JP2597196B2 - 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.

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. 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 degree of dispersion of the particles, redispersibility, storage stability is described in JP-A-60-179951 and JP-A-62-17975.
No. 151868 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.

Further, there is an increasing demand for rationalization of the electrophotographic plate making system, and specifically, it is intended to extend the period of maintenance of the plate making machine. This demands a liquid developer that can be used for a long time without replacement.

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.

Further, the dispersed resin particles produced according to the means disclosed in JP-A-60-179951 and JP-A-61-43375, when the development speed is increased or when the maintenance period is extended, the dispersion of particles Performance and redispersibility were not always satisfactory.

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

An object of the present invention is to provide a liquid developer having excellent dispersion stability, redispersibility and fixability even in an electrophotographic plate making system in which a development-fixing process is accelerated and a maintenance interval is set to be long. To provide.

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. In the above, the dispersion resin particles are a polymer containing a repeating unit represented by the following general formula (I), and a part of the polymer main chain is cross-linked to form a dispersion stabilizing resin soluble in the non-aqueous solvent. A monofunctional monomer (A) which is soluble in the non-aqueous solvent in the presence, but is insolubilized by polymerization;
A monofunctional macro having a number average molecular weight of 10 ⁴ or less, comprising a polymerizable double bond group represented by the following general formula (III) bonded to only one end of a polymer main chain comprising a repeating unit represented by the following formula: This is achieved by a liquid developer for electrophotography, which is a copolymer resin particle obtained by polymerizing a solution containing at least one monomer (M).

General formula (I) In the general formula (I), T ¹ represents —COO—, —OCO—, —CH ₂ OCO
_{-, - CH 2 COO -,} - O- or -SO ₂ - represent.

A ¹ represents an aliphatic group having 6 to 32 carbon atoms.

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

General formula (II) General formula (III) In the general formula (II), V ₀ is -O-, -S-, -COO
-, - OCO -, - CH 2 OCO- or represents a -CH ₂ COO-.

Y ₀ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

X ₁ and X ₂ may be the same or different from each other;
-, - CO -, - CO 2 -, - OCO -, - SO 2 -, (Y ₁ represents the same content as Y ₀ described above).

R ₁ and R ₂ may be the same or different from each other, may be substituted, or (X ₃ and X ₄ may be the same or different from each other, and have the same contents as X ₁ and X ₂ above, and R ₄ is the number of carbon atoms which may be substituted. indicates 1 to 18 hydrocarbon group, Y ₂ is representative of the Y ₀ indicating the same contents as] a hydrocarbon group having 1 to 18 carbon atoms.

b ₁ and b ₂ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₅
Or —COO—R ₅ via a hydrocarbon (R ₅ represents a hydrogen atom or a hydrocarbon group which may be substituted).

m, n and p may be the same or different;
Represents an integer of 4. However, m + n is at least 1 or more.

In the general formula (III), V ₁ represents -O-, -COO-,-
_{OCO -, - CH 2 OCO -} , - CH 2 COO -, - SO 2 -, - CONH-,
−SO ₂ NH−, Represents -CONHCOO- or -CONHCONH- (provided that R ₆ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

d ₁ and d ₂ may be the same or different from each other, and have the same meanings as b ₁ or b _{2 in} the general formula (II), respectively.

 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, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, isoper H, isoper L (Isoper; Exxon; Product name), Cielsol 70, Cielsol 71
(Cielsol; trade name of Cieloil), Amsco
OMS, 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 a polymer containing a repeating unit represented by the general formula (I) in a non-aqueous solvent, wherein a part of the polymer main chain is cross-linked to form a dispersion stabilizing resin soluble in the non-aqueous solvent. Below, it is manufactured by copolymerizing the monomer (A) and the macromonomer (M) (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 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, cyclohexane, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propion) 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.

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.

In a non-aqueous solvent, monomer (A) and macromonomer (M)
The dispersion stabilizing resin according to the present invention used for forming a stable resin dispersion from the solvent-insoluble copolymer formed by copolymerizing the above-mentioned compound contains a repeating unit represented by the general formula (I). The polymer is a polymer soluble in the non-aqueous solvent, in which a part of the polymer chain is crosslinked with the polymer.

Hereinafter, the repeating unit represented by formula (I) will be described in more detail.

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

In the general formula (I), T ¹ is preferably -COO-, -O
_{CO -, - CH 2 OCO -} , - CH 2 COO- or represents -O-, more preferably -COO -, - represents a CH ₂ COO- or -O-.

