JP2014066888A - Liquid developer and production method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid developer which has excellent fixing property adaptable to various kinds of recording materials and which can be fixed in a wide temperature range.SOLUTION: The liquid developer includes toner particles (C) having a core-shell structure. A core resin (b) is a resin comprising a structural unit derived from a diol (b1), a structural unit derived from a carboxyl group-containing diol (b2), and a structural unit derived from diisocyanate (b3) and satisfying expressions (1):1.060≤([b1]+[b2])/[b3]≤1.800 and (2):0.01≤[b2]/([b1]+[b2])≤0.15. In expressions (1) and (2), [b1] expresses a molar ratio of the structural unit derived from the diol (b1) to the core resin (b), [b2] expresses a molar ratio of the structural unit derived from the carboxyl group-containing diol (b2) to the core resin (b), and [b3] expresses a molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b).

Description

  The present invention relates to a liquid developer and a method for producing the same. More specifically, the present invention relates to a liquid developer useful for a wide range of applications such as an electrophotographic liquid developer, an electrostatic recording liquid developer, an oil-based ink for an inkjet printer, or an electronic paper ink, and a method for producing the same.

  When the liquid developer is used for electrophotographic liquid developer, electrostatic recording liquid developer, ink jet printer oil-based ink, or electronic paper ink, the toner particles dispersed in the liquid developer are: After fixing on the paper, it is required to firmly adhere to the paper and not easily peel off.

  As a method for fixing toner particles on a recording material, a method using a heat roller is the mainstream from the viewpoint of speeding up and safety. In recent years, from the viewpoint of energy saving, efforts have been made to simplify the temperature control mechanism of the heat roller or reduce the frequency of temperature control. Therefore, the temperature fluctuation of the heat roller tends to be larger than that of the conventional one, and accordingly, it is desired that the liquid developer can be fixed in a wide temperature range from a low temperature range to a high temperature range. . In particular, it has become a problem to prevent the occurrence of high temperature offset (a phenomenon in which the fixing quality deteriorates in a high temperature range).

  Various attempts have been made to improve the adhesion to paper after fixing (hereinafter also referred to as fixability). For example, Japanese Patent Application Laid-Open No. 2009-96994 (Patent Document 1) proposes a method for improving affinity with paper by introducing an acidic group at the terminal of a resin constituting toner particles.

JP 2009-96994 A

  The fixability is improved to some extent by the technique of Patent Document 1. However, the fixing property is still not sufficient in consideration of adapting to various recording materials such as high-quality paper that requires particularly high fixing property. Further, from the viewpoint of prevention of high temperature offset, it cannot be said to be a sufficient solution, and a further improvement in fixability has been awaited.

  The present invention has been made in view of the circumstances as described above, and an object of the present invention is a liquid that has excellent fixability that can be applied to various recording materials and can be fixed in a wide temperature range. It is in providing a developing agent and its manufacturing method.

  In order to solve the above problems, the present inventors have conducted extensive research on the structure and physical properties of toner particles contained in a liquid developer. As a result, the toner particles have a core-shell structure composed of two specific types of resins. The present invention has been completed by finding that the fixing property is drastically improved when it has a certain component, the melt viscosity, the amount of acidic groups in the resin, and the like satisfying certain conditions.

  That is, the liquid developer of the present invention is a liquid developer (X) in which toner particles (C) are dispersed in an insulating liquid (L), and the toner particles (C) are shell resin (a). The core particle (A) has a core-shell structure in which the surface of the core particle (B) containing the core resin (b) is attached or coated, and the core resin (b) is derived from the diol (b1) And a structural unit derived from the carboxyl group-containing diol (b2) and a structural unit derived from the diisocyanate (b3) and satisfying the following formulas (1) and (2), b1) has a number average molecular weight of 2000 or more and 12000 or less, and the carboxyl group-containing diol (b2) has a number average molecular weight of 90 or more and 500 or less.

1.060 ≦ ([b1] + [b2]) / [b3] ≦ 1.800 (1)
0.01 ≦ [b2] / ([b1] + [b2]) ≦ 0.15 (2)
(In the formulas (1) and (2), [b1] indicates the molar ratio of the structural unit derived from the diol (b1) to the core resin (b), and [b2] is derived from the carboxyl group-containing diol (b2). The molar ratio of the structural unit to the core resin (b) is shown, and [b3] denotes the molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b).
Here, the volume average particle diameter of the toner particles (C) is 0.01 μm or more and 100 μm or less, and the coefficient of variation of the volume distribution of the toner particles (C) is preferably 1% or more and 100% or less. .

  The average value of the circularity of the toner particles (C) is preferably 0.92 or more and 1.0 or less.

  Moreover, it is preferable that this shell resin (a) is at least 1 type chosen from the group which consists of a vinyl resin, a polyester resin, a polyurethane resin, and an epoxy resin.

  The shell resin (a) is a vinyl resin, and is preferably a homopolymer or a copolymer containing a structural unit derived from a monomer having a polymerizable double bond.

  The monomer having a polymerizable double bond is preferably a vinyl monomer (m) having a molecular chain (k).

  The vinyl monomer (m) includes a vinyl monomer (m1) having a linear hydrocarbon chain having 12 to 27 carbon atoms and a vinyl monomer (m2) having a branched hydrocarbon chain having 12 to 27 carbon atoms. It is preferably at least one selected from the group consisting of a vinyl monomer (m3) having a fluoroalkyl chain having 4 to 20 carbon atoms and a vinyl monomer (m4) having a polydimethylsiloxane chain.

  The core particles (B) preferably contain at least one of a wax (c) and a modified wax (d) in which a vinyl polymer chain is graft-polymerized to the wax.

  In the toner particles (C), the surface coverage of the core particles (B) by the shell particles (A) is preferably 50% or more.

  The liquid developer (X) is preferably a paint, a liquid developer for electrophotography, a liquid developer for electrostatic recording, an oil-based ink for inkjet printers, or an ink for electronic paper.

The core particle (B) preferably contains the core resin (b) and a colorant.
And the manufacturing method of the liquid developer of this invention is the dispersion liquid (W) of the shell particle (A) in which the shell particle (A) containing shell resin (a) is disperse | distributed in insulating liquid (L). Preparing a solution for forming core particles (B) in which the core resin (b) or the precursor (b0) of the core resin (b) is dissolved in the organic solvent (M), The core particle (B) containing the core resin (b) is formed in the dispersion (W) by dispersing the core particle (B) forming solution in the dispersion (W) of the shell particles (A). And obtaining the toner particles (C) having a core-shell structure in which the shell particles (A) are attached or coated on the surfaces of the core particles (B), and obtaining the toner particles (C). After the organic solvent (M) is distilled off, the liquid developer (X) is removed. The core resin (b) contained in the liquid developer (X) includes a structural unit derived from the diol (b1), a structural unit derived from the carboxyl group-containing diol (b2), and a diisocyanate ( a structural unit derived from b3) and satisfying the following formulas (1) and (2), the diol (b1) has a number average molecular weight of 2000 or more and 12000 or less, and the carboxyl group-containing diol (B2) is characterized in that the number average molecular weight is 90 or more and 500 or less.

1.060 ≦ ([b1] + [b2]) / [b3] ≦ 1.800 (1)
0.01 ≦ [b2] / ([b1] + [b2]) ≦ 0.15 (2)
(In the formulas (1) and (2), [b1] indicates the molar ratio of the structural unit derived from the diol (b1) to the core resin (b), and [b2] is derived from the carboxyl group-containing diol (b2). The molar ratio of the structural unit to the core resin (b) is shown, and [b3] denotes the molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b).
Here, the solubility parameter of the organic solvent (M) is preferably 8.5 to 20 (cal / cm ³ ) ^1/2 .

  Since the liquid developer of the present invention has the above-described configuration, it exhibits excellent fixability that can be applied to high-quality paper and the like, and has an excellent effect that it can be fixed in a wide temperature range.

1 is a schematic conceptual diagram of an electrophotographic image forming apparatus.

  Hereinafter, the present invention will be described in more detail with reference to embodiments. The liquid developer of the present invention is not limited to the liquid developer shown below.

[Configuration of liquid developer]
The liquid developer (X) according to the present embodiment includes an electrophotographic liquid developer, a paint, and the like used in an electrophotographic image forming apparatus (described later) such as a copying machine, a printer, a digital printing machine, and a simple printing machine. It is useful as a liquid developer for electrostatic recording, an oil-based ink for ink-jet printers, or an ink for electronic paper. Toner particles (C) are dispersed in an insulating liquid (L). The toner particles (C) have a core / shell structure in which the shell particles (A) containing the shell resin (a) are attached to or coated on the surfaces of the core particles (B) containing the core resin (b).

<Shell resin (a)>
The shell resin (a) in the present embodiment may be a thermoplastic resin or a thermosetting resin. Examples of the shell resin (a) include vinyl resin, polyester resin, polyurethane resin, epoxy resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. Etc. As the shell resin (a), two or more of the above listed resins may be used in combination.

  From the viewpoint of easily obtaining the liquid developer (X) according to the present embodiment, the shell resin (a) is preferably at least one selected from the group consisting of vinyl resins, polyester resins, polyurethane resins, and epoxy resins. More preferably, at least one of a polyester resin and a polyurethane resin can be used.

<Vinyl resin>
The vinyl resin may be a homopolymer containing a structural unit derived from a monomer having a polymerizable double bond, or may be a copolymer containing a structural unit derived from two or more monomers having a polymerizable double bond. There may be. Examples of the monomer having a polymerizable double bond include the following (1) to (9).

(1) Hydrocarbon having a polymerizable double bond The hydrocarbon having a polymerizable double bond is, for example, an aliphatic hydrocarbon having a polymerizable double bond represented by the following (1-1) or the following (1 -2) is preferably an aromatic hydrocarbon having a polymerizable double bond.

(1-1) Aliphatic hydrocarbon having a polymerizable double bond An aliphatic hydrocarbon having a polymerizable double bond is, for example, a chain having a polymerizable double bond represented by the following (1-1-1). It is preferably a hydrocarbon or a cyclic hydrocarbon having a polymerizable double bond represented by the following (1-1-2).

(1-1-1) Chain hydrocarbon having a polymerizable double bond Examples of the chain hydrocarbon having a polymerizable double bond include alkenes having 2 to 30 carbon atoms (for example, ethylene, propylene, butene). , Isobutylene, pentene, heptene, diisobutylene, octene, dodecene or octadecene); alkadienes having 4 to 30 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene or 1,7-octadiene) Etc.).

(1-1-2) Cyclic hydrocarbon having a polymerizable double bond Examples of the cyclic hydrocarbon having a polymerizable double bond include mono- or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinyl, etc.). Cyclohexene or ethylidenebicycloheptene); mono- or dicycloalkadiene having 5 to 30 carbon atoms (for example, cyclopentadiene or dicyclopentadiene) and the like.

(1-2) Aromatic hydrocarbon having a polymerizable double bond As an aromatic hydrocarbon having a polymerizable double bond, for example, styrene; styrene hydrocarbon (for example, alkyl having 1 to 30 carbon atoms, Cycloalkyl, aralkyl and / or alkenyl) substituted (eg, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene , Divinylbenzene, divinyltoluene, divinylxylene or trivinylbenzene); and vinylnaphthalene.

(2) Monomers having a carboxyl group and a polymerizable double bond and salts thereof Examples of the monomer having a carboxyl group and a polymerizable double bond include unsaturated monocarboxylic acids having 3 to 15 carbon atoms [for example, ( (Meth) acrylic acid, crotonic acid, isocrotonic acid, cinnamic acid, etc.]; unsaturated dicarboxylic acid (anhydride) having 3 to 30 carbon atoms [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citracone Acid or mesaconic acid and the like]; monoalkyl (C1-10) ester of unsaturated dicarboxylic acid having 3 to 10 carbon atoms (for example, maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, Itaconic acid monobutyl ester or citraconic acid monodecyl ester). As used herein, “(meth) acrylic (acid)” means acrylic (acid) and / or methacrylic (acid). Similarly, “(meth) acrylate” means “acrylate” and / or “methacrylate”.

  Examples of the salt of the monomer include alkali metal salts (for example, sodium salt or potassium salt), alkaline earth metal salts (for example, calcium salt or magnesium salt), ammonium salts, amine salts, and quaternary ammonium. Examples include salt.

  The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salt (for example, ethylamine salt, butylamine salt or octylamine salt); secondary amine salt (for example, diethylamine salt or dibutylamine salt) ); Tertiary amine salts (for example, triethylamine salt or tributylamine salt) and the like.

  Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt and tributyllaurylammonium salt.

  Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(3) Monomers having a sulfo group and a polymerizable double bond and salts thereof Examples of the monomer having a sulfo group and a polymerizable double bond include alkene sulfonic acids having 2 to 14 carbon atoms [for example, vinyl sulfonic acid , (Meth) allylsulfonic acid or methylvinylsulfonic acid, etc.]; styrenesulfonic acid and alkyl derivatives of styrenesulfonic acid (having 2 to 24 carbon atoms) (for example, α-methylstyrenesulfonic acid and the like); 18 sulfo (hydroxy) alkyl- (meth) acrylates [e.g., sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid, 2- (meth) acryloyloxyethane sulfonic acid or 3- (Meth) acryloyloxy-2-hydroxypropanesulfonic acid Etc.]; Sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [for example, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acrylamide-2-methylpropane Sulfonic acid or 3- (meth) acrylamide-2-hydroxypropane sulfonic acid, etc.]; alkyl (having 3 to 18 carbon atoms) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid or 2-ethylhexyl-allylsulfosuccinic acid) Poly [n (“n” represents the degree of polymerization; the same shall apply hereinafter) = 2 to 30] oxyalkylene (for example, oxyethylene, oxypropylene, oxybutylene, etc.) Polyoxyalkylene is an oxyalkylene alone. It may be a polymer An oxyalkylene copolymer may be used, and when the polyoxyalkylene is an oxyalkylene copolymer, it may be a random polymer or a block polymer.); Sulfuric acid ester of meth) acrylate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfuric acid ester or poly (n = 5-15) oxypropylene monomethacrylate sulfuric acid ester]; chemical formulas (1) to (3) below The compound etc. which are represented by these are mentioned.

