JP2597201B2 - 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.

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. In the above, the dispersed resin particles are partially crosslinked with a polymer containing a repeating unit represented by the following general formula (I), and
-PO ₃ H ₂ group, -SO ₃ H at only one end of one polymer main chain
Group, -COOH group, -OH group, -SH group, (Where Z ⁰ represents -Z ¹⁰ group or -OZ ¹⁰ group, and Z ¹⁰ represents a hydrocarbon group) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, which is formed by bonding a polar group selected from In addition, the monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and the following general formula (II)
Carboxyl group, sulfo group, hydroxyl group only at one end of the main chain of the polymer consisting of repeating units represented by
Formyl group, amino group, phosphono group, and (R ⁰ represents an —R ¹ group or —OR ¹ group, and R ¹ represents a hydrocarbon group). An oligomer having a number average molecular weight of 10 ⁴ or less formed by bonding at least one polar group selected from B)
Is a polymer resin particle obtained by polymerizing a solution containing at least one of the above.

General formula (I) In the general formula (I), T ¹ is -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. Represents -COO-Z ¹ via Wherein Z ¹ represents a hydrocarbon group having 1 to 22 carbon atoms.

General formula (II) 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-,
-S -, - CO -, - CO 2 -, - OCO -, - SO 2 -, (Y ¹ represents the same content as Y ⁰ described above).

R ² and R ³ 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, b ^2, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ⁵ or -COO-R ⁵ (R ⁵ via a hydrocarbon 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 1 or more.

 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), Shellsol 70, Cielsol 71
(Shelsol; trade name of Shell Oil Company), 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 non-aqueous solvent, wherein a part of the polymer chain is crosslinked with a polymer containing a repeating unit represented by the general formula (I), and
Only at one end of at least one polymer backbone, -PO ₃ H ₂
Group, -SO _3H group, -COOH group, -OH group, -SH group, and (Where Z ⁰ represents a —Z ¹⁰ group or —OZ ¹⁰ group, and Z ¹⁰ represents a hydrocarbon group). It is produced by polymerizing (A) and oligomer (B) (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, 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.

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

The dispersion stabilizing resin according to the present invention, which is used to convert the solvent-insoluble polymer produced by polymerizing the monomer (A) and the oligomer (B) in a non-aqueous solvent into a stable resin dispersion. Is a polymer containing a repeating unit represented by the above general formula (I), wherein a part of the polymer chain is cross-linked and at least one terminal of at least one polymer main chain is -PO ₃ H
₂ group, -SO ₃ H group, -COOH group, -OH group, -SH group, (Where Z ⁰ represents a -Z ¹⁰ group and Z ¹⁰ represents a hydrocarbon group) and is a polymer soluble in the non-aqueous solvent, which is formed by bonding a polar group selected from the group consisting of:

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-, -OC
_{O -, - 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, etc.), -OZ ² , -COO-Z ² ,-
A substituent such as OCO-Z ² (where Z ² represents an alkyl group having 6 to 22 carbon atoms, for example, a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group); No. More preferably, A ¹ represents an alkyl or alkenyl group having 8 to 22 carbon atoms. For example, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and the like can be mentioned.

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 group, -COO-Z ¹ or -CH ₂ COO-Z ¹ (wherein
Z ¹ represents an aliphatic group having 1 to 22 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, Octadecyl group, docosanyl group, pentenyl group, hexenyl group, heptenyl group,
Octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, 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 ³ or -CH ₂ COO-Z ³ (where Z ³ 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, decyl group, dodecyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group,
And the like, and these alkyl groups and alkenyl groups are those described above.
A ¹ may have the same substituents as those represented by A ¹ ).

Monomer (A) and oligomer (B) in a non-aqueous solvent
The dispersion stabilizing resin of the present invention used for converting the solvent-insoluble polymer produced by polymerizing the solvent into a stable resin dispersion contains at least one repeating unit represented by the general formula (I).
A species-containing polymer, part of which is cross-linked, and at least one end of at least one polymer backbone,
Carboxy group, sulfo group, phosphono group, hydroxyl group, mercapto group, [Where Z ⁰ represents a -Z ¹⁰ group or -OZ ¹⁰ group, and Z ¹⁰ is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably an aliphatic group having 1 to 8 carbon atoms, and which may be substituted. Groups (e.g., methyl, ethyl, propyl, butyl, hexyl,
Octyl, 2-chloroethyl, 2-methoxyethyl, butenyl, pentenyl, hexenyl, benzyl, phenethyl, bromobenzyl, methoxybenzyl, chlorobenzyl, methylbenzyl, cyclopentyl, cyclohexyl Represents an optionally substituted aryl group (eg, phenyl, tolyl, xylyl, chlorophenyl, bromophenyl, methoxyphenyl, methoxyphenyl, ethylphenyl, methoxycarbonylphenyl, etc.)] And a polymer formed by bonding at least one polar group selected from the group consisting of: here,
The polar group has a chemical structure in which the polar group is directly bonded to one end of the polymer main chain or is bonded via an arbitrary linking group.