A ¹ preferably represents an alkyl group, an alkenyl group or an aralkyl group which may have 8 to 22 carbon atoms and may be substituted. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and the like), —O—Z ² , —COO—
Z ^2, --OCO-Z ² (wherein Z ² represents an alkyl group having 6 to 22 carbon atoms, e.g., hexyl, octyl, decyl, dodecyl, hexadecyl group, octadecyl group, etc.), etc. Substituents. More preferably, A
¹ represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms. For example, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, octenyl group, decenyl group,
Dodecenyl group, tetradecenyl group, hexadecenyl group,
And octadecenyl group.

a ¹ and a ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, and a carbon atom of 1
To 3 alkyl groups, -COO-Z ³ or -CH ₂ COO-Z ³ (wherein Z ³ represents an aliphatic group having 1 to 22 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group , Hexyl group,
Octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl etc., and these aliphatic groups represent also may) have the same substituents as represented by the a ^1. More preferably, a ¹ and a ² are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.), —COO—Z ⁴ or —CH ₂ COO—Z ⁴ (here, Z ⁴ represents an alkyl group or an alkenyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, etc., and these alkyl group, alkenyl group represents an in may) have the same substituents as represented by the a ^1.

The dispersion stabilizing method of the present invention, which is used for forming a stable resin dispersion from the solvent-insoluble copolymer formed by copolymerizing the monomer (A) and the macromonomer (M) in a non-aqueous solvent. The resin is a polymer containing at least one kind of the repeating unit represented by the general formula (I) and having a part of the polymer main chain crosslinked and soluble in the non-aqueous solvent.

The polymer component of the dispersion stabilizing resin of the present invention may be a homopolymer component or a copolymer component selected from the repeating units represented by the general formula (I) or a repeating unit represented by the general formula (I). The polymer contains a copolymer component obtained by polymerizing a corresponding monomer and another monomer that can be copolymerized, and a part of the polymer main chain is crosslinked.

Any other monomer that can be copolymerized may be any as long as it contains a polymerizable double bond group. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; Ester derivatives or amide derivatives of carboxylic acids; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; and a heterocyclic compound containing a polymerizable double bond group. More specifically, for example, vinyl citrates or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); acrylics, methacrylic acid, croton Unsubstituted alkyl esters or amides of unsaturated carboxylic acids such as acids, itaconic acids, and maleic acids (eg, methyl, ethyl, propyl, butyl, 2- Chloroethyl group, 2-bromoethyl group, 2-
Fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group,
2-methoxyethyl group, 2-methanesulfonylethyl group, 2-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-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinyl Benzenecarboxamide,
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid; cyclic anhydrides of maleic acid and itaconic acid;
Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, “Polymer Data Handbook -Basic Part-” edited by The Society of Polymer Science, p1
75-184, compounds described in Baifukan (1986), for example, N-vinylpyridine, N-vinylimidazole,
-Vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine and the like).

In the polymer component of the dispersion stabilizing resin, the compound represented by the general formula (I)
The component of the repeating unit represented by is at least 30% by weight or more, preferably 50% by weight or more of all the components of the polymer,
It is more preferably at least 70% by weight.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of the monomer, there are a method of polymerizing in the presence of a polyfunctional monomer and a method of including a functional group which advances a crosslinking reaction in a polymer and crosslinking by a polymer reaction.

The dispersion stabilizing resin of the present invention has a self-bridging method due to its simple production method (for example, a long reaction time is required, the reaction is not quantitative, impurities are mixed in by using a reaction promoting aid, and the like). Functional group having a cross-linking reaction: -CONHCH ₂ OZ
⁵ (where Z ⁵ represents a hydrogen atom or an alkyl group) or a crosslinking reaction by polymerization is effective.

In the polymerization reaction, preferably, a method of crosslinking between polymer chains by polymerizing a monomer having two or more polymerizable functional groups together with a monomer corresponding to the repeating unit represented by the above formula (I) It is.

Specifically, as the polymerizable functional group, CH ₂ CHCH—, CH ₂ CHCH
−CH ₂ −, _{CH 2 = CH-CH 2 -NHCO-} , CH 2 = CH-SO 2 -, CH 2 = CH-CO-, CH 2 = CH-O-, CH 2 = CH-S-, and the like However, the monomer having two or more polymerizable functional groups may be a monomer having two or more of the same or different polymerizable functional groups.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene;
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylol Ethane, pentaerythritol, etc.) or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol and derivatives thereof)
Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid; dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid) Vinyl esters, allyl esters, vinyl amides or allyl amides; polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

Further, as a monomer having a different polymerizable functional group, for example, a carboxylic acid containing a vinyl group (e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, Itaconiloyl propionic acid, a reactant of a carboxylic anhydride and an alcohol or amine (eg, allyloxycarbonyl propionic acid,
Allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) or ester derivatives or amide derivatives containing vinyl groups (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, methacrylic acid) Allyl, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl methacrylate, vinyl oxy carbonyl methyl oxy carbonyl ethylene acrylate, N-
Allyl acrylamide, N-allyl methacrylamide,
N-allylitaconamide, methacryloylpropionic allylamide, etc.); and amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-
Condensates of aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) with a carboxylic acid having a vinyl group.