In the above chemical formulas (1) to (3), R ¹ represents an alkylene group having 2 to 4 carbon atoms. If the formula (1) contains two or more R ¹ O, 2 or more R ¹ O may be constructed using the same alkylene groups, two or more alkylene groups is constructed by combination Also good. When two or more kinds of alkylene groups are used in combination, the sequence of R ¹ in the chemical formula (1) may be a random sequence or a block sequence. R ² and R ³ each independently represents an alkyl group having 1 to 15 carbon atoms. m and n are each independently an integer of 1 to 50. Ar represents a benzene ring. R ⁴ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

  Examples of the salt of the monomer having a sulfo group and a polymerizable double bond include, for example, the same as those listed as “the salt of the monomer” in “(2) Monomer having a carboxyl group and a polymerizable double bond” above. Examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and quaternary ammonium salts.

(4) Monomer having phosphono group and polymerizable double bond and salt thereof Examples of the monomer having phosphono group and polymerizable double bond include (meth) acryloyloxyalkyl phosphoric acid monoester (wherein the carbon number of the alkyl group is 1-24) [for example, 2-hydroxyethyl (meth) acryloyl phosphate or phenyl-2-acryloyloxyethyl phosphate, etc.]; (meth) acryloyloxyalkylphosphonic acid (the alkyl group has 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid and the like.

  Examples of the salt of the monomer having a phosphono group and a polymerizable double bond include, for example, the same as those listed as “the salt of the monomer” in “(2) Monomer having a carboxyl group and a polymerizable double bond” above. Examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, and quaternary ammonium salts.

(5) Monomer having a hydroxyl group and a polymerizable double bond Examples of the monomer having a hydroxyl group and a polymerizable double bond include hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, and hydroxypropyl. (Meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1, Examples include 4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether.

(6) Nitrogen-containing monomer having a polymerizable double bond Examples of the nitrogen-containing monomer having a polymerizable double bond include monomers shown in the following (6-1) to (6-4).

(6-1) Monomer having an amino group and a polymerizable double bond Examples of the monomer having an amino group and a polymerizable double bond include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylamino Styrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, amino Examples include noimidazole and aminomercaptothiazole.

  The monomer having an amino group and a polymerizable double bond may be a salt of the monomers listed above. Examples of the salt of the monomer listed above include, for example, alkali metal salts, alkaline earth salts, and the like listed in the above “(2) monomer having a carboxyl group and a polymerizable double bond” as the “salt of the monomer”. Metal salts, ammonium salts, amine salts, and quaternary ammonium salts.

(6-2) Monomer having amide group and polymerizable double bond Examples of the monomer having an amide group and a polymerizable double bond include (meth) acrylamide, N-methyl (meth) acrylamide, N-butylacrylamide, Diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl -N-vinylacetamide, N-vinylpyrrolidone, etc. are mentioned.

(6-3) Monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond As a monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond, for example, (meth) acrylonitrile , Cyanostyrene and cyanoacrylate.

(6-4) Monomers having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond Examples of monomers having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond include nitrostyrene. Can be mentioned.

(7) Monomers having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond Examples of monomers having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond include glycidyl (meth) acrylate and the like. Is mentioned.

(8) Monomers having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond Examples of monomers having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond include vinyl chloride and vinyl bromide. , Vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene and chloroprene.

(9) Others Examples of the monomer having a polymerizable double bond include the monomers shown in the following (9-1) to (9-4) in addition to the above monomers.

(9-1) Ester having 4 to 16 carbon atoms having a polymerizable double bond Examples of the ester having 4 to 16 carbon atoms having a polymerizable double bond include vinyl acetate; vinyl propionate; vinyl butyrate; Diallyl phthalate; diallyl adipate; isopropenyl acetate; vinyl methacrylate; methyl-4-vinyl benzoate; cyclohexyl methacrylate; benzyl methacrylate; phenyl (meth) acrylate; vinyl methoxyacetate; vinyl benzoate; ethyl-α-ethoxy acrylate; Alkyl (meth) acrylate having an alkyl group of ˜11 [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Diacrylate fumarate (two alkyl groups are straight-chain alkyl groups, branched alkyl groups or alicyclic alkyl groups having 2 to 8 carbon atoms); dialkyl maleates (two The alkyl group is a linear alkyl group having 2 to 8 carbon atoms, a branched alkyl group or an alicyclic alkyl group); poly (meth) allyloxyalkanes (for example, diaryloxyethane, triaryl) Roxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane or tetrametaallyloxyethane); monomers having a polyalkylene glycol chain and a polymerizable double bond {eg, polyethylene glycol [number average molecular weight (below) "Mn") = 300] mono (meth) acrylate, polypropylene glycol (Mn = 5 0) Monoacrylate, methyl alcohol ethylene oxide (hereinafter, “ethylene oxide” is also referred to as “EO”) 10 mol adduct (meth) acrylate or lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.}; poly (meth) acrylates {E.g. poly (meth) acrylates of polyhydric alcohols [e.g. ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or Polyethylene glycol di (meth) acrylate and the like]} and the like.

(9-2) Ether having 3 to 16 carbon atoms having a polymerizable double bond Examples of the ether having 3 to 16 carbon atoms having a polymerizable double bond include vinyl methyl ether, vinyl ethyl ether, and vinyl propyl. Ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy -2'-vinyloxy diethyl ether, acetoxy styrene, phenoxy styrene and the like.

(9-3) Ketone having 4 to 12 carbon atoms having a polymerizable double bond Examples of the ketone having 4 to 12 carbon atoms having a polymerizable double bond include vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl. Examples include ketones.

(9-4) Sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond Examples of the sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond include divinyl sulfide and p-vinyl diphenyl sulfide. , Vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone and divinyl sulfoxide.

  Among the vinyl resins, specific examples of the copolymer include, for example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer. Polymer, styrene-acrylonitrile copolymer, styrene- (anhydride) maleic acid copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid-divinylbenzene copolymer, and styrene-styrenesulfonic acid -(Meth) acrylic acid ester copolymer etc. are mentioned.

  The shell resin (a) is a homopolymer or copolymer of a monomer having a polymerizable double bond described in (1) to (9) above, that is, a homopolymer or copolymer containing a constitutional unit derived from a vinyl monomer. A monomer having a polymerizable double bond of (1) to (9) and a vinyl monomer (m) having a molecular chain (k) and having a polymerizable double bond may be polymerized. It may be. Examples of the molecular chain (k) include a linear or branched hydrocarbon chain having 12 to 27 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, and a polydimethylsiloxane chain. The difference in SP value between the molecular chain (k) in the vinyl monomer (m) and the insulating liquid (L) is preferably 2 or less. In the present specification, the “SP value” is a method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

  The vinyl monomer (m) having a polymerizable double bond having a molecular chain (k) is not particularly limited, and examples thereof include the following vinyl monomers (m1) to (m4). As the vinyl monomer (m), two or more kinds of vinyl monomers (m1) to (m4) may be used in combination.

Linear hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25) and vinyl monomer (m1)
Examples of the vinyl monomer (m1) include mono-linear alkyls of unsaturated monocarboxylic acid (alkyl having 12 to 27 carbon atoms) and mono-linear alkyls of unsaturated dicarboxylic acid (carbon of alkyl). Examples include 12 to 27) esters. Examples of the unsaturated monocarboxylic acid and unsaturated dicarboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, and other carboxyl group-containing vinyl monomers having 3 to 24 carbon atoms. Etc.

  Specific examples of the vinyl monomer (m1) include, for example, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and (meta) ) Eicosyl acrylate.

Vinyl monomer (m2) having a branched hydrocarbon chain having 12 to 27 carbon atoms (preferably 16 to 25 carbon atoms) and a polymerizable double bond
Examples of such vinyl monomers (m2) include mono-branched alkyls of unsaturated monocarboxylic acids (alkyl having 12 to 27 carbon atoms) esters and mono-branched alkyls of unsaturated dicarboxylic acids (wherein the carbon number of alkyl is 12-27) Ester etc. are mentioned. Examples of the unsaturated monocarboxylic acid and unsaturated dicarboxylic acid include those similar to those listed as specific examples of the unsaturated monocarboxylic acid and unsaturated dicarboxylic acid in the vinyl monomer (m1).

  Specific examples of the vinyl monomer (m2) include 2-decyltetradecyl (meth) acrylate.

Vinyl monomer having a fluoroalkyl chain having 4 to 20 carbon atoms and a polymerizable double bond (m3)
Examples of such vinyl monomer (m3) include perfluoroalkyl (alkyl) (meth) acrylic acid ester represented by the following chemical formula (4). CH ₂ = CR—COO— (CH ₂ ) _p - (CF _{3) q} -Z: formula (4)
In the chemical formula (4), R represents a hydrogen atom or a methyl group, p is an integer of 0 to 3, q is any of 2, 4, 6, 8, 10 or 12, and Z is a hydrogen atom. Or represents a fluorine atom.

  Specific examples of the vinyl monomer (m3) include, for example, [(2-perfluoroethyl) ethyl] (meth) acrylic acid ester, [(2-perfluorobutyl) ethyl] (meth) acrylic acid ester, [(2 -Perfluorohexyl) ethyl] (meth) acrylic acid ester, [(2-perfluorooctyl) ethyl] (meth) acrylic acid ester, [(2-perfluorodecyl) ethyl] (meth) acrylic acid ester, and And [(2-perfluorododecyl) ethyl] (meth) acrylic acid ester.

Vinyl monomer having polydimethylsiloxane chain and polymerizable double bond (m4)
Examples of such a vinyl monomer (m4) include (meth) acryl-modified silicone represented by the following chemical formula (5). CH ₂ = CR—COO — ((CH ₃ ) ₂ SiO) _m —Si (CH ₃ ) ₃ : Chemical formula (5)
In the chemical formula (5), R represents a hydrogen atom or a methyl group, and m is an average value of 15 to 45.

  Specific examples of the vinyl monomer (m4) include, for example, modified silicone oils (for example, product names: “X-22-174DX”, “X-22-2426”, “X-22-2475”, etc.) Silicone Co., Ltd.).

  Among the vinyl monomers (m1) to (m4), preferred monomers are a vinyl monomer (m1) and a vinyl monomer (m2), and a more preferred monomer is a vinyl monomer (m2).

  The content of the vinyl monomer (m) is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% by mass or less, and further preferably 20% by mass with respect to the mass of the vinyl resin. % To 60% by mass. When the content of the vinyl monomer (m) is within the above range, the toner particles (C) are difficult to unite with each other.

  When the monomer having a polymerizable double bond (1) to (9), the vinyl monomer (m1), and the vinyl monomer (m2) are polymerized to form a vinyl resin, the vinyl monomer (m1) and vinyl The mass ratio [(m1) :( m2)] to the monomer (m2) is preferably 90:10 to 10:90 from the viewpoint of the particle size distribution of the toner particles (C) and the fixability of the toner particles (C). More preferably, it is 80: 20-20: 80, More preferably, it is 70: 30-30: 70.

<Polyester resin>
Examples of polyester resins include polycondensates of polyols with polycarboxylic acids, acid anhydrides of polycarboxylic acids, or lower alkyl (alkyl group having 1 to 4 carbon atoms) esters of polycarboxylic acids. A known polycondensation catalyst or the like can be used for the polycondensation reaction.

  Examples of the polyol include diol (10) and polyol (11) having a valence of 3 to 8 or more (hereinafter abbreviated as “polyol (11)”).

  Examples of the polycarboxylic acid include dicarboxylic acid (12) and polycarboxylic acid (13) having a valence of 3 to 6 or more (hereinafter abbreviated as “polycarboxylic acid (13)”). Is mentioned. Examples of the acid anhydride of polycarboxylic acid include an acid anhydride of dicarboxylic acid (12) and an acid anhydride of polycarboxylic acid (13). Examples of the lower alkyl ester of polycarboxylic acid include a lower alkyl ester of dicarboxylic acid (12) and a lower alkyl ester of polycarboxylic acid (13).

  The ratio of polyol and polycarboxylic acid is not particularly limited. The equivalent ratio of hydroxyl group [OH] to carboxyl group [COOH] ([OH] / [COOH]) is preferably 2/1 to 1/5, more preferably 1.5 / 1 to 1/4. The ratio between the polyol and the polycarboxylic acid may be set so that the ratio is more preferably 1.3 / 1 to 1/3.