As a linking group, a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom bond And any combination of the atomic groups. For example, [Where Z ⁴ and Z ⁵ are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group) Etc.], CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [Wherein Z ⁶ and Z ⁷ each independently represent a hydrogen atom, a hydrocarbon group having the same meaning as Z ¹ shown in the general formula (I), etc.] Examples include a linking group or a linking group composed of an arbitrary combination.

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 copolymerizing a corresponding monomer and another monomer that can be copolymerized, and is partially crosslinked.

Here, as another monomer copolymerizable with the monomer corresponding to the repeating unit represented by the general formula (I), for example,
In the monomer corresponding to the repeating unit represented by the general formula (I), a ¹ , a ² and T ¹ have the same meanings as those of the general formula (I), and A ¹ is an aliphatic having 1 to 5 carbon atoms. Groups (for example, methyl group, ethyl group, butyl group, pentyl group, cyclopentyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (methylsulfonyl) ethyl group, etc.) Alternatively, a monomer such as an aromatic group (for example, a phenyl group, a tolyl group, a xylyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group) can be given.

Further, specific examples of other copolymerizable monomers include, for example, acrylonitrile, methacrylonitrile,
Heterocyclic compound containing a polymerizable double bond group (specifically,
For example, compounds described in “Polymer Data Handbook -Basic Edition-”, edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986), for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, Vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.), a compound containing a carboxamide group or a sulfamide group and containing a polymerizable double bond group (for example, acrylamide, methacrylamide, diacetone acrylamide, 2-carboxyamidoethyl methacrylate, vinylbenzenecarboxamide, vinylbenzenesulfonamide, 3-sulfamidopropylmethacrylate, etc., styrene and its derivatives (for example, styrene, chlorostyrene, vinyltoluene, vinylnaphtha) Emissions, chloromethylstyrene, etc.)
And the like.

In the dispersion stabilizing resin of the present invention, the resin represented by the general formula (I)
The monomer corresponding to the repeating unit represented by is 40% by weight to 10% by weight.
0% by weight is suitable, preferably 60% to 100% by weight
It is.

In the dispersion stabilizing resin of the present invention, as a method for introducing a crosslinked structure into a 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
⁸ (where Z ⁸ 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.

Specific examples of the polymerizable functional group include CH ₂ CHCH— and 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-, but and the like, monomer having a polymerizable functional group two or more, or those of these polymerizable functional groups of the same Any monomer having two or more different monomers may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene as monomers having the same polymerizable functional group; polyhydric alcohols (for example, Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pertaerythritol, etc. ) Or polyhydroxyphenols (eg, hydroquinone, resorcin, catechol and their derivatives), methacrylic acid, acrylic acid or crotonic acid ester acids, vinyl ethers or allyl ethers; dibasic acids (eg, malonic acid) Succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, vinyl esters of itaconic acid, etc.), allyl esters, vinylamides or allyl amide compounds; polyamine (e.g.,
Condensates of ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) with carboxylic acids having a vinyl group (eg, methacrylic acid, acrylic acid, crotonic acid, allylacetic 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, Vinyl of reactants of itaconiloylpropionic acid, carboxylic anhydride and alcohol or amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) Ester derivatives or amide derivatives containing a group (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, methacryloy Vinyl propionate, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene esters, N
-Allyl acrylamide, N-allyl methacrylamide, N-allylitaconamide, methacryloylpropionic allylamide and the like); or amino alcohols (for example, aminoethanol, 1-aminopropanol,
1-aminobutanol, 1-aminohexanol, 2-
And a condensate of a carboxylic acid containing a vinyl group.

The monomer having two or more polymerizable functional groups used in the present invention is polymerized using 15% by weight or less, preferably 10% by weight or less of all monomers, and is soluble in the non-aqueous solvent of the present invention. A certain dispersion stabilizing resin is formed.

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

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
Sci. Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986), etc. It can be produced by the methods described in the reviews and the literature cited therein.

The weight average molecular weight of the dispersion stabilizing resin of the present invention is 1 × 10 ⁴
６6 × 10 ⁵ , more preferably 2 × 10 ⁴ -3 × 10 5
⁵ 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,
0.5 μm) and the particle size distribution is broadened. On the other hand, when it exceeds 6 × 10 ⁵ , the average particle size of the resin particles obtained by polymerization granulation becomes large, and it may be difficult to make the average particle size in a preferable range of 0.15 to 0.4 μm.

