yield 85
g.

50 g of the obtained oil (oligomer), 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, and the temperature was 100 ° C. For 15 hours. After cooling, the reaction solution was reprecipitated in petroleum ether 1 to obtain 42 g of a white powder. The weight average molecular weight was 7,500.

Macromonomer M-37: Macromonomer Preparation Example 38: M-38 In Macromonomer Preparation Example 37, 50 g of the obtained intermediate oligomer, a mixed solution of 2-hydroxyethyl methacrylate 2.8 g and methylene chloride 100 g, were stirred at room temperature with DCC. 4.0 g, 4-dimethylaminopyridine 0.5 g
And a mixed solution of 10 g of methylene chloride was added dropwise over 1 hour.
The mixture was further stirred for 4 hours. The precipitated crystals are filtered off,
The operation of reprecipitating the filtrate in methanol 1 was performed twice,
The obtained powder was dried under reduced pressure. The yield was 43 g and the weight average molecular weight was 7,300.

Macromonomer M-38: Production Example 1 of dispersion stabilizing resin: P-1 Octadecyl methacrylate 80 g, macromonomer M
A mixed solution of 20 g of -1 and 150 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. Add 1.0 g of ACV and react for 4 hours, then add 0.3 g of ACV and add 2 hours and AC
0.3 g of V. was added and reacted for 3 hours. After cooling, methanol 2
After re-precipitation and aggregation, the obtained white powder was dried to obtain 76 g of a powder having a weight average molecular weight of 4.8 × 10 ⁴ .

Dispersion stabilizing resin P-1: Production Examples 2-15 of Dispersion Stabilizing Resin: P-2 to P-15 Production Example 1 was repeated except that octadecyl methacrylate and macromonomer M-1 were replaced with the compounds shown in Table 3 below in Production Example 1 of P-1. By reacting in the same manner as in Example 1, each dispersion stabilizing resin was produced. Weight average molecular weight of each resin 3.5 × 10 ⁴ 〜
It was 5.0 × 10 ⁴ .

Production Example 16 of dispersion stabilizing resin: P-16 70 g of octadecyl methacrylate, macromonomer M
-10, 30 g, thiomalic acid 0.8 g, toluene 100 g and isopropyl alcohol 50 g in a nitrogen stream at a temperature of 8
Warmed to 0 ° C. 1,1'-azobis (cyclohexane-1
0.8 g of carbocyanide) (abbreviation: ABCC) was added and reacted for 4 hours.
0.3 g of CC was added and reacted for 4 hours. After cooling, the precipitate was reprecipitated in methanol 2, aggregated and dried to obtain 78 g of a white powder. The weight average molecular weight was 3.8 × 10 ⁴ .

Dispersion stabilizing resin P-16: Production Examples 17 to 25 of Dispersion Stabilizing Resin: P-17 to P-25 In the production examples of P-16, octadecyl methacrylate, macromonomer M-10 and mercapto compound (thiomalic acid) are compounds corresponding to Table 4 below. In place of each other, the same reaction as in Production Example 16 was carried out, and each of the resins P-17 to P-25 was reacted.
Was manufactured. Weight average molecular weight of each resin is 3.0 × 10 ⁴ to 4 ×
It was 10 ⁴ .

Production Examples 26 to 31 of Dispersion Stabilizing Resins: P-26 to P-31 In the same manner as in Production Example 1, except that the azobis compound shown in Table 5 below was used in place of the polymer initiator ACV, the operation was the same as in Production Example 1. Thus, each resin was manufactured.

The weight average molecular weight of each of the obtained resins is 3.0 × 10 ^{4 to} 6 × 10
^{Was 4} .

Production Example 32 of dispersion stabilizing resin: P-32 n-dodecyl methacrylate 85 g, macromonomer M
A mixed solution of -28 (15 g) and toluene (150 g) was heated to a temperature of 75 ° C under a nitrogen stream. Add 1.0g of AIBN for 4 hours,
Further, 0.5 g of AIBN was added and reacted for 3 hours. Or even AI
After adding 0.3 g of BN, the mixture was heated to a temperature of 90 ° C. and reacted for 2 hours. After cooling, the reaction product was reprecipitated in methanol 2 and the precipitated viscous substance was collected by decantation and dried under reduced pressure. The yield of the transparent viscous material is 76 g and the weight average molecular weight is 4.3
× 10 ⁴

Dispersion stabilizing resin P-32: Production Examples of Dispersion Stabilizing Resin 33-42: P-33-P-42 In the production examples of P-32, except that n-dodecyl methacrylate and macromonomer M-28 were replaced with a mixture corresponding to Table 6 below. In the same manner as in Production Example 32, each resin P
-33 to P-42 were produced. The weight average molecular weight of each resin is 3.
It was 5 × 10 ^{4 to} 4.5 × 10 ⁴ .