  Examples of the diol (10) include alkylene glycols having 2 to 30 carbon atoms (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexane). Diols, octanediols, decanediols, dodecanediols, tetradecanediols, neopentyl glycols, 2,2-diethyl-1,3-propanediols, etc .; alkylene ether glycols with Mn = 106 or more and 10,000 or less (for example, diethylene glycol, triethylene glycol) , Dipropylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene ether glycol); alicyclic diols having 6 to 24 carbon atoms (for example, 1,4-cyclohexane) Dimethanol or hydrogenated bisphenol A, etc.); Mn = 100 to 10,000 alkylene oxide of the above alicyclic diol (hereinafter, “alkylene oxide” is also referred to as “AO”) adduct (addition mole number is 2 to 100) ( For example, 1,4-cyclohexanedimethanol EO 10 mol adduct); bisphenols having 15 to 30 carbon atoms (for example, bisphenol A, bisphenol F or bisphenol S) AO [for example, EO, propylene oxide (hereinafter “PO”) Or butylene oxide, etc.] The above-mentioned AO adducts (for example, bisphenol A) of adducts (addition mole number 2-100) or polyphenols having 12-24 carbons (for example, catechol, hydroquinone, resorcinol, etc.) O2-4 mol adduct or bisphenol A PO2-4 mol adduct); weight average molecular weight (hereinafter also referred to as “Mw”) = 100 or more and 5000 or less polylactone diol (for example, poly-ε-caprolactone diol, etc.); Examples thereof include polybutadiene diol having Mw of 1000 or more and 20000 or less.

  Of these, the diol (10) is preferably an AO adduct of alkylene glycol and bisphenols, more preferably an AO adduct of bisphenols alone or a mixture of an AO adduct of bisphenols and an alkylene glycol.

  Examples of the polyol (11) include aliphatic polyhydric alcohols having a valence of 3 to 8 or more and a carbon number of 3 to 10 (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitan or sorbitol, etc.); AO (2 to 4 carbon atoms) adduct (2 to 100 carbon atoms) of trisphenol having 25 to 50 carbon atoms (for example, 2 to 4 mol adduct of trisphenol EO or trisphenol) Polyamide PO 2-4 mol adduct, etc.); n = 3-50 novolak resin (eg phenol novolac or cresol novolac, etc.) AO (carbon number 2-4) adduct (addition mol number 2-100) (eg , Phenol novolac PO2 molar adduct or phenol novolac EO4 AO (carbon number is 2 to 4) adduct (addition mole number is 2) of polyphenols having 6 to 30 carbon atoms (for example, pyrogallol, phloroglucinol or 1,2,4-benzenetriol). -100) (eg, pyrogallol EO 4 mole adduct, etc.); n = 20-2000 acrylic polyol {eg, monomer having hydroxyethyl (meth) acrylate and other polymerizable double bond [eg, styrene, (meth) Acrylic acid or a copolymer with (meth) acrylic acid ester, etc.].

  Of these, the polyol (11) is preferably an aliphatic polyhydric alcohol and an AO adduct of a novolac resin, and more preferably an AO adduct of a novolac resin.

  Examples of the dicarboxylic acid (12) include alkane dicarboxylic acids having 4 to 32 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid or octadecanedicarboxylic acid); 32 alkene dicarboxylic acids (eg maleic acid, fumaric acid, citraconic acid or mesaconic acid); branched alkenedicarboxylic acids having 8 to 40 carbon atoms [eg dimer acid or alkenyl succinic acid (eg dodecenyl succinic acid, penta Decenyl succinic acid or octadecenyl succinic acid etc.]]; branched alkanedicarboxylic acids having 12 to 40 carbon atoms [eg alkyl succinic acid (eg decyl succinic acid, dodecyl succinic acid or octadecyl succinic acid etc.) etc. ]; Carbon number 8-20 Aromatic dicarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid or naphthalene dicarboxylic acid) and the like.

  Of these, preferred as the dicarboxylic acid (12) are alkene dicarboxylic acids and aromatic dicarboxylic acids, and more preferred are aromatic dicarboxylic acids.

  Examples of the polycarboxylic acid (13) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid or pyromellitic acid).

  Examples of the acid anhydride of dicarboxylic acid (12) and polycarboxylic acid (13) include trimellitic acid anhydride and pyromellitic acid anhydride. Examples of lower alkyl esters of dicarboxylic acid (12) and polycarboxylic acid (13) include methyl ester, ethyl ester, and isopropyl ester.

<Polyurethane resin>
Examples of the polyurethane resin include polyisocyanate (14) and active hydrogen-containing compound {for example, water; polyol [for example, diol (10) (including diol having a functional group other than hydroxyl group) or polyol (11), etc.] Polycarboxylic acid [for example, dicarboxylic acid (12) or polycarboxylic acid (13)]; polyester polyol obtained by polycondensation of polyol and polycarboxylic acid; ring-opening polymer of lactone having 6 to 12 carbon atoms; Polyamine (15); polythiol (16); a combination of these and the like}, or a terminal isocyanate group prepolymer obtained by reacting polyisocyanate (14) with the active hydrogen-containing compound. And the isocyanate group of the terminal isocyanate group prepolymer To be a primary and / or secondary monoamine (17) and the amino group-containing polyurethane resin obtained by reaction of equivalent amounts.

  The content of the carboxyl group in the polyurethane resin is preferably 0.1% by mass or more and 10% by mass or less.

  Examples of the polyisocyanate (14) include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same applies to <polyurethane resin> hereinafter); aliphatic having 2 to 18 carbon atoms. Polyisocyanates; modified products of these polyisocyanates (for example, modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups or oxazolidone groups); A combination of two or more types can be mentioned.

  Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate; 2,4- or 2,6-tolylene diisocyanate (hereinafter also referred to as “TDI”); crude TDI; m- or p- Α, α, α ′, α′-tetramethylxylylene diisocyanate; 2,4′- or 4,4′-diphenylmethane diisocyanate (hereinafter also referred to as “MDI”); crude MDI {for example, crude diaminophenyl Methane [For example, a condensation product of formaldehyde and an aromatic amine (one or two or more may be used in combination), or diaminodiphenylmethane and a small amount (for example, 5% by mass to 20% by mass) ), A mixture with a polyamine having 3 or more amine groups, etc.] Or polyallyl polyisocyanate, etc .; 1,5-naphthylene diisocyanate; 4,4 ′, 4 ″ -triphenylmethane triisocyanate; m- or p-isocyanatophenylsulfonyl isocyanate; Is mentioned.

  Examples of the aliphatic polyisocyanate include a chain aliphatic polyisocyanate and a cyclic aliphatic polyisocyanate.

  Examples of chain aliphatic polyisocyanates include ethylene diisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate (hereinafter also referred to as “HDI”); dodecamethylene diisocyanate; 1,6,11-undecane triisocyanate; Lysine diisocyanate; 2,6-diisocyanatomethyl caproate; bis (2-isocyanatoethyl) fumarate; bis (2-isocyanatoethyl) carbonate; 2-isocyanatoethyl-2,6-di Isocyanatohexanoate; a combination of two or more of these may be used.

  Examples of the cycloaliphatic polyisocyanate include isophorone diisocyanate (hereinafter also referred to as “IPDI”); dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI); cyclohexylene diisocyanate; methylcyclohexylene diisocyanate (hydrogenated TDI); Examples thereof include bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate; 2,5- or 2,6-norbornane diisocyanate; a combination of two or more of these.

  Examples of the modified polyisocyanate include a polyisocyanate compound containing at least one of a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group, and an oxazolidone group. . Examples of modified polyisocyanates include, for example, modified MDI (for example, urethane-modified MDI, carbodiimide-modified MDI, or trihydrocarbyl phosphate-modified MDI); urethane-modified TDI; a combination of two or more of these [for example, modified MDI and urethane-modified TDI (For example, combined use with an isocyanate-containing prepolymer, etc.).

  Of these, the polyisocyanate (14) is preferably an aromatic polyisocyanate having 6 to 15 carbon atoms and an aliphatic polyisocyanate having 4 to 15 carbon atoms, and more preferably TDI, MDI, HDI, Hydrogenated MDI and IPDI.

  Examples of the polyamine (15) include an aliphatic polyamine having 2 to 18 carbon atoms and an aromatic polyamine (for example, having 6 to 20 carbon atoms).

  Examples of the aliphatic polyamine having 2 to 18 carbon atoms include, for example, a chain aliphatic polyamine; a chain aliphatic polyamine alkyl (1 to 4 carbon atoms) substituted; a chain aliphatic polyamine hydroxyalkyl (carbon number). 2-4) Substituents; cycloaliphatic polyamines and the like.

  Examples of chain aliphatic polyamines include alkylene diamines having 2 to 12 carbon atoms (for example, ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine or hexamethylene diamine); polyalkylenes (having 2 to 6 carbon atoms). ) Polyamines [for example, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine] and the like.

  Examples of the alkyl (substituted carbon number of 1 to 4) substituted chain aliphatic polyamine and the hydroxyalkyl (chained carbon number 2 to 4) substituted chain aliphatic polyamine include dialkyl (carbon number of 1 to 3). Examples include aminopropylamine; trimethylhexamethylenediamine; aminoethylethanolamine; 2,5-dimethyl-2,5-hexamethylenediamine; methyliminobispropylamine.

  Examples of the cycloaliphatic polyamine include alicyclic polyamines having 4 to 15 carbon atoms [for example, 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylene). Dianiline) or 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like]; a heterocyclic polyamine having 4 to 15 carbon atoms [for example, Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.].

  Examples of the aromatic polyamine (having 6 to 20 carbon atoms) include, for example, unsubstituted aromatic polyamines; alkyl groups (for example, methyl groups, ethyl groups, n- or isopropyl groups, and butyl groups having 1 to 4 carbon atoms). Aromatic polyamines having an alkyl group); aromatic polyamines having electron-withdrawing groups (for example, halogen atoms such as Cl, Br, I and F, alkoxy groups such as methoxy and ethoxy groups, and nitro groups); secondary An aromatic polyamine having an amino group is exemplified.

  Non-substituted aromatic polyamines include, for example, 1,2-, 1,3- or 1,4-phenylenediamine; 2,4′- or 4,4′-diphenylmethanediamine; crude diphenylmethanediamine (for example, polyphenylpolyamine). Methylenepolyamine); diaminodiphenylsulfone; benzidine; thiodianiline; bis (3,4-diaminophenyl) sulfone; 2,6-diaminopyridine; m-aminobenzylamine; triphenylmethane-4,4 ′, 4 ″ -triamine; Naphthylenediamine; a combination of two or more of these.

  Examples of the aromatic polyamine having an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n- or isopropyl group, and a butyl group) include 2,4- or 2,6- Tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1, 3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diamino Citylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1 , 5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5 5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetrabutyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4- Diaminodiphenylmethane, 3,5-diisopropyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl Diphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5 5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenyl And rusulfone and a combination of two or more of these.

  Aromatic polyamines having electron withdrawing groups (for example, halogen atoms such as Cl, Br, I and F, alkoxy groups such as methoxy and ethoxy groups, and nitro groups) include, for example, methylene bis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4- Phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3,3 ′ -Dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide Bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4- Aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromo) Aniline), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline and the like.

As the aromatic polyamine having a secondary amino group, for example, a part or all of —NH _{2 in} the above-described unsubstituted aromatic polyamine, aromatic polyamine having an alkyl group, and aromatic polyamine having an electron withdrawing group is —NH—. Substituted with R ′ (R ′ is an alkyl group, for example, a lower alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group) [for example, 4,4′-di (methylamino) diphenylmethane Or 1-methyl-2-methylamino-4-aminobenzene]; polyamide polyamine; dicarboxylic acid (for example, dimer acid) and excess (more than 2 moles per mole of acid) polyamines (for example, the above alkylene diamine or polyalkylene) Low molecular weight polyamide polyamines obtained by condensation with polyamines, etc .; Polyamines; hydrides of cyanoethylation products of polyether polyols (such as polyalkylene glycol, etc.).

  Examples of the polythiol (16) include alkanedithiols having 2 to 36 carbon atoms (for example, ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, etc.).

  Examples of the primary and / or secondary monoamine (17) include alkylamines having 2 to 24 carbon atoms (for example, ethylamine, n-butylamine, isobutylamine, diethylamine or n-butyl-n-dodecylamine). Is mentioned.

<Epoxy resin>
Examples of the epoxy resin include a ring-opening polymer of polyepoxide (18); polyepoxide (18) and an active hydrogen-containing compound [for example, water, diol (10), dicarboxylic acid (12), polyamine (15) or polythiol (16 And the like; and a cured product of polyepoxide (18) and an acid anhydride of dicarboxylic acid (12).

  The polyepoxide (18) is not particularly limited as long as it has two or more epoxy groups in the molecule. From the viewpoint of the mechanical properties of the cured product, preferred as the polyepoxide (18) is one having two epoxy groups in the molecule. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 or more and 1000 or less, and more preferably 90 or more and 500 or less. When the epoxy equivalent is 1000 or less, the crosslinked structure becomes dense, and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, if the epoxy equivalent is less than 65, synthesis of the polyepoxide (18) may be difficult.

  Examples of the polyepoxide (18) include aromatic polyepoxy compounds and aliphatic polyepoxy compounds.

  Examples of aromatic polyepoxy compounds include glycidyl ethers of polyhydric phenols, glycidyl esters of aromatic polycarboxylic acids, glycidyl aromatic polyamines, and glycidylates of aminophenols.