The resin polymer for dispersion stabilization used in the present invention specifically contains a monomer corresponding to the repeating unit represented by the general formula (I), the above-mentioned polyfunctional monomer and the polar group. A method of polymerizing a mixture of chain transfer agents with a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or
Without using the chain transfer agent, a method of polymerizing using a polymerization initiator containing the polar group, or a method of using a compound containing the polar group for both the chain transfer agent and the polymerization initiator, Further, in the above three methods, after a polymerization reaction using a compound containing an amino group, a halogen atom, an epoxy group, an acid halide group, or the like as a substituent of a chain transfer agent or a polymerization initiator, a polymer reaction is further performed. And a method of introducing the polar group by reacting with these functional groups.

As the chain transfer agent to be used, for example, the polar group or a mercapto compound containing a substituent capable of being derived from the polar group (eg, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-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-
Mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptophenol Mercaptoethylamine, 2-mecapluimidazole, 2-mercapto-3-pyridinol, etc.) or the above-mentioned polar group or an iodized alkyl compound containing a substituent derivable to the polar group (for example, iodoacetic acid, iodopropionic acid, -Iodoethanol,
2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Examples of the polymerization initiator containing the “polar group” or a substituent derivable to the “polar group” include, for example, 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- (5-
Hydroxy-3,4,5,6-tetrahydropyrimidine-2-
Yl) propane], 2,2'-azobis {2-methyl-N
-[1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl]
Propioamide｝, 2,2'-azobis [2-methyl-N
-(2-hydroxyethyl) -propioamide], 2,
2'-azobis (2-amidinopropane) and the like.

These chain transfer agents or polymerization initiators are each 0.1 to 15% by weight based on 100 parts by weight of all monomers, and are preferably
0.5 to 10% by weight.

The dispersion stabilizing resin of the present invention produced as described above has a polar group bonded only to one end of the polymer main chain,
It is presumed that the component that interacts with the insoluble resin particles and is soluble in the non-aqueous solvent is crosslinked, thereby significantly improving the affinity for the non-aqueous solvent. It is considered that aggregation and precipitation of particles are suppressed, and redispersibility is significantly improved.

Monomers used in producing the non-aqueous dispersion resin,
Monofunctional monomers (A) which are soluble in the non-aqueous solvent but are insolubilized by polymerization can be distinguished from oligomers (B).

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

General formula (III) In the formula (III), G is -COO-, -OCO-, -CH ₂ OCO-, -C
H ₂ COO-, -O-, Represents Here, J ¹ is a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group,
Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl A 3-methoxypropyl group).

J represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2,2-dichloroethyl, 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.).

d ¹ and d ^2, which may be the same or different, each represents the same content as b ¹ or b ² in the general formula (II).

Specific monomers (A) include, for example, those having 1 to 1 carbon atoms.
6 vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid Alkyl esters or amides of a carboxylic acid having 1 to 4 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group as the alkyl group) Group, trifluoroethyl group, 2-hydroxyethyl group, 2
-Cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2- (N, N-dimethylamino)
Ethyl group, 2- (N, N-diethylamino) ethyl group, 2
-Carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
Chloropropyl group, 2-furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc .; styrene derivatives (eg, styrene, vinyltoluene, α-methyl) Styrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid;
Maleic acid, cyclic anhydride of itaconic acid; acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook-Basic Edition" edited by the Society of Polymer Science, Japan, p175-184, compounds described in Baifukan (1986), for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine and the like ) And the like.

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

The oligomer (B) is an oligomer having a number average molecular weight of 10 ⁴ or less, which is formed by bonding the above-mentioned specific polar group to only one end of the main chain of a polymer comprising a repeating unit represented by the general formula (II). It is.

In general formula (II), the hydrocarbon groups contained in b ¹ , b ² , Y ⁰ , Y ¹ and Y ² each have the indicated carbon number (as an unsubstituted hydrocarbon group). The groups may be substituted.

In the general formula (II), 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 and the like, and 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-
A methyl-2-pentenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl Group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.) And an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.).

X ¹ and X ² may be the same or different from each other, -O-,
-S -, - 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 ² and R ³ 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 above-mentioned preferable aliphatic groups for Y ⁰ . However, X ^3, X ⁴ may be the same or different, above-mentioned X ^1,
X ² has the same content as R ² , R ⁴ represents an optionally substituted alkylene group, alkenylene group or aralkyl group having 1 to 18 carbon atoms, and Y ² has the same content as Y ⁰ .