Production Example 1 of Latex Particles 1: A mixed solution of 100 g of D-1 vinyl acetate, 12 g of dispersion stabilizing resin P-4 and 380 g of Isopar H was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 0.8 g of AIBN was added and reacted for 4 hours, and 0.4 g of AIBN was further added and reacted for 2 hours. Twenty minutes after the addition of the initiator, cloudiness occurred, and the reaction temperature was raised to 88 ° C.
The temperature was raised to 0 ° C and the mixture was stirred for 1 hour to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a nylon cloth of 200 mesh, and the resulting white dispersion was a latex having a polymerization rate of 90% and an average particle size of 0.20 μm.

Production Examples 2 to 19 of Latex Particles: D-2 to D-29 Production Example 1 was the same as Production Example 1 of latex particles except that the dispersion stabilizing resin P-4 was replaced with each compound shown in Table 7 below.
Each latex particle was produced under the same conditions as described above. The conversion of each latex particle was 80-85%.

Production example 30 of latex particles: D-30 100 g of vinyl acetate, 5 g of crotonic acid, dispersion stabilizing resin P-
5 and 14 g of Isopar E were heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.3 g of 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN) was added, and after 6 hours of reaction, the temperature was raised to 100 ° 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.
%, And a latex having an average particle size of 0.24 μm.

Production Example 31 of Latex Particles: D-31 14 g of dispersion stabilizing resin P-16, 100 g of vinyl acetate, 4-
A mixed solution of 6.0 g of pentenoic acid and 380 g of Isopar G,
The mixture was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. AIB
0.7 g of N. 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 nylon cloth of 200 mesh, and the obtained white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 32 of latex particles: D-32 A mixed solution of 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 14 g of dispersion stabilizing resin P-25 and 380 g of n-decane,
The mixture was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 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 nylon cloth of 200 mesh, and the obtained white dispersion was latex having an average particle size of 0.26 μm.

Production Example 33 of Latex Particles: D-33 Methyl methacrylate 100 g, Dispersion stabilizing resin P-20
A mixed solution of 25 g and 470 g of n-decane was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. Add 1.0g of AIVN 2
Reacted for hours. A few minutes after the addition of the initiator, blue turbidity started and the reaction temperature rose to 90 ° C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex having a particle size of 0.35 μm.

Production Example 34 of Latex Particles: D-34 A mixed solution of 100 g of styrene, 14 g of dispersion stabilizing resin P-8, and 380 g of Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 0.6 g of AIVN was added and reacted for 4 hours, and 0.30 of AIVN was further added and reacted for 3 hours. After cooling, the mixture was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was latex having a particle size of about 0.20 μm.

Production Example 35 of Latex Particles (Comparative Example A) In Production Example 1 of latex particles D-1, the dispersion stabilizing resin P-4 (12 g) and the dispersion stabilizing resin P-
In the same manner as in Production Example 1 except that 20 g of poly (octadecyl methacrylate) was used instead of 4 (8 g), the resulting white dispersion was a latex having a polymerization rate of 85% and an average particle size of 0.25 μm. Was.

Production Example 36 of Latex Particles (Comparative Example B) A mixed solution of 20 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate and 385 g of Isopar H was prepared. 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-60-179951) Production Example 37 of Latex Particles (Comparative Example C) 20 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 1 g of monomer (I) having the following chemical structure, and Isopar H The operation was carried out in the same manner as in Production Example 1 except that a mixed solution of 385 g was used. The resulting white dispersion has a conversion of 86% and an average particle size of 0.24μ.
m latex. (Latex particles described in JP-A-62-151868) Monomer (I) Example 1 dodecyl methacrylate / acrylic acid (copolymerization ratio: 95 /
5 weight ratio) copolymer 10g, nigrosine 10g and shell sol 7
30 g of 1 was put together with glass beads in a paint shaker (Tokyo Seiki Co., Ltd.) 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-mentioned nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol), [octadecene-half-maleic acid octadecylamide copolymer] 0.08
The liquid developer for electrostatography was prepared by diluting g into 1 of the shell sol 71.

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

Comparative Liquid Developer A: Latex Particle Production Example 35 Resin Dispersion Comparative Liquid Developer B: Latex Particle Production Example 36 Resin Dispersion Comparative Liquid Developer C: Latex Particle Production Example 37 Resin Dispersion The liquid developer is used as a developer for the fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.), and ELP Master II type electrophotographic tourism material (manufactured by Fuji Photo Film Co., Ltd.) is exposed and developed. Processed. Plate making speed is 5
Performed at plate / min. In addition, 200 ELP Master II types
After the zero-sheet processing, the presence or absence of toner contamination on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 20% original.

 The results are shown in Table-8.