  Examples of the polyglycol glycidyl ether include bisphenol F diglycidyl ether; bisphenol A diglycidyl ether; bisphenol B diglycidyl ether; bisphenol AD diglycidyl ether; bisphenol S diglycidyl ether; halogenated bisphenol A diglycidyl; Bisphenol A diglycidyl ether; catechin diglycidyl ether; resorcinol diglycidyl ether; hydroquinone diglycidyl ether; pyrogallol triglycidyl ether; 1,5-dihydroxynaphthalene diglycidyl ether; dihydroxybiphenyl diglycidyl ether; octachloro-4,4'-dihydroxy Biphenyl diglycidyl ether; tetramethylbiphenyl dig Dihydroxynaphthylcresol triglycidyl ether; tris (hydroxyphenyl) methane triglycidyl ether; dinaphthyltriol triglycidyl ether; tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether; p-glycidylphenyldimethyltolylbisphenol A glycidyl ether; Trismethyl-t-butyl-butylhydroxymethane triglycidyl ether; 9,9′-bis (4-hydroxyphenyl) furorange glycidyl ether; 4,4′-oxybis (1,4-phenylethyl) tetracresol glycidyl ether; 4,4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, bis (dihydroxynaphthalene) tetraglycidyl ether Glycidyl ether of phenol or cresol novolac resin; glycidyl ether of limonene phenol novolak resin; diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin; phenol and glyoxal, glutaraldehyde, or Examples include polyglycidyl ethers of polyphenols obtained by the condensation reaction of formaldehyde; polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcin and acetone.

  Examples of the glycidyl ester of aromatic polyvalent carboxylic acid include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.

  Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. It is done.

  As the aromatic polyepoxy compound, in addition to the above-listed compounds, p-aminophenol triglycidyl ether (an example of a glycidylated product of aminophenol); diglycidyl obtained by reacting tolylene diisocyanate or diphenylmethane diisocyanate with glycidol Examples thereof include urethane compounds; glycidyl group-containing polyurethane (pre) polymers obtained by reacting tolylene diisocyanate or diphenylmethane diisocyanate, glycidol and polyol; diglycidyl ethers of AO adducts of bisphenol A, and the like.

  Examples of the aliphatic polyepoxy compound include a chain aliphatic polyepoxy compound and a cyclic aliphatic polyepoxy compound.

  The aliphatic polyepoxy compound may be a copolymer of diglycidyl ether and glycidyl (meth) acrylate.

  Examples of the chain aliphatic polyepoxy compounds include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.

  Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, Polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and polyglycerol polyglycidyl ether Is mentioned.

  Examples of the polyglycidyl ester of a polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate and diglycidyl pimelate.

  Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.

  Examples of the cycloaliphatic polyepoxy compound include trisglycidyl melamine, vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy -6-methylcyclohexylmethyl) butylamine and dimer acid diglycidyl ester. Examples of the cycloaliphatic polyepoxy compound include hydrogenated products of the above aromatic polyepoxide compounds.

<Polyamide resin>
Examples of the polyamide resin include a ring-opening polymer of lactam, a polycondensate of aminocarboxylic acid, a polycondensate of polycarboxylic acid and polyamine, and the like.

<Polyimide resin>
Examples of the polyimide resin include aliphatic polyimide resins (for example, condensation polymers obtained from aliphatic carboxylic dianhydrides and aliphatic diamines), and aromatic polyimide resins (for example, aromatic carboxylic dianhydrides). And condensation polymers obtained from aliphatic diamines or aromatic diamines).

<Silicon resin>
Examples of the silicon resin include compounds having at least one of a silicon-silicon bond, a silicon-carbon bond, a siloxane bond, and a silicon-nitrogen bond in a molecular chain (for example, polysiloxane, polycarbosilane, or polysilazane). Etc.

<Phenolic resin>
Examples of the phenol resin include condensation polymers obtained from phenols (for example, phenol, cresol, nonylphenol, lignin, resorcin, or catechol) and aldehydes (for example, formaldehyde, acetaldehyde, or furfural).

<Melamine resin>
Examples of the melamine resin include a polycondensate obtained from melamine and formaldehyde.

<Urea resin>
Examples of urea resins include polycondensates obtained from urea and formaldehyde.

<Aniline resin>
Examples of aniline resins include those obtained by reacting aniline and aldehydes under acidic conditions.

<Ionomer resin>
Examples of the ionomer resin include a monomer having a polymerizable double bond (for example, an α-olefin monomer or a styrene monomer) and an α, β-unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, maleic acid, A copolymer with itaconic acid, maleic acid monomethyl ester, maleic anhydride or maleic acid monoethyl ester, etc., and a part or all of the carboxylic acid in the copolymer is a carboxylate (eg, potassium salt, sodium salt) , Magnesium salt or calcium salt).

<Polycarbonate resin>
Examples of the polycarbonate resin include condensation polymers of bisphenols (for example, bisphenol A, bisphenol F, or bisphenol S) and phosgene or carbonic acid diester.

<Crystalline / Amorphous>
The shell resin (a) may be a crystalline resin (a1), an amorphous resin (a2), or a crystalline resin (a1) and an amorphous resin (a2). It may be used in combination. From the viewpoint of fixability of the toner particles (C), the shell resin (a) is preferably a crystalline resin (a1).

  In the present specification, “crystallinity” means a ratio (Tm / Ta) between a softening point of a resin (hereinafter also referred to as “Tm”) and a maximum melting temperature of the resin (hereinafter also referred to as “Ta”). It means that it is 0.8 or more and 1.55 or less, and the result obtained by the differential scanning calorimeter (hereinafter also referred to as DSC) does not show a stepwise endothermic change but has a clear endothermic peak. means. In the present specification, “non-crystalline” means that the ratio of Tm to Ta (Tm / Ta) is larger than 1.55. Tm and Ta can be measured by the following method.

  Tm can be measured using a Koka type flow tester (for example, product name: “CFT-500D”, manufactured by Shimadzu Corporation). Specifically, while a 1 g measurement sample is heated at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied to the measurement sample by a plunger, and the measurement sample is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm. . Then, the relationship between “plunger descent amount (flow value)” and “temperature” is drawn on a graph. The temperature at which the plunger descending amount is ½ of the maximum value of the descending amount is read from the graph, and this value (temperature when half of the measurement sample is pushed out of the nozzle) is defined as Tm.

  Ta can be measured using a differential scanning calorimeter (for example, product name: “DSC210”, manufactured by Seiko Instruments Inc.). Specifically, first, a sample used for measuring Ta is pretreated. After the sample is melted at 130 ° C., the temperature is lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then the temperature is lowered from 70 ° C. to 10 ° C. at a rate of 0.5 ° C./minute. Next, the sample is heated at a heating rate of 20 ° C./min by DSC method to measure the endothermic change of the sample, and the relationship between the “endothermic amount” and “temperature” is plotted on a graph. At this time, the temperature of the endothermic peak observed between 20 ° C. and 100 ° C. is Ta ′. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is defined as Ta '. Then, the sample is stored at (Ta′-10) ° C. for 6 hours, and then stored at (Ta′-15) ° C. for 6 hours.

  Next, by the DSC method, the sample subjected to the pretreatment was cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 20 ° C./min to measure the endothermic change. The relationship between the "heat absorption and heat generation" and "temperature" is plotted on a graph. The temperature at which the endotherm takes the maximum value is taken as the maximum peak temperature (Ta) of heat of fusion.

<Heat of fusion>
As for shell resin (a), it is desirable for the heat of fusion by DSC of the shell resin (a) to satisfy the following formulas (3) to (4).
5 ≦ H1 ≦ 70 (3)
0.2 ≦ H2 / H1 ≦ 1.0 (4)
In the formulas (3) and (4), H1 represents the heat of fusion (J / g) at the first temperature rise by DSC, and H2 represents the heat of fusion (J / g) at the second temperature rise by DSC.

  H1 is an index of the melting rate of the shell resin (a). In general, a resin having heat of fusion has a sharp melt property and can be melted with a small amount of energy. Therefore, if a resin having heat of fusion is selected as the shell resin (a), the energy required for fixing can be reduced. Therefore, it is preferable to select a resin having heat of fusion as the shell resin (a). However, if the heat of fusion of the resin is too large, it may be difficult to sufficiently melt the resin. Preferably 6 ≦ H1 ≦ 65, and more preferably 7 ≦ H1 ≦ 65.

  H2 / H1 in the above formula (4) is an index of the crystallization rate of the shell resin (a). In general, when particles made of resin (resin particles) are melted and then cooled and used, if the crystal component in the resin particles is not crystallized, the resistance value of the resin particles decreases, or the resin There is a problem that the particles are plasticized. When such a malfunction occurs, the performance of the resin particles obtained by cooling may differ from the originally designed performance. From the above, it is necessary to quickly crystallize the crystal component in the resin particles so as not to affect the performance of the resin particles. H2 / H1 is more preferably 0.3 or more, and further preferably 0.4 or more. Further, if the crystallization speed of the shell resin (a) is high, H2 / H1 approaches 1.0. Therefore, H2 / H1 preferably takes a value close to 1.0.

  In addition, H2 / H1 in the above formula (4) does not theoretically exceed 1.0, but it may exceed 1.0 in the actual measurement value by DSC. Even when the actual measurement value (H2 / H1) by DSC exceeds 1.0, the above formula (4) is satisfied.

  H1 and H2 can be measured according to JIS-K7122 (1987) “Method for measuring the transition heat of plastic”. Specifically, first, 5 mg of shell resin (a) is sampled and placed in an aluminum pan. Using a differential scanning calorimeter (for example, product name: “RDC220”, manufactured by SII Nano Technology Inc., or product name: “DSC20”, Seiko Instruments Inc., etc.) The temperature (melting point) at the endothermic peak of the shell resin (a) due to melting is measured at 10 ° C., and the area S1 of the endothermic peak is obtained. And H1 is computable from the area | region S1 of the calculated | required endothermic peak. After calculating H1, after cooling to 0 ° C at a cooling rate of 90 ° C / min, the temperature (melting point) at the endothermic peak of the shell resin (a) due to melting was measured at a rate of temperature increase of 10 ° C per minute. The area S2 of the endothermic peak is obtained. And H2 is computable from the area | region S2 of the calculated | required endothermic peak.

<Melting point>
The melting point of the shell resin (a) is preferably 0 ° C. or higher and 220 ° C. or lower, more preferably 30 ° C. or higher and 200 ° C. or lower, and further preferably 40 ° C. or higher and 80 ° C. or lower. From the viewpoints of the particle size distribution of the toner particles (C) and the powder flowability, heat-resistant storage stability and stress resistance of the liquid developer (X), the melting point of the shell resin (a) is the liquid developer (X). It is preferable that it is more than the temperature when manufacturing. If the melting point of the shell resin is lower than the temperature at which the liquid developer is produced, it may be difficult to prevent the toner particles from uniting with each other, and it may be difficult to prevent the toner particles from splitting. . In addition, the distribution width in the particle size distribution of the toner particles is difficult to be narrowed. In other words, there is a possibility that the variation in the particle size of the toner particles becomes large.

  In this specification, the melting point is based on a method prescribed in ASTM D3418-82 using a differential scanning calorimeter (product name: “DSC20” or “SSC / 580” manufactured by Seiko Instruments Inc.). Measured.

<Mn (number average molecular weight) and Mw (weight average molecular weight)>
The number average molecular weight (hereinafter also referred to as Mn) [obtained by measurement by gel permeation chromatography (hereinafter also referred to as “GPC”)] of the shell resin (a) is preferably 100 or more and 5000000 or less, preferably Is 200 or more and 5000000 or less, more preferably 500 or more and 500000 or less.

In the present specification, Mn and weight average molecular weight (hereinafter also referred to as Mw) of resins (excluding polyurethane resins) are determined under the following conditions using GPC for the soluble content of tetrahydrofuran (hereinafter also referred to as “THF”). Measuring device: “HLC-8120” (product name, manufactured by Tosoh Corporation)
Column: “TSKgelGMHXL” (product name, manufactured by Tosoh Corporation) (2) and “TSKgelMultiporeHXL-M” (product name, manufactured by Tosoh Corporation) (1)
Sample solution: 0.25 mass% THF solution Injection amount of THF solution into the column: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (Product name: TSK standard POLYSYRENE, manufactured by Tosoh Corporation) 12 points (Molecular weight: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000) 1090000, 2890000).

In this specification, Mn and Mw of the polyurethane resin are those measured using GPC under the following conditions Measuring device: “HLC-8220GPC” (product name, manufactured by Tosoh Corporation)
Column: “Guardcolum α” (1) and “TSKgel α-M” (1)
Sample solution: 0.125 mass% dimethylformamide solution Injection amount of dimethylformamide solution to the column: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (Product name: TSK standard POLYSYRENE, manufactured by Tosoh Corporation) 12 points (Molecular weight: 500, 1050, 2800, 5970, 9100, 18100, 37900, 96400, 190000, 355000) 1090000, 2890000).

<SP value>
In the present specification, the solubility parameter is referred to as SP value.

The SP value of the shell resin (a) is preferably 7 (cal / cm ³ ) ^1/2 or more and 18 (cal / cm ³ ) ^1/2 or less, more preferably 8 (cal / cm ³ ) ^1/2. It is 14 (cal / cm ³ ) ^1/2 or less.