Further specific examples of R ² and R ³ include: [R ⁶ and R ^{7 each} represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms), a halogen atom, or the like], 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, etc.), cyano group, alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -CO
OR ⁵ or -CH ₂ COOR ⁵ (R ⁵ is a hydrogen atom or a carbon atom of 1 to 18
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 above) .

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

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.

Further, in the oligomer (B) 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).

As the other copolymer component, any compound may be used as long as it is a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, and 4-pentenoic acid, and esters or amides of these unsaturated carboxylic acids;
22 fatty acid vinyl esters or allyl esters; vinyl ethers; styrene and styrene derivatives;
Heterocyclic compounds containing an unsaturated bond are exemplified. Specifically, for example, the compounds exemplified for the above-mentioned monomer (A) and the like can be mentioned, but it should not be construed that the invention is limited thereto.

In the total of the repeating units of the oligomer (B), the repeating unit represented by the general formula (II) accounts for 40% by weight of the whole.
Is preferably contained, more preferably 60
~ 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.

A polar group which is bound to only one end of a polymer main chain having a number average molecular weight of 1 × 10 ⁴ or less containing at least one kind of the repeating unit represented by the general formula (II), In the formula, R ⁰ represents a —R ¹ group or —OR ¹ group, and R ¹ preferably represents a hydrocarbon group having 1 to 18 carbon atoms. More preferably, the hydrocarbon group of R ¹ is an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 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, or the like; Group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Alternatively, in the polar group of the present invention, the amino group is -NH ₂ , -NHR
⁸ or Represents R ⁸ and R ⁹ represent a hydrocarbon group having 1 to 18 carbon atoms, and preferably represent a hydrocarbon group having 1 to 8 carbon atoms,
Specifically, the same meaning as the hydrocarbon group of the above-described R ^1.

Still more preferably, as the hydrocarbon group for R ¹ , R ⁸ and R ⁹ , 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 the polar group is directly bonded to one end of the polymer main chain of the oligomer (B) or is bonded via an arbitrary linking group. Examples of the group connecting the component (II) 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, and a silicon atom). Atoms), and any combination of heteroatom-heteroatom bond atomic groups.

Among the oligomers (B) of the present invention, preferred are those represented by the formula (IVa) or (IVb).

Formula (IVa) Formula (IVb) In the formulas (IVa) and (IVb), b ¹ , b ² , R ² , R ³ , X ¹ , X ² , V ⁰ ,
Y ⁰ , m and n represent the same contents as the symbols of the formula (II).

Q represents the above-mentioned polar group bonded to one end of the formula (II).

W is a simple bond or [R ¹⁰ and R ¹¹ represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group)] , CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [R ¹² and R ¹³ each independently represent a hydrogen atom, a hydrocarbon group or the like having the same content as the above-mentioned Y ⁰ ] or a single linking group selected from an atomic group or an arbitrary combination thereof. Represents a linking group.

When the upper limit of the number average molecular weight of the oligomer (B) exceeds 1 × 10 ⁴ , the printing durability decreases. On the other hand, if the molecular weight is too small, soiling tends to occur, so it is preferably 1 × 10 ³ or more.

In addition, it is preferable that the polymer main chain of the oligomer (B) does not contain a copolymer component containing the polar group.

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

Specifically, P. Dreyfuss, RPQuirk, Encycl.Polym.Sc
i.Eng., 7, 551 (1987 ), Nakajo Yoshiki, Yuya Yamashita "dye and medicine", 30, 232 (1985), Akira Ueda, Susumu Nagai "Science and Industry", a review of such as 60, 57 (1986) And the method described in the literature 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'-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].

Examples of the chain transfer agent having a specific polar group in the molecule include a mercapto compound, a disulfide compound, an iodine-substituted compound and the like, and preferably a mercapto compound. For example, thioglycolic acid, 2-mercaptopropionic acid, thiomalic acid, 2-
Mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptoethylamine, thiosalicylic acid, α
-Thioglycerin, 2-phosphonoethyl mercaptan,
Hydroxythiophenol and derivatives of these mercapto compounds are exemplified.

These polymerization initiators and / or chain transfer agents are used at a ratio of 0.5 to 20% by weight based on the total amount of the monomer corresponding to the repeating unit represented by the general formula (II) and other polymerizable monomers. And preferably 1 to 10% by weight.