The monomer having two or more polymerizable functional groups used in the present invention is polymerized using 10% by weight or less, preferably 5% by weight or less of all monomers, and is soluble in the non-aqueous solvent of the present invention. A certain resin is formed.

The weight average molecular weight of the dispersion stabilizing resin of the present invention is 1 × 10
^{4 to} 2 × 10 ⁵ is preferable, and more preferably 2.5 × 10 ⁴ to 1 ×
10 ^five . When the weight average molecular weight is less than 1 × 10 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5 μm) and the particle size distribution becomes wide. Further, when it exceeds 2 × 10 ⁵ , the average particle size of the resin particles obtained by polymerization granulation becomes too small, and 0.15 to 0.4
It may be difficult to make the average particle size uniform in a preferable range of μm.

The dispersion stabilizing resin polymer used in the present invention is, specifically, a monomer corresponding to a repeating unit represented by the general formula (I), which is a known method, and the above-mentioned polyfunctional monomer. A method in which polymerization is carried out with a polymerization initiator (for example, an azobis-based compound, a peroxide, or the like) at least in the coexistence is simple and preferable.

The polymerization initiator used here is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of all monomers.
% By weight.

The dispersion stabilizing resin of the present invention produced as described above interacts with the insoluble resin particles and is adsorbed on the insoluble resin particles. The affinity of the particles to which the dispersion stabilizing resin is adsorbed with the non-aqueous solvent is remarkably improved because the dispersion stabilizing resin soluble in the non-aqueous solvent is crosslinked. In addition to the improved amphiphilicity at the insoluble resin particle interface, the dispersion stabilizing resin present in the non-aqueous solvent without being adsorbed by the particles is further dispersed between the particles adsorbed by the dispersion stabilizing resin. It is presumed that the approach of is three-dimensionally suppressed.

It is considered that these factors suppress the aggregation and precipitation of the insoluble particles, and significantly improve the redispersibility.

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) which is copolymerized with the monomer (A). be able to.

Examples of the monomer (A) include vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, etc.); acrylic acid, methacrylic acid, crotonic acid , Alkyl esters or alkylamides having 1 to 3 carbon atoms of unsaturated carboxylic acids such as itaconic acid and maleic acid; styrene,
Styrene derivatives such as vinyltoluene, chlorostyrene and α-methylstyrene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and itaconic acid, anhydrides or amidates; hydroxyethyl methacrylate, hydroxyethyl acrylate , Methoxyethyl methacrylate, ethoxyethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, trimethoxysilylpropyl methacrylate, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, 2-cyanoethyl methacrylate, 2-chloroethyl methacrylate, N-vinyl Hydroxy group, amino group, amide group, shear group such as pyridine, N-vinylimidazole, 2-furfurylethyl methacrylate Group, a sulfonic acid group, a carbonyl group, a halogen atom, can be mentioned a polymerizable monomer such as containing various polar groups such as a heterocyclic group.

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

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

In general formulas (II) and (III), b ₁ , b ₂ , Y ₀ , Y ₁ , Y
_2, d _1, hydrocarbon group contained in the d ₂ and R ₆ have each indicated number of carbon atoms (the hydrocarbon group unsubstituted), these hydrocarbon groups may be substituted.

The repeating unit represented by formula (II) used in the present invention will be further described.

V ₀ is, -O -, - S -, - COO -, - OCO -, - CH 2 OCO
- or represents a -CH ₂ COO-.

Y ₀ preferably represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms. Preferred aliphatic groups include alkyl groups having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, Hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (for example, 2-methyl-1-
Propenyl group, 2-butenyl group, 2-pentenyl group, 3
-Methyl-2-pentenyl group, 1-pentenyl group, 1-
A hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group,
Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
Examples thereof include an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, and the like).

X ₁ and X ₂ may be the same or different from each other;
-, - CO -, - COO -, - OCO -, - SO 2 -, (Y ₁ denote the same contents as the Y ₀₎ represent. More preferably, -O-, -CO-, -COO-, -OCO- or Represents

R ₁ and R ₂ may be the same or different from each other, may be substituted, or Having 1 to 18 carbon atoms (an aliphatic group such as an alkyl group, an alkenyl group, an aralkyl group or an alicyclic group). Is shown. Preferred specific examples of these aliphatic groups include the same contents as the preferred aliphatic groups for Y ₀ described above, provided that X ₃ and X ₄ may be the same or different.
X ₁ represents the same content as X ₂ , R ₄ represents an optionally substituted alkylene group having 1 to 18 carbon atoms, alkenylene group or aralkyl group, and Y ₂ represents the same content as Y ₀ .