<Shell particles (A)>
Shell particles (A) in the present embodiment include shell resin (a). Any known method can be adopted as the method for producing the shell particles (A), and the method is not particularly limited. For example, the following methods [1] to [7] can be mentioned.
[1]: The shell resin (a) is pulverized dry using a known dry pulverizer such as a jet mill.
[2]: The powder of the shell resin (a) is dispersed in an organic solvent and pulverized wet using a known wet disperser such as a bead mill or a roll mill.
[3]: The solution of the shell resin (a) is sprayed using a spray dryer or the like and dried.
[4]: A poor solvent is added or cooled to the solution of the shell resin (a) to supersaturate the shell resin (a) and precipitate it.
[5]: Disperse the solution of the shell resin (a) in water or an organic solvent.
[6]: The precursor of the shell resin (a) is polymerized in water by an emulsion polymerization method, a soap-free emulsion polymerization method, a seed polymerization method, a suspension polymerization method, or the like.
[7]: The shell resin (a) precursor is polymerized by dispersion polymerization or the like in an organic solvent.

  Of these methods, the methods [4], [6] and [7] are preferable from the viewpoint of ease of production of the shell particles (A), and more preferably the methods [6] and [7]. Is preferred.

<Core resin (b)>
The core resin (b) in the present embodiment includes a structural unit derived from a diol (b1) having an Mn of 2000 or more and 12000 or less, a structural unit derived from a carboxyl group-containing diol (b2) having an Mn of 90 or more and 500 or less, And a structural unit derived from (b3), which satisfies the following formulas (1) and (2).

1.060 ≦ ([b1] + [b2]) / [b3] ≦ 1.800 (1)
0.01 ≦ [b2] / ([b1] + [b2]) ≦ 0.15 (2)
(In the formulas (1) and (2), [b1] indicates the molar ratio of the structural unit derived from the diol (b1) to the core resin (b), and [b2] is derived from the carboxyl group-containing diol (b2). The molar ratio of the structural unit to the core resin (b) is shown, and [b3] denotes the molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b).
Strictly speaking, the molar ratio [b1] of the structural unit derived from the diol (b1) to the core resin (b) is the mixing molar ratio of the diol (b1) during the production of the core resin (b). Although different, both molar ratios are considered the same herein. This is because the molecular weight of the molecule that is desorbed by dehydration condensation of the diol (b1) is smaller than the molecular weight of the diol (b1) and can be ignored. The same applies to [b2] and [b3].

  Here, the above formula (1) is an index of the melt viscosity of the core resin (b), and in the above formula (1), the larger ([b1] + [b2]) / [b3], the more the core resin ( The melt viscosity of b) decreases and the melt viscosity of the core resin (b) increases as ([b1] + [b2]) / [b3] decreases.

  When the liquid developer (X) of the present embodiment is used as a paint, a liquid developer for electrophotography, a liquid developer for electrostatic recording, an oil-based ink for inkjet printers, or an ink for electronic paper ([b1] + [ If b2]) / [b3] exceeds 1.800, the melt viscosity becomes low and hot offset tends to occur in a high temperature range, which is not preferable. ([b1] + [b2]) / [b3] is If it is less than 1.060, the melt viscosity becomes high, and the fixability in a low temperature range is lowered, which is not preferable.

  Therefore, in the above formula (1), ([b1] + [b2]) / [b3] needs to be 1.060 or more and 1.800 or less, preferably 1.150 or more and 1.700 or less. And more preferably 1.200 or more and 1.600 or less.

  Moreover, the said Formula (2) shows the suitable range of the carboxyl group which is an acidic group which a core resin (b) has, and [b2] / ([b1] + [b2]) is large in the said Formula (2). The core resin (b) has many acidic groups, and the smaller [b2] / ([b1] + [b2]), the fewer acidic groups the core resin (b) has.

  When the liquid developer (X) of the present embodiment is used as a paint, an electrophotographic liquid developer, an electrostatic recording liquid developer, an oil-based ink for an ink jet printer, or an ink for electronic paper, [b2] / ([[ If b1] + [b2]) is less than 0.01, the affinity with paper is lowered, so that the fixing property is not sufficient, and [b2] / ([b1] + [b2]) is 0.15. Exceeding this is not preferable because the melt viscosity becomes high and the fixability in a low temperature range is lowered.

  Therefore, in the above formula (2), [b2] / ([b1] + [b2]) needs to be 0.01 or more and 0.15 or less. When [b2] / ([b1] + [b2]) occupies this range, both fixability and chargeability can be achieved.

  [B2] / ([b1] + [b2]) is preferably 0.02 or more and 0.10 or less, and more preferably 0.02 or more and 0.05 or less. .

  Here, as the diol (b1) having a Mn of 2000 or more and 12000 or less, a diol (10) having a Mn of 2000 or more and 12000 or less is used.

  Examples of the carboxyl group-containing diol (b2) having an Mn of 90 or more and 500 or less include 2,2-bis (hydroxymethyl) propionic acid (hereinafter also referred to as DMPA), 2,2-bis (hydroxymethyl) heptanoic acid, 2 , 2-bis (hydroxymethyl) octanoic acid, tartaric acid, 2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid and the like are used.

  Moreover, as diisocyanate (b3), what was illustrated as diisocyanate among the said polyisocyanate (14) can be mentioned.

  The Mn, melting point, glass transition temperature (hereinafter also referred to as Tg), and SP value of the core resin (b) can be adjusted to a suitable range depending on the application.

For example, when the liquid developer (X) of the present embodiment is used for electrophotography, electrostatic recording, or the like, Mn is preferably 1000 or more and 5000000 or less, more preferably 2000 or more and 500000 or less. Preferably it is. In this case, the melting point is preferably 20 ° C. or higher and 300 ° C. or lower, more preferably 80 ° C. or higher and 250 ° C. or lower. In this case, Tg is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 150 ° C. or lower. In this case, the SP value is preferably 8 (cal / cm ³ ) ^1/2 or more and 16 (cal / cm ³ ) ^1/2 or less, more preferably 9 (cal / cm ³ ) ^1/2. It is 14 (cal / cm ³ ) ^1/2 or less.

  Here, Tg may be measured by the DSC method or may be measured using a flow tester. In the case of measuring Tg by the DSC method, for example, a differential scanning calorimeter (product name: “DSC20” or “SSC / 580” or the like, both manufactured by Seiko Instruments Inc.) is used as ASTM D3418-82. It is preferable to measure Tg according to the method specified in 1.

  When measuring Tg using a flow tester, it is preferable to use a Koka type flow tester (for example, product name: “CFT500 type” manufactured by Shimadzu Corporation). An example of Tg measurement conditions in this case is shown below.

Load: 3MPa
Temperature increase rate: 3.0 ° C / min
Die diameter: 0.50mm
Die length: 10.0mm
<Core particle (B)>
The core particle (B) in the present embodiment contains the core resin (b). The core particle (B) can be produced from the core resin (b) by a method similar to the method for producing the shell particle (A) described above.

<Toner particles (C)>
The toner particles (C) according to the present embodiment have a core-shell structure, and the shell particles (A) containing the shell resin (a) are the core particles (B) containing the core resin (b). It may be attached to the surface, or the shell particles (A) may be coated on the surfaces of the core particles (B). Here, the coating means that the shell particles (A) are continuously adhered to form a coating.

  The particle diameter of the shell particles (A) is preferably smaller than the particle diameter of the core particles (B). From the viewpoint of uniformity of particle size of the toner particles (C), the particle size ratio [(volume average particle size of shell particles (A)) / (volume average particle size of core particles (B)]] is 0.001 or more and 0. It is preferable that it is within the range of .3 or less. More preferably, the lower limit of the particle size ratio is 0.003 and the upper limit is 0.25. When the particle size ratio is larger than 0.3, the shell particles (A) are difficult to be efficiently adsorbed on the surface of the core particles (B), and thus the distribution range in the particle size distribution of the obtained toner particles (C) is widened. Tend. On the other hand, when the particle size ratio is smaller than 0.001, it may be difficult to produce the shell particles (A).

  The volume average particle size of the shell particles (A) is set to a particle size suitable for obtaining toner particles (C) having a desired particle size, and the particle size ratio is within the preferable range. Can be adjusted as appropriate. The volume average particle diameter of the shell particles (A) is preferably 0.0005 μm or more and 30 μm or less. The upper limit of the volume average particle diameter of the shell particles (A) is more preferably 20 μm, and even more preferably 10 μm. The lower limit of the volume average particle diameter of the shell particles (A) is more preferably 0.01 μm, still more preferably 0.02 μm, and most preferably 0.04 μm. For example, when it is desired to obtain toner particles (C) having a volume average particle diameter of 1 μm, the volume average particle diameter of the shell particles (A) is preferably 0.0005 μm or more and 0.3 μm or less, more preferably 0.00. It is 001 μm or more and 0.2 μm or less. For example, when it is desired to obtain toner particles (C) having a volume average particle diameter of 10 μm, the volume average particle diameter of the shell particles (A) is preferably 0.005 μm or more and 3 μm or less, more preferably 0.05 μm or more. 2 μm or less. For example, when it is desired to obtain toner particles (C) having a volume average particle size of 100 μm, the volume average particle size of the shell particles (A) is preferably 0.05 μm or more and 30 μm or less, more preferably 0.1 μm or more. 20 μm or less.

  From the viewpoint of easily controlling the particle size ratio within the above preferable range, the volume average particle size of the core particles (B) is preferably 0.1 μm or more and 300 μm or less, more preferably 0.5 μm or more and 250 μm or less. More preferably, it is 1 μm or more and 200 μm or less.

  In the present specification, the “volume average particle size” is a laser type particle size distribution measuring device (for example, product name: “LA-920”, manufactured by Horiba, Ltd., or product name “Multisizer III”, manufactured by Coulter, Inc. ); Measuring device using laser Doppler method as optical system (product name: “ELS-800”, manufactured by Otsuka Electronics Co., Ltd.); Flow type particle image analyzer (for example, product name: “FPIA-3000S”, Sysmex Corporation) Etc.). When the volume average particle diameter is measured with a different measuring apparatus, if a difference occurs in the measured value, the measured value by “ELS-800” is adopted.

  The mass ratio [(A) :( B)] of the shell particles (A) and the core particles (B) is preferably 1:99 to 70:30. From the viewpoint of the uniformity of the particle diameter of the toner particles (C) and the heat resistance stability of the liquid developer (X), the ratio [(A) :( B)] is more preferably 2:98 to 50:50. More preferably, it is 3: 97-35: 65. If the content (mass ratio) of the shell particles is too low, the blocking resistance of the toner particles may be lowered. On the other hand, if the content (mass ratio) of the core particles is too high, fixability at low temperatures may be deteriorated.

  The shape of the toner particles (C) is preferably spherical from the viewpoint of the fluidity of the liquid developer (X) and its melt leveling property. Specifically, the average value of the circularity (average circularity) of the toner particles (C) is preferably 0.92 or more and 1.0 or less, more preferably 0.97 or more and 1.0 or less. More preferably, it is 0.98 or more and 1.0 or less. The closer the average circularity of the toner particles (C) is to 1.0, the closer the toner particles (C) have a spherical shape. If the core particles (B) are spherical, the toner particles (C) are likely to be spherical. Therefore, the core particles (B) are preferably spherical.

  In this specification, the average circularity is the circumference of a toner particle (C) in which the circumference of a circle having an area equal to the projected area of the toner particle (C) is detected optically. The value divided by the length. Specifically, the average circularity is measured using a flow type particle image analyzer (for example, product name: “FPIA-3000”, manufactured by Sysmex Corporation). Specifically, in a predetermined container, 100 ml to 150 ml of water from which impure solids have been removed in advance is added, and a surfactant as a dispersant (for example, product name: “Dry Well”, manufactured by Fuji Photo Film Co., Ltd.) 0 Add 1 ml or more and 0.5 ml or less, and further add about 0.1 g or more and 9.5 g or less of the measurement sample. For the suspension in which the measurement sample is dispersed in this manner, an ultrasonic disperser (for example, product name: “Ultrasonic Cleaner Model VS-150”, manufactured by Welbo Clear) is used for about 1 minute or more 3 Dispersion processing is performed for a minute or less. Thus, the dispersion concentration is set to 3000 / μL or more and 10000 / μL or less. And the shape and particle size distribution of a measurement sample are measured using the sample solution after a dispersion process.

  The volume average particle diameter of the toner particles (C) is preferably determined as appropriate depending on the application, but is generally preferably 0.01 μm or more and 100 μm or less. The upper limit of the volume average particle diameter of the toner particles (C) is more preferably 40 μm, still more preferably 30 μm, and most preferably 20 μm. The lower limit of the volume average particle diameter of the toner particles (C) is more preferably 0.3 μm, and further preferably 0.5 μm.

  From the viewpoint of particle size uniformity of the toner particles (C), the coefficient of variation of the volume distribution of the toner particles (C) is preferably 1% or more and 100% or less, more preferably 1% or more and 50% or less. More preferably, it is 1% or more and 30% or less, and most preferably 1% or more and 25% or less. In the present specification, the coefficient of variation of the volume distribution is measured using a particle size distribution measuring device such as a laser particle size distribution measuring device (for example, product name: “LA-920”, manufactured by Horiba, Ltd.).

  From the viewpoint of the particle size uniformity of the toner particles (C), the fluidity of the liquid developer (X) and the heat stability of the liquid developer (X), the core particles (A) formed by the shell particles (A) in the toner particles (C) The surface coverage of B) is preferably 50% or more, more preferably 80% or more. The surface coating means that the shell particles (A) are attached or coated on the surfaces of the core particles (B). Moreover, the surface coverage of the core particle (B) by the shell particle (A) can be obtained based on the following formula (5) from image analysis of an image obtained by a scanning electron microscope (SEM), for example. The shape of the toner particles (C) can be controlled by changing the surface coverage obtained by the following formula (5).