Preferred examples of the oligomer (B) used in the present invention are represented by the general formula (IVa) or (IVb). The site represented by QW- in these formulas will be more specifically exemplified 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 k ₁ -S- (B) -3: HOOC (CH ₂ k ₂ OOC (CH ₂ k ₁ -S- (B) -4: HOOC (CH ₂ k ₂ NHCO (CH ₂ k ₁ -S- (B) -7: HO (CH ₂ k ₁ -S- (B) -8: H ₂ N (CH ₂ k ₂ -S- (B) -12: HO ₃ S (CH ₂ ) ₂ S− (B) -29: HOOC (CH ₂ ) ₂ NH (CH ₂ k ₁ -S- (B) -30: HOOC (CH ₂ k ₂ -CONH (CH ₂ k ₂ -S-) It is composed of at least one kind of each of the monomer (A) and the oligomer (B). Importantly, if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, a desired dispersion resin is obtained. More specifically, it is preferable to use 0.05 to 10% by weight, more preferably 0.1% by weight, of the oligomer (B) represented by the general formula (II) based on the monomer (A) to be insolubilized. -5% by weight, and even more preferably 0.3-3% 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 oligomer (B) 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 oligomer (B), 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 oligomer (B) together with the polymerization initiator,
Alternatively, a method of optionally adding the remaining monomer mixture together with the polymerization initiator to a mixed solution containing the whole amount of the dispersion stabilizing resin and a part of the mixture of the monomer (A) and the oligomer (B), And a method of optionally adding a mixed solution of a dispersion stabilizing resin and a monomer (A) and an oligomer (B) together with a polymerization initiator in a non-aqueous solvent, and the like. be able to.

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

The soluble resin as the dispersion stabilizing resin is used in an amount of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer (A) and the oligomer (B) used above. .

The amount of the polymerization initiator is suitably from 0.1 to 5% by weight based on the total amount of the monomer (A) and the oligomer (B).

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

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

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

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

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

When the resin particles of the present invention are used as a liquid developer, the details of the reason why the redispersion and the fixability of the toner image are significantly improved as described above are unknown, but in the polymerization granulation method of the resin particles of the present invention, Even after polymerization granulation without using the oligomer (B), the above effect was not observed even if the oligomer (B) was added by post-addition. This is considered that the oligomer (B) used in the resin particles of the present invention has modified the surface of the resin particles.

That is, because the polar group specified and bonded only to one end of the polymer main chain is polymerized and granulated in a non-aqueous solvent, it is bonded to the resin particles by an anchor effect, and the polymer main chain is It is presumed that one of the main factors is that the part modifies the surface of the resin particles and improves the affinity with the dispersion medium.

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, for example, No. 2955, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol.
And those specifically described on page 44 are used.

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

The amounts of the main components of the liquid developer of the present invention will be described below.

The amount of the toner particles containing a resin and a coloring agent used as a main component is preferably 0.5 parts by weight to 50 parts by weight based on 1,000 parts by weight of the carrier liquid. 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 in an amount of 0.1 to 1000 parts by weight of the carrier liquid.
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. Therefore, the amount of each additive is controlled within this limit. It is necessary.

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

Production Example 1 of dispersion stabilizing resin 1: 97 g of P-1 octadecyl methacrylate, thioglycolic acid 3
g, a mixed solution of 5.0 g of divinylbenzene and 200 g of toluene were heated to a temperature of 85 ° C. while stirring under a nitrogen stream. 1,1 ′
-Azobis (cyclohexane-1-carbonitrile)
(Abbreviation ACHN) 0.8g, react for 4 hours, then AC
Add 0.4 g of HN and react for 2 hours, then add 0.2 g of ACHN
In addition, the reaction was performed for 2 hours. After cooling, the mixed solution was reprecipitated in 1.5 liters of methanol, and the white powder was collected by filtration and dried.
88 g were obtained. The weight average molecular weight of the obtained polymer is 30,000
Met.

Production Examples 2 to 9 of Dispersion Stabilizing Resins: P-2 to P-9 In Production Example 1, except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate, the operation was performed in exactly the same manner as in Production Example 1. Each dispersion stabilizing resin was manufactured.

Production Examples 10 to 22 of Dispersion Stabilizing Resins: P-10 to P-22 In Production Example 1, instead of 5 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.

Production Example 23 of dispersion stabilizing resin: P-23 octadecyl methacrylate 97 g, thiomalic acid 3 g,
4.5 g of divinylbenzene, 150 g of toluene and 50 of ethanol
g of the mixed solution was heated to a temperature of 60 ° C. under a nitrogen stream. 2,2 ′
-Azobis (isobutyronitrile) (abbreviation AIBN)
5 g was added and reacted for 5 hours, then 0.3 g of AIBN was added and reacted for 3 hours, and further 0.2 g of AIBN was added and reacted for 3 hours. After cooling, the precipitate was reprecipitated in 2 l of methanol, and the white powder was collected by filtration and dried. In a yield of 85 g, the weight average molecular weight of the polymer was 35,000.