Further examples of R ₁ and R ₂ include: (R ₇ and R ₈ represent a hydrogen atom, an alkyl group, a halogen atom, etc.), CH 、 CH, (X ₃ , X ₄ , Y ₂ , R ₄ , and p have the same meaning as the above symbols).

b ₁ and b 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-R ₅ or -CH ₂ COOR ₅ (R ₅ is a hydrogen atom or a carbon atoms 1 to 1
8 represents an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically represents the same contents as those described for Y ₀ ) Express.

Further, m, n and p may be the same or different and each represents a number of 0, 1, 2, 3, and 4, provided that m + n is at least 1 or more.

Specific examples of the repeating unit represented by the general formula (II) are described below. However, the content of the present invention is not limited to these. In the following, a is H or CH ₃ , R is a C _1-18 alkyl group, R ′ is a hydrogen atom or a C _1-18 alkyl group, k ₁ and k ₂ are integers of 1 to 12, l ₁ and l _{2 each} represent an integer of 1 to 100.

In the general formula (III), V ₁ represents -O-, -COO-,-
_{OCO -, - CH 2 OCO -} , - CH 2 COO -, - SO 2 -, - CONH-,
−SO ₂ NH−, Represents -CONHCOO- or -CONHCONH-. Here, R ₆ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. Preferably an aliphatic group having 1 to 18 carbon atoms as the hydrocarbon group, specifically include those of the same contents as those described above Y _0.

d ₁ and d _2, which may be the same or different from each other, the same meanings as b ₁ or b ₂ in the general formula (II). A preferred range of d ₁ and d ₂ are each a content similar to that described for b ₁ and b ₂ as described above.

More preferably, _one of b ₁ and b _{2 in} the general formula (II) and _one of d ₁ and d _{2 in} the general formula (III) are a hydrogen atom.

As described above, the macromonomer used in the present invention has a compound represented by the general formula (II) only at one terminal of a polymer main chain containing at least the repeating unit represented by the general formula (II).
The polymerizable double bond group represented by I) is directly bonded,
Alternatively, it has a chemical structure linked by an arbitrary linking group. 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) of the present invention are those represented by the formula (IV).

Formula (IV) In the formula (IV), b ₁ , b ₂ , d ₁ , d ₂ , Y ₀ , V ₀ , V ₁ , R ₁ , R ₂ ,
X ₁ , X ₂ , m and n represent the same contents as described in the general formulas (II) and (III), respectively.

W is a simple bond or (R ₉ and R ₁₀ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group)), CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [R ₁₁ and R ₁₂ each represent a hydrogen atom or a hydrocarbon group representing the same content as the above-mentioned Y ₀ ] or a single linking group selected from an atomic group such as Represents

The upper limit of the number average molecular weight of the macromonomer (M) 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 that it is preferably 1 × 10 ³ or more.

Particularly preferable examples of each of Y ₀ , V ₀ , V ₁ , b ₁ , b ₂ , d ₁ , and d _{2 in} the general formulas (II), (III), and (IV) are shown.

The _{V 0, -COO -, - OCO} -, - O -, - CH 2 COO-
Or -CH ₂ OCO- is an alkyl or alkenyl group 18 or less carbon atoms as Y ₀ is, as the V ₁ as the all (where, R ₆ is hydrogen atom) is, b _1, b _2, d _1, d ₂
As a hydrogen atom or a methyl group.

Shown below in general formula (IV) The following shows a specific example. However, the content of the present invention is not limited to these. In the following, b is an H or CH _3, the integer m ₁ is 2 to 12, n ₁ represents an integer of 1 to 12.

Further, in the macromonomer (M) used in the present invention, other repeating units may be contained as a copolymer component together with the repeating units represented by the general formula (II).

The other copolymerization component may be any repeating unit composed of another monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). Such other monomers include, for example, acrylic acid, methacrylic acid,
Itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4
-Unsaturated carboxylic acids such as pentenoic acid and esters or amides of these unsaturated carboxylic acids; fatty acid vinyl esters or allyl esters having 1 to 22 carbon atoms; vinyl ethers; styrene and styrene derivatives; And heterocyclic compounds. In particular,
For example, the compounds exemplified for the above-mentioned monomer (A) and the like are exemplified, but not limited thereto.

In the saturation of the repeating unit of the macromonomer (M), the repeating unit represented by the general formula (II)
%, 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 original plate The effect of improving the performance cannot be seen.

The macromonomer (M) 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, Adv.
Polym.Sci., 58 , 1 (1984), V.Percec, Appl.Polym.Sci.,
285 , 95 (1984), R. Asami, M. TakaRi, Makvamol. Chem. Sup
pl., 12 , 163 (1985), P. Remp. et al., Makvamol. Chem. Sup.
pl., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (198
7), 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.