Surface coverage (%) = {S1 / (S1 + S2)} × 100 (5)
(In Formula (5), S1 shows the area of the core particle (B) covered with the shell particle (A), and S2 is the area of the core particle (B) not attached or coated with the shell particle (A)). Is shown.)
In the present specification, the surface coverage is an average value of the results of measurement for 50 particles.

  The surface average center line roughness (Ra) of the toner particles (C) is preferably 0.01 μm or more and 0.8 μm or less from the viewpoint of the fluidity of the liquid developer (X). The surface average centerline roughness (Ra) is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and the centerline of the roughness curve, and is a scanning probe microscope system (for example, Toyo Technica). Etc.).

  From the viewpoint of the particle size distribution of the toner particles (C) and the heat stability of the liquid developer (X), the core-shell structure of the toner particles (C) is 1% by mass or more with respect to the mass of the toner particles (C). 70% by mass or less (more preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 35% by mass or less) of film-like shell particles (A), and 30% by mass or more and 99% by mass or less (more It is preferably composed of 50% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 90% by mass or less) core particles (B).

  From the viewpoint of the fixing property of the toner particles (C) and the heat stability of the liquid developer (X), the content of the toner particles (C) in the liquid developer (X) is preferably 10% by mass or more and 50% by mass. Or less, more preferably 15% by mass or more and 45% by mass or less, and further preferably 20% by mass or more and 40% by mass or less.

<Additives>
The toner particles (C) in the present embodiment preferably contain a colorant in at least one of the shell particles (A) and the core particles (B), and more preferably the core particles (B) are the core resin. (B) and a colorant. In addition, the toner particles (C) may contain additives other than the colorant (for example, wax, filler, antistatic agent, release agent, charge control agent) on at least one of the shell particles (A) and the core particles (B). , UV absorbers, antioxidants, antiblocking agents, heat stabilizers, flame retardants, etc.).

<Colorant>
As the colorant, known pigments can be used without any particular limitation, but the following colorants are preferably used from the viewpoints of cost, light resistance and colorability. In terms of color composition, the colorants shown below are usually classified into black pigments, yellow pigments, magenta pigments, and cyan pigments. Colors other than black (color images) are basically yellow pigments, magenta pigments, and cyan pigments. It is toned by subtractive color mixing. Further, as the colorant, those obtained by subjecting the following pigments to surface treatment using an acidic or basic solvent may be used. For example, an acidic or basic synergist is added to the following pigments: You may use together.

Examples of the black pigment include carbon black.
Examples of yellow pigments include disazo yellow pigments such as CI (Color Index) Pigment Yellow 12, 13, 14, 17, 55, 81, 83, 180, and 185.

  Examples of the magenta pigment include azo lake type magenta pigments such as CIPigment Red 48, 57 (Kermin 6B), 5, 23, 60, 114, 146 and 186; insoluble azo magenta pigments; CIPigment Examples include thioindigo magenta pigments such as Red 88 and CIPigment Violet 36 and 38; quinacridone magenta pigments such as CIPigment Red 122 and 209; naphthol magenta pigments such as CIPigment Red 269 and the like. The magenta pigment preferably contains at least one of quinacridone pigments, carmine pigments and naphthol pigments, more preferably two or three of these three pigments. It is preferred that it is included.

  Examples of cyan pigments include copper phthalocyanine blue cyan pigments such as C.I. Pigment Blue 15: 1 and 15: 3; and phthalocyanine green pigments.

<Wax>
The core particle (B) preferably contains at least one of a wax (c) and a modified wax (d) in which a vinyl polymer chain is graft-polymerized to the wax. However, the shell particles (A) may contain at least one of wax (c) and modified wax (d).

  From the viewpoint of heat resistance stability of the liquid developer (X), at least one of the wax (c) and the modified wax (d) in which a vinyl polymer chain is graft-polymerized to the wax is used as an additive. It is preferably contained in (core layer).

  The content of the wax (c) is preferably 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less with respect to the mass of the core particle (B). The content of the modified wax (d) is preferably 10% by mass or less, more preferably 0.5% by mass or more and 8% by mass or less with respect to the mass of the core particle (B). When both the wax (c) and the modified wax (d) are contained, the total content of the wax (c) and the modified wax (d) is preferably 25% by mass or less with respect to the mass of the core particles (B). More preferably, it is 1 mass% or more and 20 mass% or less.

  Examples of the wax (c) include synthetic wax (eg, polyolefin wax); natural wax (eg, paraffin wax, microcrystalline wax, carnauba wax, carbonyl group-containing wax, or a combination thereof). Of these, paraffin wax and carnauba wax are preferred as the wax (c). Examples of the paraffin wax include petroleum waxes whose main component is a linear saturated hydrocarbon having a melting point of 50 ° C. or higher and 90 ° C. or lower and having 20 to 36 carbon atoms. Examples of carnauba wax include animal and plant waxes having a melting point of 50 ° C. or more and 90 ° C. or less and a carbon number of 16 to 36.

  Mn of the wax (c) is preferably 400 or more and 5000 or less, more preferably 1000 or more and 3000 or less, and further preferably 1500 or more and 2000 or less, from the viewpoint of releasability. In this specification, Mn of wax (c) is measured using GPC. When measuring Mn of the wax (c), for example, o-dichlorobenzene can be used as the solvent, and polystyrene can be used as the reference substance.

  When the wax (c) and the modified wax (d) are used in combination, the wax (c), together with the modified wax (d), is a melt-kneading process in the absence of a solvent and a heat-dissolving mixing process in the presence of an organic solvent. It is preferable to disperse in the core resin (b) after at least one of the treatments. In this way, by allowing the modified wax (d) to coexist during the wax dispersion treatment, the wax base portion of the modified wax (d) is efficiently adsorbed on the surface of the wax (c), or the wax of the modified wax (d). Part of the base portion is efficiently entangled with the matrix structure of the wax (c). Thereby, the affinity between the surface of the wax (c) and the core resin (b) is improved, and the wax (c) can be more uniformly encapsulated in the core particles (B). Therefore, it becomes easy to control the dispersion state of the wax (c).

  Examples of the wax used in the modified wax (d) include the same as those listed as specific examples of the wax (c). Preferred wax materials used in the modified wax (d) are also the above waxes. The thing similar to what was enumerated as a preferable material of (c) is mentioned. Examples of the monomer having a polymerizable double bond include those similar to the monomers (1) to (9) having a polymerizable double bond constituting the vinyl resin described above. Among these, preferred are The monomer (1), the monomer (2) and the monomer (6). As the monomer having a polymerizable double bond, any one of the monomers (1) to (9) may be used alone, or two or more kinds may be used in combination.

  The amount of the wax component in the modified wax (d) (including the unreacted wax) is preferably 0.5% by mass or more and 99.5% by mass or less, more preferably 1% by mass or more and 80% by mass or less. More preferably, it is 5 mass% or more and 50 mass% or less, Most preferably, it is 10 mass% or more and 30 mass% or less.

  From the viewpoint of heat stability of the liquid developer (X), the Tg of the modified wax (d) is preferably 40 ° C. or higher and 90 ° C. or lower, more preferably 50 ° C. or higher and 80 ° C. or lower.

  The Mn of the modified wax (d) is preferably 1500 or more and 10,000 or less, more preferably 1800 or more and 9000 or less. When the Mn of the modified wax (d) is 1500 or more and 10,000 or less, the mechanical strength of the toner particles (C) becomes good.

  The method for producing such a modified wax (d) is not particularly limited. For example, the wax (c) is dissolved or dispersed in a solvent (for example, toluene or xylene) and heated to 100 ° C. or more and 200 ° C. or less, and then the monomer having a polymerizable double bond is polymerized, and then the solvent is distilled off. As a result, the modified wax (d) can be obtained.

Examples of the method of mixing the wax (c) and the modified wax (d) include the methods described in [i] to [iii] below. Of the following [i] to [iii], the following [ii] is preferably used.
[I]: The wax (c) and the modified wax (d) are melted and kneaded at a temperature equal to or higher than the respective melting points.
[Ii]: The wax (c) and the modified wax (d) are dissolved or suspended in the organic solvent (u) described later, and then precipitated in the liquid by cooling crystallization or solvent crystallization, or It is deposited in the gas by spray drying or the like.
[Iii]: The wax (c) and the modified wax (d) are dissolved or suspended in an organic solvent (u) described later, and then mechanically wet pulverized using a disperser or the like.

  Examples of the method for dispersing the wax (c) and / or the modified wax (d) in the core resin (b) include, for example, the wax (c) and / or the modified wax (d) and the core resin (b), respectively. The method of mixing these, after melt | dissolving or disperse | distributing to a solvent is mentioned.

<Insulating liquid>
Examples of the insulating liquid (L) include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, polysiloxanes, and the like. Specific examples include hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, and the like. Are, for example, Isopar E, Isopar G, Isopar H, Isopar L (Isopar: trade name of Exxon), Shellsol 70, Shellsol 71 (Shellsol: trade name of Shell Oil), Amsco OMS, Amsco 460 ( Amsco: trade name of Spirits), IP solvent 2028 (trade name of Idemitsu Kosan), silicone oil, liquid paraffin and the like. These may be used alone or in combination of two or more.

  Of these, from the viewpoint of odor, the insulating liquid (L) is preferably a solvent having a boiling point of 100 ° C. or higher, and more preferably a hydrocarbon solvent having 10 or more carbon atoms (for example, dodecane, isododecane). And liquid oil paraffin) and silicone oil, and liquid paraffin is more preferable.

The dielectric constant of the insulating liquid (L) is preferably 1 or more and 4 or less at 20 ° C. Thereby, the charge maintenance property of the liquid developer can be improved. The relative dielectric constant of the insulating liquid (L) is calculated using the dielectric constant of the insulating liquid (L) obtained by the bridge method (JIS C2101-1999). Specifically, the empty capacitance C ₀ (pF) before filling with the insulating liquid (L) and the equivalent parallel capacitance C _x (pF) filled with the insulating liquid (L). ) And is substituted into the following formula (6) to calculate the dielectric constant ε of the insulating liquid (L). The relative dielectric constant of the insulating liquid (L) is obtained by the ratio between the calculated ε and the relative dielectric constant of the air 1.000585.

ε = C _x / C ₀ (6)
The solvent contained in the liquid developer (X) according to the present embodiment is preferably substantially only the insulating liquid (L), but the liquid developer is preferably 1% by mass or less, more preferably. May contain other organic solvents in the range of 0.5 mass% or less.

<Method for producing liquid developer>
The manufacturing method of the liquid developer (X) according to the present embodiment is not particularly limited, but when manufactured by the manufacturing method of the present embodiment, the toner particles (C) in the liquid developer (X) This is particularly preferable because the particle size distribution can be narrowed.

The manufacturing method of the present embodiment includes the following steps [I] to [IV].
Step [I]: A dispersion liquid (W) of shell particles (A) in which the shell particles (A) containing the shell resin (a) are dispersed in the insulating liquid (L) is prepared.
Step [II]: A solution for forming core particles (B) in which the core resin (b) or the precursor (b0) of the core resin (b) is dissolved in the organic solvent (M) is prepared.
Step [III]: A core containing the core resin (b) in the dispersion (W) by dispersing the solution for forming the core particles (B) in the dispersion (W) of the shell particles (A). Particles (B) are formed, and toner particles (C) having a core-shell structure in which the shell particles (A) are attached to or coated on the surfaces of the core particles (B) are obtained.
Step [IV]: After the step of obtaining the toner particles (C), the organic solvent (M) is distilled off to obtain a liquid developer (X).

  The core resin (b) contained in the liquid developer (X) has a constitutional unit derived from the diol (b1), a constitutional unit derived from the carboxyl group-containing diol (b2), and a constitution derived from the diisocyanate (b3). And satisfying the above formulas (1) and (2), the diol (b1) has a number average molecular weight of 2000 or more and 12000 or less, and the carboxyl group-containing diol (b2) is: The number average molecular weight is 90 or more and 500 or less.

In addition, the method for producing a liquid developer according to the present embodiment preferably includes the following step [V].
Step [V]: A dispersion in which a colorant is dispersed (colorant dispersion) is prepared.

Hereinafter, each process will be described in detail.
<Process [I]>
In step [I], the dispersion liquid (W) can be produced by producing the shell particles (A) and then dispersing the shell particles (A) in the insulating liquid (L). There is no particular limitation.