Production Examples 24 to 29 of dispersion stabilizing resin: P-24 to P-29 In the above Production Example 23, instead of thiomalic acid 3 g,
Production Example 23 was repeated except that the mercapto compound in Table 3 below was used.
A dispersion stabilizing resin was produced in the same manner as described above.

Production Example 30 of Dispersion Stabilizing Resin: P-30 A mixture of 94 g of hexadecyl methacrylate, 1.0 g of diethylene glycol dimethacrylate, 150 g of toluene and 50 g of isopropyl alcohol was heated to a temperature of 90 ° C. under a nitrogen stream. 6 g of 2,2'-azobis (4-cyanovaleric acid) (abbreviated as ACV) was added and reacted for 8 hours. After cooling, the reaction solution was reprecipitated in 1.5 l of methanol, and the white powder was collected by filtration and dried. In a yield of 83 g, the weight average molecular weight of the polymer was 65,
000.

Production Example 31 of dispersion stabilizing resin; P-31 A mixed solution of 92 g of docosanyl methacrylate, 1.5 g of ISP-22GA (manufactured by Okamura Oil Co., Ltd.), 150 g of toluene and 50 g of ethanol was heated to a temperature of 80 ° C. under a nitrogen stream. did. 4, 4'-
8 g of azobis (4-cyanopentanol) was added and reacted for 8 hours. After cooling, the reaction solution was reprecipitated in 1.5 l of methanol, and the white powder was collected by filtration and dried. In a yield of 78 g, the weight average molecular weight of the polymer was 41,000.

Production Example 32 of Dispersion Stabilizing Resin: P-32 A mixed solution of 95 g of octadecyl methacrylate, 5 g of 2-mercaptoethylamine, 5 g of divinylbenzene and 200 g of toluene was heated to 85 ° C. in a nitrogen stream. ACHN
Was added and reacted for 8 hours.

Next, 8 g of glutaconic anhydride and 1 ml of concentrated sulfuric acid were added and reacted at a temperature of 100 ° C. for 6 hours. After cooling, methanol
The precipitate was reprecipitated in 1.5 l, and the white powder was collected by filtration and dried. 83g yield
And the weight average molecular weight was 31,000.

Production Example 33 of dispersion stabilizing resin: P-33 octadecyl methacrylate 95 g, thioglycolic acid 3
g, ethylene glycol dimethacrylate 6 g, toluene 1
A mixed solution of 50 g and 50 g of ethanol was heated under a nitrogen stream.
Heated to 80 ° C. Add 2 g of ACV and react for 4 hours.
0.5 g of ACV was added and reacted for 4 hours. After cooling, the precipitate was reprecipitated in 1.5 l of methanol, and the white powder was collected by filtration and dried. Yield 80
In g, the weight average molecular weight was 35,000.

Production Example 34 of dispersion stabilizing resin: P-34 A mixed solution of 94 g of tridecyl methacrylate, 6 g of 2-mercaptoethanol, 9 g of divinylbenzene, 150 g of toluene and 50 g of ethanol was heated to a temperature of 80 ° C. under a nitrogen stream. Add 4 g of ACHN and react for 4 hours, then add 2 g of ACHN
The reaction was performed for 4 hours.

After cooling, it was washed again in 1.5 l of methanol, the methanol was removed by decantation, and the viscous product was dried. 75g yield
And the weight average molecular weight was 29,000.

Production Example 35 of Dispersion Stabilizing Resin P-35 A mixture of 50 g of the dispersion stabilizing resin P-34, 100 g of toluene, 10 g of succinic anhydride and 0.5 g of pyridine was heated to 90 ° C.
For 10 hours. After cooling, reprecipitate in 0.8 l of methanol,
The methanol was removed by decantation and the viscous material was dried. The yield was 43 g and the weight average molecular weight was 30,000.

Production Examples 36 to 39 of Dispersion Stabilizing Resin: P-36 to P-39 In Production Example 35 of Dispersion Stabilizing Resin P-35, dicarboxylic anhydrides shown in Table 4 below were used instead of succinic anhydride. Except for the above, each dispersion stabilizing resin was produced in the same manner as in Production Example 35.

Production Example 40 of dispersion stabilizing resin: P-40 86 g of octadecyl methacrylate, 10 g of N-methoxymethylacrylamide, 4 g of thioglycolic acid, toluene 1
A mixture of 50 g and 50 g of isopropanol was heated to a temperature of 80 ° C. under a stream of nitrogen.

0.8 g of ACHN was added and reacted for 8 hours. Next, Dean-S
Using a tark, 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 1.5 l of methanol, and the white powder was collected by filtration and dried. The yield was 82 g and the weight average molecular weight was 45,000.