As described above, where plate making is performed using each developer under plate making conditions,
The developer which did not cause staining of the developing device and had a clear image on the 2,000th 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 from each developer is printed by a conventional method, and the number of printed sheets until the occurrence of missing characters or solid blurring in the printed image is compared. As a result, the master plate obtained by using the developer of the present invention and Comparative Example A was 10,000
It did not occur even with more than one sheet, and occurred on 7000 sheets in the master plate using Comparative Example B, and occurred on 9000 sheets in the master plate using Comparative Example C.

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.

That is, in the case of Comparative Example A, there was no problem with the number of printed sheets, but the developing device was significantly stained and could not withstand continuous use.

In Comparative Examples B and C, the plate making speed was 5
When used at a high speed of 2 sheets / min (conventionally, plate making speed of 2 to 3 sheets / min), the developing device (especially on the back electrode plate) becomes stained. (E.g., decrease in Dmax, blurred thin lines, etc.). In Comparative Example C, the number of printed master plates was reduced by 10% or more compared to the present invention, and in Comparative Example B, it was reduced by 30% or more.

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

Example 2 100 g of white decomposition product 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 0.25 μm was obtained.

32 g of the above black resin dispersion, FOC-1600 (Nissan Chemical Co., Ltd.)
The liquid developer was prepared by diluting 20 g of hexadecyl alcohol) and 0.05 g of zirconium naphthenate into one of the shell sols 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 31 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 is passed through a 200-mesh nylon cloth to remove the remaining dye,
A 0.25 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.

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 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 2 of latex particles
g, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-1800
A liquid developer was prepared by diluting 15 g (Ottadecyl alcohol, manufactured by Nissan Chemical Co., Ltd.) and 0.020 half-docosanilamide of a copolymer of diisobutylene and maleic anhydride to 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 10,000 sheets were printed 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-3 obtained in Production Example 3 of latex particles, 4.2 g of the above-described alkali blue dispersion and 0.06 g of a semi-docosanyl amidated copolymer of diisobutylene and maleic anhydride were added to Isopar G 1 To obtain 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 31 In Example 5, D-
A liquid developer was prepared in the same manner as in Example 5, except that each latex shown in Table 9 below was used instead of 3.

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 aging.

(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] 1. A liquid developer for electrophotography comprising at least a resin 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. A polymerizable double bond group represented by the following general formula (I) is bonded to only one end of a polymer main chain containing at least one of the polymer components represented by IIa) or (IIb) A comb-type copolymer comprising at least a monofunctional macromonomer (M) having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ^{4 and} a monomer represented by the following general formula (III): In the presence of a soluble dispersion stabilizing resin, a solution containing at least one monofunctional monomer (A) which is soluble in the non-aqueous solvent but insolubilized by polymerization is obtained by a polymerization reaction. Electrostatic imaging characterized by being obtained polymer resin particles Use liquid developer. General formula (I) Wherein (I), V is _{-COO -, - OCO-, CH 2} m OCO-,
CH _{2 m} COO−, −O−, −CONHCOO−, −CONHCO−, −
SO ₂ −, −CO−, Represents Here, Z ₁ represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 to 3. a ₁ and a ₂ may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO
-Z ₂ or -COO-Z ₂ via a hydrocarbon (Z ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group). General formula (IIa) General formula (IIb) In formula (IIa) or (IIb), X ₀ represents the same content as V in formula (I). Q ₀ represents an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Q is -CN or Represents Here, Y represents a hydrogen atom, a halogen atom, an alkoxy group or —COOZ ₃ (Z ₃ represents an alkyl group, an aralkyl group or an aryl group). b ₁ and b ₂ may be the same or different from each other, and represent the same contents as a ₁ and a ₂ in the formula (I). General formula (III) In formula (III), X ₁ has the same content as X ₀ in formula (IIa), and Q ₁ has the same content as Q ₀ in formula (II a). d ₁ and d ₂ may be the same or different from each other and represent the same contents as a ₁ and a ₂ in the formula (I). However, in the macromonomer (M) component represented by the general formula (II) and the monomer component represented by the general formula (III), Q
_At least _one of ₀ and Q ₁ has 10 to 2 carbon atoms.
Represents an aliphatic group of 2. 2. The dispersion stabilizing resin according to claim 1, wherein one end of the polymer main chain comprises -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, -OH group, -SH
Group, (Here, Z ₀ represents a -Z ₁₀ group or -OZ ₁₀ group, and Z ₁₀ represents a hydrocarbon group), a formyl group, and a weight-average molecular weight of 2 × 10 3 formed by bonding a polar group selected from an amino group. ^{4. The} liquid developer for electrophotography according to claim 1, wherein the liquid developer is a comb copolymer of ^{4 to} 2 × 10 ⁵ .