In the case where the shell particles (A) are dispersed in the insulating liquid (L) after the shell particles (A) are produced, it is preferable to use any one of the following methods [4] to [6]. It is more preferable to use [6]. Moreover, when manufacturing the shell particles (A) by a polymerization reaction or the like in the insulating liquid (L), it is preferable to use any one of the following methods [1] to [3]. More preferably, it is used.
[1]: When the shell resin (a) is a vinyl resin, the monomer is polymerized by a dispersion polymerization method or the like in a solvent containing the insulating liquid (L). Thereby, the dispersion liquid (W1) of the shell particles (A) is directly produced. If necessary, a solvent other than the insulating liquid (L) is distilled off from the dispersion liquid (W) of the shell particles (A). When the solvent other than the insulating liquid (L) is distilled off, the low boiling point component of the insulating liquid (L) may be distilled off. This is the same in the process of distilling off solvents other than the insulating liquid (L) shown below.
[2]: When the shell resin (a) is a polyaddition resin such as polyester resin or polyurethane resin or a condensation resin, a precursor (monomer or oligomer, etc.) or a solution of the precursor is appropriately dispersed if necessary. The precursor is dispersed in the insulating liquid (L) in the presence of the agent, and then the precursor is cured by heating or addition of a curing agent. If necessary, a solvent other than the insulating liquid (L) is distilled off.
[3]: When the shell resin (a) is a polyaddition resin such as a polyester resin or a polyurethane resin or a condensation resin, a precursor (monomer or oligomer, etc.) or a solution of the precursor (starting material is liquid) It is preferable, but it may be liquefied by heating), and after dissolving an appropriate emulsifier, an insulating liquid (L) serving as a poor solvent is added to reprecipitate the precursor. Thereafter, the precursor is cured by adding a curing agent or the like, and a solvent other than the insulating liquid (L) is distilled off as necessary.
[4]: Obtained in advance by a polymerization reaction (any polymerization reaction such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same applies to [5] and [6] below). The obtained shell resin (a) is pulverized using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then classified. Thereby, shell particle | grains (A) are obtained. The obtained shell particles (A) are dispersed in the insulating liquid (L) in the presence of a suitable dispersant.
[5]: Resin solution in which the shell resin (a) obtained in advance by the polymerization reaction is dissolved (this resin solution may be obtained by polymerizing the shell resin (a) in a solvent. ) In the form of a mist. Thereby, shell particle | grains (A) are obtained. The obtained shell particles (A) are dispersed in the insulating liquid (L) in the presence of a suitable dispersant.
[6]: Resin solution in which shell resin (a) obtained by polymerization reaction is dissolved (this resin solution may be obtained by polymerizing shell resin (a) in a solvent. ), A poor solvent (preferably an insulating liquid (L)) is added, or the resin solution obtained by preliminarily dissolving the shell resin (a) by heating is cooled, and further appropriate. Shell particles (A) are precipitated by the presence of a dispersant. If necessary, a solvent other than the insulating liquid (L) is distilled off.

When manufacturing the shell particles (A) and then dispersing the shell particles (A) in the insulating liquid (L), the manufacturing method of the shell particles (A) is not particularly limited, and is a dry process shown in [7] below. A method of manufacturing the shell particles (A) may be used, or a method of manufacturing the shell particles (A) by a wet method represented by the following [8] to [13] may be used. From the viewpoint of easy manufacture of the shell particles (A), the manufacturing method of the shell particles (A) is preferably wet, more preferably [10], [12] or [13] below. The following [12] or [13] is more preferable.
[7]: The shell resin (a) is pulverized dry using a known dry pulverizer such as a jet mill.
[8]: The shell resin (a) powder is dispersed in an organic solvent, and is pulverized wet using a known wet disperser such as a bead mill or a roll mill.
[9]: The solution of shell resin (a) is sprayed using a spray dryer or the like and dried.
[10]: A poor solvent is added to the solution of the shell resin (a) or cooled to supersaturate the shell resin (a) to precipitate it.
[11]: Disperse the solution of the shell resin (a) in water or an organic solvent.
[12]: The precursor of the shell resin (a) is polymerized in water by an emulsion polymerization method, a soap-free emulsion polymerization method, a seed polymerization method, a suspension polymerization method, or the like.
[13]: The precursor of the shell resin (a) is polymerized by dispersion polymerization or the like in an organic solvent.

  Examples of the dispersant in [2] and [4] to [6] include a known surfactant (s) and an oil-soluble polymer (t). Further, as the dispersion aid, for example, an organic solvent (u) and a plasticizer (v) can be used in combination.

  Examples of the surfactant (s) include an anionic surfactant (s-1), a cationic surfactant (s-2), an amphoteric surfactant (s-3), and a nonionic surfactant ( s-4). In addition, you may use 2 or more types of surfactant together as surfactant (s).

  Examples of the anionic surfactant (s-1) include ether carboxylic acid (salt) having an alkyl group having 8 to 24 carbon atoms [for example, (poly) oxyethylene (having 1 to 100 repeating units) lauryl ether. Sodium acetate etc.]; ether sulfate ester salt having an alkyl group having 8 to 24 carbon atoms [for example, (poly) oxyethylene (having 1 to 100 repeating units) sodium lauryl sulfate etc.]; alkyl having 8 to 24 carbon atoms Sulfosuccinic acid ester salts having a group [e.g. sodium mono or dialkyl sulfosuccinic acid ester, monosodium mono or dialkyl sulfosuccinic acid ester, (poly) oxyethylene (with 1-100 repeat units) mono sodium or dialkyl sulfosuccinic acid ester, or , (Po ) Oxyethylene (with 1-100 repeat units) mono or dialkyl sulfosuccinate disodium etc.]; (poly) oxyethylene (1-100 repeat units) coconut oil fatty acid sodium monoethanolamide sulfate; 8 carbon atoms Sulfonate having an alkyl group of ˜24 (for example, sodium dodecylbenzene sulfonate); phosphate ester salt having an alkyl group having 8 to 24 carbon atoms [for example, sodium lauryl phosphate or (poly) oxyethylene (The number of repeating units is 1 to 100) sodium lauryl ether phosphate, etc .; fatty acid salts (for example, sodium laurate or triethanolamine laurate); acylated amino acid salts (for example, palm oil fatty acid methyl taurine sodium), etc. All It is.

  Examples of the cationic surfactant (s-2) include quaternary ammonium salt type cationic surfactants and amine salt type cationic surfactants. Examples of quaternary ammonium salt type cationic surfactants include tertiary amines and quaternizing agents (eg, alkyl halides such as methyl chloride, methyl bromide, ethyl chloride, and benzyl chloride, dimethyl sulfate, dimethyl carbonate, Or the compound etc. which are obtained by reaction with ethylene oxide etc. are mentioned. Specific examples of the quaternary ammonium salt type cationic surfactant include didecyldimethylammonium chloride, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), polyoxyethylenetrimethylammonium chloride and stearamide. Examples thereof include ethyl diethylmethylammonium methosulfate.

  Examples of amine salt type cationic surfactants include primary to tertiary amines such as inorganic acids (for example, hydrochloric acid, nitric acid, sulfuric acid or hydroiodic acid) or organic acids (for example, acetic acid, formic acid, oxalic acid, And compounds obtained by neutralization with lactic acid, gluconic acid, adipic acid or alkyl phosphoric acid). Examples of the primary amine salt type cationic surfactant include inorganic acid salts or organic acid salts of aliphatic higher amines (for example, higher amines such as laurylamine, stearylamine, hardened tallow amine or rosinamine); lower amines Higher fatty acid (for example, stearic acid or oleic acid) salts and the like. Examples of secondary amine salt type cationic surfactants include inorganic acid salts of aliphatic amines such as ethylene oxide adducts of aliphatic amines or organic acid salts thereof.

  Examples of the amphoteric surfactant (s-3) include carboxybetaine-type amphoteric surfactants [for example, fatty acid amidopropyldimethylaminoacetic acid betaines having 10 to 18 carbon atoms (such as coconut oil fatty acid amidopropyl betaine), alkyls, etc. (C10-C18) dimethylaminoacetic acid betaine (such as lauryldimethylaminoacetic acid betaine) or imidazolinium-type carboxybetaine (such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine) And the like]; sulfobetaine-type amphoteric surfactants [for example, fatty acid amidopropylhydroxyethylsulfobetaine having 10 to 18 carbon atoms (for example, coconut oil fatty acid amidopropyldimethylhydroxyethylsulfobetaine), or Methyl alkyl (carbon number 10 to 18) such as dimethyl hydroxyethyl sulfobetaine (such as lauryl hydroxy sulfobetaine)]; amino acid type amphoteric surfactants (e.g. β- lauryl aminopropionic acid sodium, etc.) and the like.

  Examples of the nonionic surfactant (s-4) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.

  As the AO addition type nonionic surfactant, for example, AO (having 2 to 4 carbon atoms, preferably 2) adduct of higher alcohol (8 to 18 carbon atoms) (addition moles per active hydrogen) 1-30); alkyl (carbon number 1-12) phenol EO adduct (addition mole number 1-30); higher amine (carbon number 8-22) AO (carbon number 2-4, preferably 2) Adduct (1-40 added moles per active hydrogen); EO adduct of fatty acids (8-18 carbon atoms) (1-60 added moles per active hydrogen); Polypropylene Glycol (Mn = 200 to 4000) EO adduct (1 to 50 moles added per active hydrogen); polyoxyethylene (3 to 30 repeat units) alkyl (6 to 20 carbon atoms) allyl ether Sorbitan monolaure Too EO adduct (1-30 mol added per active hydrogen) and sorbitan monooleate EO adduct (1-30 added mol per active hydrogen) (2-8 valences) Or higher valence) fatty acid (carbon number 8-24) ester EO adduct (number of added moles per active hydrogen 1-30) of alcohol (carbon number 2-30).

  Examples of the polyhydric alcohol type nonionic surfactant include polyvalent (2 to 8 or more valent) alcohols (having 2 to 8 carbon atoms) such as glycerin monooleate, sorbitan monolaurate and sorbitan monooleate. 30) fatty acid (having 8 to 24 carbon atoms) esters; fatty acid (having 10 to 18 carbon atoms) alkanolamides such as lauric acid monoethanolamide and lauric acid diethanolamide.

  Examples of the oil-soluble polymer (t) include a polymer having at least one of an alkyl group having 4 or more carbon atoms, a dimethylsiloxane group, and a functional group having a fluorine atom. More preferably, the oil-soluble polymer (t) has at least one group of an alkyl group having affinity for the insulating liquid (L), a dimethylsiloxane group, and a functional group having a fluorine atom, and the core resin (b). It has a chemical structure that has an affinity for.

  The oil-soluble polymer (t) is a monomer having an alkyl group having 4 or more carbon atoms, a monomer having a dimethylsiloxane group (or a reactive oligomer) among the monomers (1) to (9) having the polymerizable double bond. And at least one monomer having a fluorine atom is more preferably polymerized or copolymerized.

  The organic solvent (u) may be an insulating liquid (L) or an organic solvent other than the insulating liquid (L) (for example, an organic solvent (M) described later other than the insulating liquid (L)). Or other solvents). Since the solvent other than the insulating liquid (L) is distilled off after the preparation of the dispersion liquid (W) of the shell particles (A), it is preferable that the solvent is easily distilled off, for example, the insulating liquid (L It is preferable that the boiling point is lower than.

  The plasticizer (v) may be added to the insulating liquid (L) as necessary when dispersing the shell particles (A), or may be added to a solvent containing the core resin (b) and the like. .

  It does not specifically limit as a plasticizer (v), What is shown to the following plasticizers (v1)-(v6) is mentioned.

  Examples of the plasticizer (v1) include phthalate esters (for example, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and the like).

  Examples of the plasticizer (v2) include aliphatic dibasic acid esters (for example, di-2-ethylhexyl adipate or 2-ethylhexyl sebacate).

  Examples of the plasticizer (v3) include trimellitic acid esters (for example, tri-2-ethylhexyl trimellitic acid or trioctyl trimellitic acid) and the like.

  Examples of the plasticizer (v4) include phosphate esters (for example, triethyl phosphate, tri-2-ethylhexyl phosphate or tricresyl phosphate).

  Examples of the plasticizer (v5) include fatty acid esters (such as butyl oleate).

  Examples of the plasticizer (v6) include combinations of the materials listed in the plasticizers (v1) to (v5).

<Process [II]>
In step [II], the core particle (B) forming solution is prepared by dissolving the core resin (b) or the precursor (b0) of the core resin (b) in the organic solvent (M).

  As a method for dissolving the core resin (b) or the precursor (b0) of the core resin (b) in the organic solvent (M), any method may be used, and a known method can be used. For example, the core resin (b) or the precursor (b0) of the core resin (b) is added to the organic solvent (M) and then stirred, and the core resin (b) or the core resin ( The method of heating after putting the precursor (b0) of b) is mentioned.

The organic solvent (M) is not particularly limited as long as it can dissolve the core resin (b) at room temperature or under heating, but the SP value of the organic solvent (M) is preferably 8.5 (cal / cm ^3). ) ^1/2 or more and 20 (cal / cm ³ ) ^1/2 or less, more preferably 10 (cal / cm ³ ) ^1/2 or more and 19 (cal / cm ³ ) ^1/2 or less. When a mixed solvent is used as the organic solvent (M), the weighted average value of the SP values calculated from the SP values of the respective solvents on the assumption that additivity is established may be within the above range. If the SP value of the organic solvent (M) is outside the above range, the solubility of the core resin (b) or the precursor (b0) of the core resin (b) may be insufficient.

  The organic solvent (M) preferably has an SP value within the above range, and is preferably selected as appropriate depending on the material of the core resin (b) or the precursor of the core resin (b) (b0). . Examples of the organic solvent (M) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit and cyclohexane. Halogenated solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene and perchloroethylene; esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate Or ether ether solvents; ether solvents such as diethyl ether, THF, dioxane, ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; acetone, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol Amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compounds solvents such as N-methylpyrrolidone; mixed solvents in which two or more of the above solvents are mixed, etc. Is mentioned.

  From the viewpoint of odor and easiness of evaporation, the boiling point of the organic solvent (M) is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.

  Preferable organic solvents (M) include, for example, acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent of two or more thereof.