Oligomer Production Example 1: 100 g of oligomer B-1 2,3-diacetoxypropyl methacrylate,
A mixture of 5 g of 3-mercaptopropionic acid, 150 g of toluene and 50 g of methanol was stirred at a temperature of 7 while stirring under a nitrogen stream.
Warmed to 0 ° C. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 4 hours. Further, 0.4 g of AIBN was added and reacted for 4 hours. After cooling, the reaction solution was mixed with methanol / water [(4/1) volume ratio] mixed solution 2
The precipitate was reprecipitated in l, the methanol solution was separated by decantation, and the viscous substance was dried to obtain 75 g of a colorless viscous substance. The number average molecular weight of the polymer was 3,300.

Oligomer Production Examples 2 to 13: Oligomer B-2 to B-13 In the same manner as in Production Example 1, except that the mercapto compound shown in Table 5 below was used in place of 5 g of 3-mercaptopropionic acid in Production Example 1, Operate each oligomer B-2 to B
-13 was produced. The number average molecular weight of the obtained oligomer is
It was 2,500-5,000.

Oligomer Production Examples 14 to 33: Oligomer B-14 to B-33 In Production Example 1, except that monomers corresponding to Table 6 were used instead of 2,3-diacetoxypropyl methacrylate. By operating in the same manner as in Example 1, each oligomer B-
14-B-33 were produced. The number average molecular weight of the obtained oligomer was 2,500 to 3,500.

Oligomer Production Example 34: Oligomer B-34 A mixed solution of 100 g of 2- (n-octylcarbonyloxy) ethyl crotonate, 150 g of toluene and 50 g of ethanol was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 2,
8 g of 2'-azobis (cyanovaleric acid) (abbreviated as ACV) was added and reacted for 5 hours. Further, 2 g of ACV was added and reacted for 4 hours. After cooling the obtained reaction solution, it was reprecipitated in a mixed aqueous solution of methanol / water [(4/1) volume ratio]. The aqueous methanol solution was separated by decantation, and the viscous substance was dried. The number average molecular weight of the polymer was 2,600 in a yield of 70 g.

Oligomer Preparation Examples 35 to 43: Oligomer B-35 to B-43 In Preparation Example 34, except that the azobis compound of Table 7 below was used in place of the polymer initiator ACV, the same operation as in Preparation Example 34 was performed. Each oligomer B-35 to B-43 was prepared. The number average molecular weight of the obtained oligomer was 2,000 to 4,000.

Production Example 1 of Latex Particles: D-1 A mixed solution of 18 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 0.8 g of oligomer B-1 and 380 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. Heated. 2,2 ′
-Azobis (isovaleronitrile) (abbreviated as AIVN)
0.8 g was added and reacted for 2 hours, and 0.3 g of AIVN was further added and reacted for 2 hours. Twenty minutes after the addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. The temperature was raised to 100 ° C. and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth.
The latex was 89% and had an average particle size of 0.23 μm.

Latex particle production examples 2 to 30: D-2 to D-30 In latex particle production example 1, except that the dispersion stabilizing resin and oligomer were replaced with the compounds shown in Table 8 below,
Each latex particle was produced under the same conditions as in Production Example 1.
The conversion of each latex particle was 85-90%.

Production Example 31 of Latex Particles: D-31 16 g of dispersion stabilizing resin P-7, 100 g of vinyl acetate, 5 g of crotonic acid, 0.8 g of oligomer B-36 and Isopar E
468 g of the mixed solution was heated to 70 ° C. while stirring under a nitrogen stream. After adding 1.3 g of AIVN and reacting for 6 hours, the temperature was 100
C. and the mixture was stirred for 1 hour, and the remaining vinyl acetate was distilled off. After cooling, pass through a 200 mesh nylon cloth,
The obtained white dispersion has a polymerization rate of 88% and an average particle size of 0.22 μm.
Latex.

Production Example 32 of Latex Particles: D-32 18 g of dispersion stabilizing resin P-27, 100 g of vinyl acetate, 4-
A mixed solution of 6.0 g of pentenoic acid, 0.8 g of oligomer B-22 and 380 g of Isopar G was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. Add 0.7g of AIBN and react for 4 hours,
Further, 0.5 g of AIBN was added and reacted for 2 hours. 20 after cooling
After passing through a 0-mesh nylon cloth, the obtained white dispersion was a latex having a conversion of 89% and an average particle size of 0.23 μm.

Manufacturing Example 33 of Latex Particles: D-33 18 g of dispersion stabilizing resin P-32, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 0.6 g of oligomer B-1 and n-
While stirring the mixed solution of 380 g of decane under a nitrogen stream,
Heated to 75 ° C. 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. 200 after cooling
After passing through a mesh nylon cloth, the resulting white dispersion was a latex having a conversion of 88% and an average particle size of 0.20 μm.