The dispersion resin of the present invention comprises at least one of each of a monomer (A) and a macromonomer (M). It is important that the resin synthesized from these monomers be insoluble in the non-aqueous solvent. Thus, a desired dispersion resin can be obtained. More specifically, the macromonomer (M) is preferably used in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the insoluble monomer (A). More preferably, the content is 0.3 to 3% by weight. The molecular weight of the dispersion resin of the present invention is 10 ³ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersion resin used in the present invention as described above, generally, the dispersion stabilizing resin and the monomer (A) as described above are used.
And the macromonomer (M) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin, the monomer (A) and the macromonomer (M), and a method of dissolving the monomer (A) in a solution in which the dispersion stabilizing resin is dissolved. )
And a method of dropping the macromonomer (M) together with the polymerization initiator, or the polymerization is carried out in a mixed solution containing the entire amount of the dispersion stabilizing resin and a mixture of the monomer (A) and the macromonomer (M). A method of optionally adding the remaining monomer mixture together with the initiator, and further, a dispersion stabilizing resin and a monomer (A) and a macromonomer (M) in a non-aqueous solvent.
And a method of arbitrarily adding a mixed solution together with a polymerization initiator, and any of these methods can be used for production.

The total amount of the monomer (A) and the macromonomer (M) 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 soluble resin that is the dispersion stabilizing resin is 1 to 1 with respect to 100 parts by weight of the total amount of the monomer and macromonomer used above.
00 parts by weight, preferably 5 to 50 parts by weight.

The amount of polymerization initiator depends on the total amount of monomer and macromonomer.
0.1 to 5% by weight is suitable.

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.

In particular, in the non-aqueous dispersion resin described in JP-A-62-151868, a monomer containing at least two ester bonds or the like, which can be copolymerized with a monomer that is polymerized and insolubilized, is contained in the molecule. These are resin particles obtained by coexisting a monomer.These are significantly improved in dispersibility and printing durability compared to conventional particles. When the processing speed of a plate making machine using a master plate (for example, EPL-560, EPL-820, etc., manufactured by Fuji Photo Film Co., Ltd.) or the processing speed of the plate making machine was increased, there was still a problem in the dispersibility of the particles. However, when the resin particles used in the present invention are used, no problem occurs even under such severe conditions.

As described above, 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.

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 as described in JP-B-44-22955. As described above, there is a method of using a monomer containing a dye in advance to produce a dye-containing copolymer 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. 16, No. 2,
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 composed mainly of a resin (and a coloring agent optionally used) are used in an amount of 0.5 to 1000 parts by weight of the carrier liquid.
It is preferably from 50 to 50 parts by weight. 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 can be added in an amount of about 0.5 to 100 parts by weight based on 1,000 parts by weight of the carrier liquid.
The charge control agent as described above is used for 1,000 parts by weight of the carrier liquid.
0.001 to 1.0 part by weight is preferred. 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, if the electric resistance of the liquid developer in a state where the toner particles are removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high quality continuous tone image.
It is necessary to control the amount of each additive within this limit.

(Examples) Production examples of the dispersion stabilizing resin, production examples of latex particles, and examples of the present invention will be described below, but the present invention is not limited thereto.

Production Example 1 of dispersion stabilizing resin 1: P-1 octadecyl methacrylate 100 g, divinylbenzene
A mixed solution of 2 g and 200 g of toluene was heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 3.0 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 4 hours.
Add 1.0g of AIBN and react for 2 hours.
0.5 g was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in methanol 1.5, and the white powder was collected by filtration and dried to obtain 88 g of a powder. The weight average molecular weight of the obtained polymer was 3.3 × 10 ⁴ .

Production Examples 2 to 14 of Dispersion Stabilizing Resins: P-2 to P-14 In Production Example 1, except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate, the same operation as in Production Example 1 was performed. Each dispersion stabilizing resin was manufactured. The weight average molecular weight of each resin was 3.0 × 10 ^{4 to} 5 × 10 ⁴ .

Production Examples 15 to 27 of Dispersion Stabilizing Resins: P-15 to P-27 In Production Example 1, instead of 2 g of divinylbenzene, which is a polyfunctional monomer for crosslinking, a polyfunctional monomer shown in Table 2 below was used. Each dispersion stabilizing resin was produced in the same manner as in Production Example 1 except that the polymer or oligomer was used. The weight average molecular weight of each resin was 3 × 10 ^{4 to} 6 × 10 ⁴ .

Production Example 28 of dispersion stabilizing resin: P-28 A mixture of 95 g of octadecyl methacrylate, 5 g of N-methoxymethylacrylamide, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75 ° C. under a nitrogen stream. A.
3.0 g of IBN was added and reacted for 8 hours. Next, Dean-Star
Using k, the mixture was heated to a temperature of 110 ° C. and stirred for 6 hours. The solvent used, isopropanol, and methanol produced as a by-product of the reaction were removed. After cooling, the precipitate was reprecipitated in methanol 1.5, and the white powder was collected by filtration and dried. The yield is 82 g and the weight average molecular weight is
It was 5.6 × 10 ⁴ .

Production Example 1 of Macromonomer 1: 96 g of M-1 2- (n-hexylcarbonyloxy) ethyl methacrylate, 4 g of thioglycolic acid and 200 g of toluene
Was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 8 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 an oily substance. The number average molecular weight of the polymer was 5,600.

Macromonomer Preparation Examples 2 to 21: M-2 to M-21 In Macromonomer Preparation Example 1, except that only 2- (n-hexylcarbonyloxy) ethyl methacrylate was replaced with a compound corresponding to Table 3 below. The reaction was carried out in the same manner as in Production Example 1 to synthesize a macromonomer. The number average molecular weight of each obtained macromonomer was in the range of 5,000 to 7,000.

Production Example 22 of Macromonomer: M-22 A mixed solution of 96 g of 2,3-diacetoxypropyl methacrylate, 4 g of thioethanol and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. AIBN 1.
0 g was added and reacted for 4 hours. Add 0.5 g of AIBN and add 3
After that, 0.3 g of AIBN was further added and reacted for 3 hours.
The reaction solution was cooled to room temperature, 9.6 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 50 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 methanol 2. 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 number average molecular weight of 3,800 in a yield of 54 g.

Production Examples of Macromonomer 23 to 29: M-23 to M-29 In the production example of macromonomer M-22, 2,3-diacetoxypropyl methacrylate and an unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) were used. In place of each, the macromonomers in Table 4 below were each produced in the same manner as in the production example of M-22. The number average molecular weight of each of the obtained macromonomers was in the range of 3,000 to 6,000.

Production Example 30 of Macromonomer: M-30 A mixed solution of 96 g of 2- [3-methoxycarbonylpropylcarbonyloxy] ethyl methacrylate, 4 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran,
The mixture was heated to 70 ° C. under a nitrogen stream. 1.0 g of AIBN was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 4 hours. Next, the reaction solution was cooled in a water bath to a temperature of 20 ° C., 6.3 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, an operation of reprecipitating in methanol 2 was performed twice to obtain 54 g of a pale yellow viscous substance. The number average molecular weight was 4,300.

Production example 31 of macromonomer: M-31 2,3-dipropyloxypropyl methacrylate 95 g,
150 g of tetrahydrofuran and 50 of isopropyl alcohol
g of the mixed solution was heated to a temperature of 75 ° C. under a nitrogen stream. Four,
4'-azobis (4-cyanovaleric acid) (abbreviation: ACV)
4.0 g was added and reacted for 5 hours. Further, 1.0 g of ACV was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 of water, and the oil was collected by decantation and dried under reduced pressure. The yield was 85 g.

50 g of this oil (oligomer), 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 2,
1.0 g of 2'-methylenebis (6-t-butyl-p-cresol) was added, and the mixture was stirred at 100 ° C for 15 hours. After cooling,
The reaction solution was reprecipitated in petroleum ether 1 to obtain 36 g of a transparent viscous substance. The number average molecular weight was 3,600.

Production Example 32 of Macromonomer: M-32 In Production Example 31 of the macromonomer, a mixed solution of 50 g of the obtained intermediate oligomer (oil), 5.6 g of 2-hydroxyethyl methacrylate, and 100 g of methylene chloride was added.
Under stirring at room temperature, a mixed solution of 9.0 g of DCC, 0.5 g of 4-dimethylaminopyridine and 20 g of methylene chloride was added dropwise over 1 hour. The mixture was further stirred for 4 hours. The precipitated crystals were separated by filtration, and the operation of reprecipitating the filtrate in petroleum ethanol 1 was performed twice, and the obtained oil was dried under reduced pressure. The yield is
The number average molecular weight was 3,000 at 28 g.

Production Example 33 of Macromonomer: M-33 A mixed solution of 95 g of 2- (n-nonylcarbonyloxy) ethyl crotonate and 200 g of tetrahydrofuran was heated to a temperature of 75 ° C. under a nitrogen stream. 5 g of 2,2'-azobis (cyanoheptal) was added and reacted for 8 hours.

After cooling, the temperature of the reaction solution was adjusted to 20 ° C. in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour and then at 60 ° C. for 6 hours.

The obtained reaction product was cooled and then reprecipitated in methanol 2 twice to obtain 62 g of a colorless and transparent viscous substance.
The number average molecular weight was 6,200.

Production Examples of Macromonomer 34 to 41: M-34 to M-41 In the production example of macromonomer M-1, the methacrylate monomer [2- (n-hexylcarbonyloxy)
Ethyl methacrylate), a mercapto compound (corresponding to thioglycolic acid) and an epoxy group-containing monomer (corresponding to glycidyl methacrylate)
In the same manner as in Production Example No.-1, macromonomers in Table 5 below were produced.