Production Example 34 of latex particles: D-34 20 g of dispersion stabilizing resin P-1, 100 g of isopropyl methacrylate, 0.8 g of oligomer B-23 and n-decane 47
0 g of the mixed solution was heated to 70 ° C. while stirring under a nitrogen stream. 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 was a latex having a conversion of 85% and an average particle size of 0.25 μm.

Production Example 35 of Latex Particles: D-35 While stirring a mixed solution of 16 g of dispersion stabilizing resin P-2, 100 g of styrene, 0.9 g of oligomer B-6 and 380 g of Isopar H under a nitrogen stream, the temperature was raised to 60 ° C. Heated. AIV
0.6 g of N. was added and reacted for 4 hours, and 0.3 g of AIVN was further added and reacted for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a conversion of 84% and an average particle size of 0.23.
μm latex.

Production Example 36 of Latex Particles (Comparative Example A) In Production Example 1 of latex particles, oligomer B-
Except for Example 1, the procedure was the same as in Production Example 1. The resulting white dispersion was a latex having a conversion of 85% and an average particle size of 0.25 μm.

Production Example 37 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 had a conversion of 85% and an average particle size of 0.22.
μm latex. (Latex equivalent to JP-A-60-179951) Preparation Example 38 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 prepared in the same manner as in Production Example 1 except that 385 g of a mixed solution was used. The obtained white dispersion has a polymerization rate of 86% and an average particle size of 0.1.
It was a 24 μm latex. (Latex equivalent to JP-A-62-151868) Monomer [I] Example 1 Dodecyl methacrylate / acrylic acid (copolymerization ratio: 95 /
(5 weight ratio) 10 g of the copolymer, 10 g of nigrosine and 30 g of Shellsol 71 were placed in a paint shaker (Tokyo Seiki Co., Ltd.) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

The resin dispersion D-1 of Production Example 1 of latex particles was added to 30
g, 2.5 g of the above nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd .: tetradecyl alcohol), [octadecene-half-maleic acid octadecylamide copolymer] 0.08
The liquid developer for electrostatography was prepared by diluting g into 1 of Shellsol 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 36 Resin Dispersion Comparative Liquid Developer B: Latex Particle Production Example 37 Resin Dispersion Comparative Liquid Developer C: Latex Particle Production Example 38 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 photosensitive 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 30% original.

 The results are shown in Table-9.

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. The present invention, Comparative Example A
The master plate obtained by using the developer of Comparative Example C did not generate even with 10,000 sheets or more, and the master plate using Comparative Example B generated with 8000 sheets.

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

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 0.24 μm was obtained.

32g 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 1 of Shellsol 71.

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

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

Example 3 100 g of the white dispersion obtained in Production Example 32 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.

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 placed in 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-23 obtained in Production Example 23 of latex particles, 4.2 g of the above-mentioned alkali blue dispersion, and 0.06 g of a half-docosanyl amidated copolymer of diisobutylene and maleic anhydride were added to Isopar G. By diluting to 1, a liquid developer was prepared.

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-
Instead of using each latex of Table 10 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 three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

(Effect of the Invention) According to the present invention, a developer having excellent dispersion stability, redispersibility, and fixability was obtained. In particular, even when used under very high plate-making speed, the developing device was not stained, and both 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. .

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), a part of which is cross-linked, and at least one terminal of at least one polymer main chain, a -PO ₃ H ₂ group, a -SO ₃ H group,
-COOH group, -OH group, -SH group, (Where Z ⁰ represents -Z ¹⁰ group or -OZ ¹⁰ group, and Z ¹⁰ represents a hydrocarbon group) in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, which is formed by bonding a polar group selected from In addition, one of the main chains of a polymer comprising a monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization and a repeating unit represented by the following general formula (II): Only at the terminal carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and (R ⁰ represents an —R ¹ group or —OR ¹ group, and R ¹ represents a hydrocarbon group). An oligomer having a number average molecular weight of 10 ⁴ or less formed by bonding at least one polar group selected from B)
, Which are polymer resin particles obtained by polymerizing a solution containing at least one of the following. General formula (I) In the general formula (I), T ¹ is -COO-, -OCO-, -CH ₂ OCO-,-
Represents CH ₂ COO-, -O- or -SO _2- . 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. Represents -COO-Z ¹ via Wherein Z ¹ represents a hydrocarbon group having 1 to 22 carbon atoms. General formula (II) In the general formula (II), V ⁰ is -O-, -S-, -COO-, -OC
O -, - 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-,-
S -, - CO -, - CO 2 -, - OCO -, - SO 2 -, (Y ¹ represents the same content as Y ⁰ described above). R ² and R ³ 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 1 or more.