Production example of latex particles: D-1 A mixed solution of 20 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1.0 g of macromonomer M-1 and 380 g of Isopar H was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. Heated. A.
Add 0.8g of IBN and react for 4 hours, then add 0.4g of AIBN
In addition, the reaction was performed 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 1 hour to distill off unreacted vinyl acetate. After cooling
After passing through a 200-mesh nylon cloth, the obtained white dispersion was a latex having a conversion of 90% and an average particle size of 0.25 μm.

Production Example 2 of Latex Particles: D-2 A mixed solution of 18 g of dispersion stabilizing resin P-2, 100 g of vinyl acetate, 1.0 g of macromonomer M-2 and 385 g of Isopar H was stirred under a stream of nitrogen while heating. Heated to 70 ° C. 2,2'-azobis (isovaleronitrile) (abbreviation A.
(IVN) was added thereto and reacted for 2 hours.
After adding 4 g and reacting for 2 hours, 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 the resulting white dispersion was a latex having a polymerization rate of 85% and an average particle size of 0.22 μm.

Production Examples 3 to 31 of latex particles: D-3 to D-31 Same as Production Example 2 except that the dispersion stabilizing resin and the macromonomer were changed to the compounds shown in Table 6 below in Production Example 2 of latex particles. Each latex particle was manufactured under the following conditions. The conversion of each latex particle was 80-85%.

Production Example 32 of Latex Particles: D-32 A mixed solution of 20 g of dispersion stabilizing resin P-10, 100 g of vinyl acetate, 5 g of crotonic acid, 1.0 g of macromonomer M-6 and 468 g of Isopar E was stirred under a nitrogen stream. While the temperature
Heated to 70 ° C. After adding 1.3 g of AIVN and reacting for 6 hours, 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 the resulting white dispersion had a polymerization rate of 85% and an average particle size of 0.1.
23 μm latex.

Production Example 33 of Latex Particles: D-33 19 g of dispersion stabilizing resin P-12, 100 g of vinyl acetate, 4-
A mixed solution of 6.0 g of pentenoic acid, 1.5 g of macromonomer M-7 and 380 g of Isopar G was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 0.7 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 nylon cloth of 200 mesh, and the obtained white dispersion was a latex having an average particle size of 0.24 μm.

Production Example 34 of Latex Particles: D-34 A mixed solution of 20 g of dispersion stabilizing resin P-14, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of macromonomer M-1 and 380 g of n-decane was passed through a nitrogen stream. The mixture was heated to a temperature of 75 ° C. with stirring. 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 0.2 μm.

Production Example 35 of Latex Particles: D-35 While stirring a mixed solution of 20 g of dispersion stabilizing resin P-3, 100 g of isopropyl methacrylate, 1.0 g of macromonomer M-8 and 470 g of n-decane, while stirring under a nitrogen stream, the temperature was lowered. 70
Warmed to ° C. 1.0 g of AIVN was added and reacted for 2 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 had an average particle size of 0.30 μm.
Latex.

Production Example 36 of Latex Particles: D-36 A mixed solution of 20 g of dispersion stabilizing resin P-13, 100 g of styrene, 0.6 g of macromonomer M-25 and 380 g of Isopar H was stirred at a temperature of 60 under a nitrogen stream. Warmed to ° C.
Add 0.6g of AIVN and react for 4 hours, then 0.3g of AIVN
In addition, the reaction was performed for 3 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 0.25 μm.

Production Example 37 of Latex Particles (Comparative Example A) The same procedure was followed as in Production Example 1 of latex particles except for the macromonomer (M-1), and the resulting white dispersion was 85% polymerized and had an average particle size of 85%. It was a latex having a diameter of 0.25 μm.

Production Example 38 of Latex Particles (Comparative Example B) A mixed solution of 18 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 has a conversion of 85% and an average particle size of 0.22μ.
m latex. (Corresponding to latex particles of JP-A-60-179951) Production Example 39 of Latex Particles (Comparative Example C) 18 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 1 g of monomer (I) having the following chemical structure, and isopar H was used as a mixed solution of 385 g, and the other operations were the same as in Production Example 1.

The resulting white dispersion has a conversion of 86% and an average particle size of 0.24μ.
m latex. (Equivalent to latex particles of JP-A-62-151868) Production Example 40 of Latex Particles (Comparative Example D) A mixed solution of 12 g of a dispersion stabilizing resin having the following structure (described in JP-A-61-43577), 100 g of vinyl acetate and 388 g of Isopar H was prepared. The same operation was performed.

The resulting white dispersion has a conversion of 85% and an average particle size of 0.20 μm.
m latex.

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.

Using the resin dispersion (D-1) of Production Example 1 of latex particles
30 g, the above-mentioned nigrosine dispersion 2.5 g, FOC-1400 (manufactured by Nissan Chemical Co., Ltd .: tetradecyl alcohol) 15 g, [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 D) Four types of liquid developers A, B, C, and D 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 37 Resin Dispersion Comparative Liquid Developer B: Latex Particle Production Example 38 Resin Dispersion Comparative Liquid Developer C: Latex Particle Production Example 40 Resin Dispersion Comparative liquid developer D: resin dispersion of latex particle production example 40 These liquid developers were used as a developer for a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.), and were used as electrophotographic photosensitive materials. An ELP Master II type (Fuji Photo Film Co., Ltd.) was exposed and developed. 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 30% original.

 The results are shown in Table-7.

When the respective developers were subjected to plate making under the plate making conditions described above, only the case of the present invention was a developer which did not cause staining of the developing device and had a clear image on the 2000th plate making plate.

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, Comparative Example A, Comparative Example C and Comparative Example D did not generate even at 10,000 sheets or more, and the master plate using Comparative Example B produced 8,000 sheets. Occurred.

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

Further, in the case of Comparative Examples B and C, if the plate making speed is as fast as 5 sheets / min (conventionally, plate making speed of 2 to 3 sheets / min), the developing device (especially on the back electrode plate) And the quality of the copied image on the plate is affected (reduction of Dmax, blurring of thin lines, etc.) after about 2,000 sheets. The number of printed master plates was satisfactory in Comparative Example C, but decreased in Comparative Example B.

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

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 0.25 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 33 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 3 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 of octadecyl alcohol (manufactured by Nissan Chemical Co., Ltd.) and 0.02 g of half-docosanilamide of a 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 10,000 sheets were printed were clear.

Further, after leaving this developer for 3 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 placed in a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

White resin dispersion obtained in Production Example 23 of latex particles
A liquid developer was prepared by diluting 30 g, 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 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. 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 27 In Example 5, the D-
Except for using each latex of Table 8 below in place of 23,
A liquid developer was prepared in the same manner as in Example 5.

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 3 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 (1)

(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 polymer containing a repeating unit represented by I), wherein a part of the polymer main chain is crosslinked, and in the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent, the polymer is soluble in the nonaqueous solvent. However, it is represented by the following general formula (III) only at one end of a polymer main chain comprising a monofunctional monomer (A) which is insolubilized by polymerization and a repeating unit represented by the following general formula (II). Copolymer resin obtained by polymerizing a solution containing at least one monofunctional macromonomer (M) having a number-average molecular weight of 10 ⁴ or less formed by bonding polymerizable double bond groups. Liquid for electrostatography characterized by being particles Developer. General formula (I) In the general formula (I), T ¹ represents —COO—, —OCO—, —CH ₂ OCO—,
-CH ₂ COO -, - O- or -SO ₂ - represent. A ¹ represents an aliphatic group having 6 to 32 carbon atoms. a ¹ and a ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-Z ¹ or a hydrocarbon group having 1 to 8 carbon atoms. -COO-Z ¹ (wherein Z ¹ represents a hydrocarbon group having 1 to 22 carbon atoms) via represent. General formula (II) General formula (III) In the general formula (II), V ₀ is -O-, -S-, -COO
-, - OCO -, - CH 2 OCO- or represents a -CH ₂ COO-. Y ₀ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. X ₁ and X ₂ may be the same or different from each other, -O-,
_{-CO -, - CO 2 -,} - OCO -, - SO 2 -, (Y ₁ represents the same content as Y ₀ described above). R ₁ and R ₂ may be the same or different from each other, may be substituted, or (X ₃ and X ₄ may be the same or different from each other, and have the same contents as X ₁ and X ₂ above, and R ₄ is the number of carbon atoms which may be substituted. indicates 1 to 18 hydrocarbon group, Y ₂ is representative of the Y ₀ indicating the same contents as] a hydrocarbon group having 1 to 18 carbon atoms. b ₁ and b ₂ may be the same or different from each other, and represent a hydrogen atom,
Represents a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₅ through -COO-R ₅ or hydrocarbon (R ₅ represents a hydrogen atom or an optionally substituted hydrocarbon group). m, n and p may be the same or different;
Represents an integer. However, m + n is at least 1 or more. In the general formula (III), V ₁ represents —O—, —COO—, —OC
_{O -, - CH 2 OCO -} , - CH 2 COO -, - SO 2 -, - CONH -, -
SO ₂ NH-, Represents -CONHCOO- or -CONHCONH- (provided that R ₆ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). d ₁ and d ₂ may be the same or different from each other, and have the same meanings as b ₁ or b _{2 in} the general formula (II), respectively.