  From the viewpoint of the particle size distribution of the toner particles (C), the viscosity of the core particle (B) forming solution is preferably 10 mPa · s or more and 50000 mPa · s or less, more preferably 100 mPa · s or more and 10000 mPa · s or less. . Here, the viscosity of the core particle (B) forming solution is preferably measured using, for example, a B-type viscometer. The organic solvent (M) is preferably selected so that the viscosity of the core particle (B) forming solution is within the above range.

  The precursor (b0) of the core resin (b) is not particularly limited as long as it can become the core resin (b) by a chemical reaction.

  Examples of the precursor (b0) of the core resin (b) include a combination of a prepolymer (α) having a reactive group (hereinafter abbreviated as “prepolymer (α)”) and a curing agent (β). It is done.

  The “reactive group” of the prepolymer (α) refers to a group that can react with the curing agent (β). In this case, as a method of obtaining the core resin (b) by reacting the precursor (b0) of the core resin (b), the prepolymer (α) and the curing agent (β) are dispersed in the insulating liquid (L). For example, a method of reacting the prepolymer (α) and the curing agent (β) by heating.

Examples of the combination of the reactive group of the prepolymer (α) and the curing agent (β) include the following [14] to [15].
[14]: The reactive group of the prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1).
[15]: The reactive group of the prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group.

  In the above combination [14], the functional group (α1) capable of reacting with the active hydrogen compound is preferably an isocyanate group (α1a) and a blocked isocyanate group (α1b).

  The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes (for example, acetoxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.); lactams (for example, γ-butyrolactam, ε-caprolactam, etc. Or γ-valerolactam); aliphatic alcohols having 1 to 20 carbon atoms (for example, ethanol, methanol or octanol); phenols (for example, phenol, m-cresol, xylenol or nonylphenol); active methylene compounds (Eg acetylacetone, ethyl malonate or ethyl acetoacetate); basic nitrogen-containing compounds (eg N, N-diethylhydroxylamine, 2-hydroxypi Jin, pyridine N- oxide or 2-mercaptopyridine); and combinations of these and the like. Of these, oximes are preferred as the blocked isocyanate group (α1b), and methyl ethyl ketoxime is more preferred.

  As the constituent unit of the prepolymer (α) having a reactive group, polyurethane (αz) is preferable.

  Examples of the polyurethane (αz) include a polyaddition product of the diol (10) and the polyisocyanate (14), a polycondensation product of the diol (10) and the dicarboxylic acid (12), and a polylactone. Examples thereof include polyaddition products of the above-mentioned polyisocyanate (14) and the like (for example, a ring-opening polymer of ε-caprolactone).

Examples of the method of incorporating a reactive group into polyurethane (αz) include the methods shown in the following [16] to [17].
[16]: One of the two or more constituent components is excessively used to leave the functional group of the constituent component at the terminal.
[17]: One of the two or more components is excessively used to leave the functional group of the component at the terminal (a prepolymer is obtained), and the remaining functional group can react with the functional group The functional group is reacted, or the remaining functional group is reacted with a compound containing a functional group capable of reacting with the functional group.

  In the method [16], a hydroxyl group-containing polyurethane prepolymer and an isocyanate group-containing polyurethane prepolymer are obtained.

  In the method [17], an isocyanate group-containing prepolymer is obtained by reacting the prepolymer obtained in the method [16] with a polyisocyanate.

  For example, when an isocyanate group-containing polyurethane prepolymer is obtained by reacting a hydroxyl group-containing polyurethane polymer with an isocyanate group-containing polyurethane prepolymer, the equivalent ratio ([NCO] / [OH]) of the isocyanate group [NCO] and the hydroxyl group [OH] of the hydroxyl group-containing polyurethane is , Preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and even more preferably 2.5 / 1 to 1.5 / 1. The ratio of the polyisocyanate to the hydroxyl group-containing polyurethane prepolymer may be set. Even when the skeleton is changed or when a prepolymer having a terminal group is obtained, it is preferable that the ratio of the constituent components is the same as that described above only by changing the constituent components.

  The number of reactive groups contained in one molecule of the prepolymer (α) is preferably 1 or more, more preferably 1.5 to 3 on average, and still more preferably 1.8 on average. There are 2.5 or less. When the number of reactive groups contained in one molecule of the prepolymer (α) is within the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) increases.

  Mn of the prepolymer (α) is preferably 500 or more and 30000 or less, more preferably 1000 or more and 20000 or less, and further preferably 2000 or more and 10,000 or less.

  The Mw of the prepolymer (α) is preferably 1000 or more and 50000 or less, more preferably 2000 or more and 40000 or less, and further preferably 4000 or more and 20000 or less.

  The viscosity of the prepolymer (α) is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, at 100 ° C. By setting the viscosity of the prepolymer (α) to 200 Pa · s or less, core particles (B) having a narrow distribution width in the particle size distribution can be obtained.

  As the active hydrogen group-containing compound (β1) in the above combination [14], for example, polyamine (β1a) which may be blocked with a detachable compound (hereinafter abbreviated as “polyamine (β1a)”); Examples include polyol (β1b); polymercaptan (β1c); water and the like. Of these, the polyamine (β1a) and water are preferred as the active hydrogen group-containing compound (β1), and more preferred are blocked polyamines and water.

  Examples of the polyamine (β1a) include those listed as specific examples of the polyamine (15). The polyamine (β1a) is preferably 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine or a mixture thereof.

  When the polyamine (β1a) is a polyamine blocked with a detachable compound, examples of the polyamine include the polyamines and ketones having 3 to 8 carbon atoms (for example, acetone, methyl ethyl ketone or methyl). A ketimine compound obtained from an isobutyl ketone and the like; an aldimine compound obtained from an aldehyde compound having 2 to 8 carbon atoms (eg, formaldehyde or acetaldehyde); an enamine compound; an oxazolidine compound and the like.

  Examples of the polyol (β1b) include the same as those listed as specific examples of the diol (10) and the polyol (11). Of these, preferred as the polyol (β1b) are the diol (10) alone and a mixture of the diol (10) and a small amount of polyol (11).

  Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

  If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using the reaction terminator (βs) together with the active hydrogen group-containing compound (β1) at a constant ratio, it is possible to adjust the molecular weight of the resin (b) to a predetermined value. For the same reason, a reaction terminator (βs) can be used together with the compound (β2) capable of reacting with the active hydrogen-containing group in the combination [15].

  Examples of the reaction terminator (βs) include monoamines (eg, diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine or diethanolamine); monoamines blocked (eg, ketimine compounds); monools (eg, Such as methanol, ethanol, isopropanol, butanol or phenol); monomercaptan (eg, butyl mercaptan or lauryl mercaptan); monoisocyanate (eg, lauryl isocyanate or phenyl isocyanate); monoepoxide (eg, butyl glycidyl ether), etc. It is done.

  The active hydrogen-containing group (α2) of the prepolymer (α) in the combination [15] includes a hydroxyl group (for example, an alcoholic hydroxyl group or a phenolic hydroxyl group) (α2b), a carboxyl group (α2d), and And an organic group (α2e) blocked with a detachable compound. Of these, the hydroxyl group (α2b) is preferred.

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group in the combination [15] include polyisocyanate (β2a), polycarboxylic acid (β2c), polyacid anhydride (β2d), and the like. Of these, polyisocyanate (β2a) is preferable as the compound (β2).

  Examples of the polyisocyanate (β2a) include those listed as specific examples of the polyisocyanate (14). Preferred examples of the polyisocyanate (β2a) include preferable specific examples of the polyisocyanate (14). As listed above.

  Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). Among these, the polycarboxylic acid (β2c) is preferably a polycarboxylic acid (β2c). It is a mixture of dicarboxylic acid (β2c-1) alone and dicarboxylic acid (β2c-1) and a small amount of polycarboxylic acid (β2c-2).

  Examples of the dicarboxylic acid (β2c-1) include those similar to those listed as specific examples of the dicarboxylic acid (12) and the polycarboxylic acid (13), and are preferable as the dicarboxylic acid (β2c-1). These are the same as those listed as preferred specific examples of the dicarboxylic acid (12) and the polycarboxylic acid (13).

  Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride.

  The ratio of the curing agent (β) in the precursor (b0) of the core resin (b) is not particularly limited. The ratio ([α] / [β]) of the equivalent [α] of reactive groups in the prepolymer (α) to the equivalent [β] of active hydrogen-containing groups in the curing agent (β) is preferably 1 / 2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2 What is necessary is just to set the ratio of the hardening | curing agent ((beta)) in the precursor (b0) of (b). In addition, when a hardening | curing agent ((beta)) is water, water is handled as a bivalent active hydrogen compound.

<Step [III]>
In step [III], the core particle (B) -containing core particle (B) is contained in the insulating liquid (L) by dispersing the core particle (B) forming solution in the dispersion liquid (W) of the shell particles (A). B) is formed, and toner particles (C) having a core-shell structure in which the shell particles (A) are attached to or coated on the surfaces of the core particles (B) are formed.

  A method for dispersing the core particle (B) forming solution in the dispersion liquid (W) of the shell particles (A) is not particularly limited, but the core particle (B) forming solution is added to the shell particle (A) using a dispersing device. It is preferable to disperse in the dispersion liquid (W).

  Generally as a dispersion apparatus, if it is marketed as an emulsifier or a disperser, it can be used without being specifically limited. Examples of the dispersing apparatus include batch type emulsifiers such as homogenizer (manufactured by IKA), polytron (product name, manufactured by Kinematica) and TK auto homomixer (product name, manufactured by Tokushu Kika Kogyo Co., Ltd.); Dar (product name, manufactured by Ebara Manufacturing Co., Ltd.), TK Philmix, TK Pipeline Homo Mixer (all product names, manufactured by Special Machine Industries Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), Continuous emulsifiers such as Thrasher, Trigonal wet milling machine (Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech Co., Ltd.) and Fine Flow Mill (Pacific Kiko Co., Ltd.); Microfluidizer (Product name) , Mizuho Kogyo Co., Ltd.), Nanomizer (product name, manufactured by Nanomizer) and APV Gaurin (product name, manufactured by Gaulin) Membrane emulsifiers such as membrane emulsifiers (produced by Chilling Industries Co., Ltd.); Vibratory emulsifiers such as Vibro mixers (produced by Chillers Industries Co., Ltd.); Examples thereof include a sonic emulsifier. Among these apparatuses, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are preferable from the viewpoint of the particle size distribution of the toner particles.

  The temperature when the core particle (B) forming solution is dispersed in the dispersion (W) of the shell particles (A) is not particularly limited, but is preferably 0 ° C. or higher and 150 ° C. or lower (under pressure), more preferably. Is 5 ° C. or higher and 98 ° C. or lower. When the viscosity of a solution obtained by dispersing the core particle (B) forming solution in the dispersion (W) of the shell particles (A) (hereinafter also referred to as resin particle dispersion (X ′)) is high, It is preferable to lower the viscosity of the core particle (B) forming solution to a preferred range by increasing the temperature at which the core particle (B) forming solution is dispersed in the dispersion (W) of the shell particles (A). . The preferable range of the viscosity of the solution for forming the core particle (B) is as described in the description of the above step [II], and is 10 mPa · s or more and 50000 mPa · s or less (viscosity measured with a B-type viscometer). It is.

  The mixing ratio of the dispersion liquid (W) of the shell particles (A) and the core particle (B) forming solution is not particularly limited. However, the dispersion (W) of the shell particles (A) is based on 100 parts by mass of the core resin (b) or the core resin (b) precursor (b0) dissolved in the core particle (B) forming solution. It is preferably contained in an amount of 50 parts by mass or more and 2000 parts by mass or less, and more preferably 100 parts by mass or more and 1000 parts by mass or less. If 50 parts by mass or more of the dispersion (W) of the shell particles (A) is contained in 100 parts by mass of the core resin (b) or the precursor (b0) of the core resin (b), the resin particle dispersion ( The dispersion state of the core resin (b) or the precursor (b0) of the core resin (b) in X ′) is improved. It is economical if the dispersion (W) of the shell particles (A) is contained in an amount of 2000 parts by mass or less with respect to 100 parts by mass of the core resin (b) or the precursor (b0) of the core resin (b).

The core-shell structure is formed by dispersing the core particle (B) forming solution in the dispersion (W) of the shell particles (A). The adsorption force of the shell particles (A) to the core particles (B) is It is preferable to control according to the method shown in the following [18] to [20].
[18]: The shell particles (A) and the core particles (B) are charged with opposite polarities. At this time, the larger the charge of each of the shell particles (A) and the core particles (B), the stronger the adsorption force of the shell particles (A) to the core particles (B). The coverage of the shell particles (A) with respect to the surface is increased.
[19]: If the shell particles (A) and the core particles (B) are charged with the same polarity, the coverage of the shell particles (A) on the surface of the core particles (B) is lowered. At this time, if at least one of the surfactant (s) and the oily polymer (t) (especially those having the opposite polarity between the shell particles (A) and the core particles (B)) is used, the core particles (B ) Of the shell particles (A) becomes stronger, and thus the coverage of the shell particles (A) on the surface of the core particles (B) becomes higher.
[20]: When the SP value difference is reduced between the dispersion (W) of the shell particles (A) and the solution for forming the core particles (B), the adsorptive power of the shell particles (A) to the core particles (B) increases. Therefore, the coverage of the shell particles (A) on the surface of the core particles (B) is increased.

  A core-shell structure in which the shell particles (A) are attached to the surfaces of the core particles (B) is formed, or the core particles in which the shell particles (A) are coated on the surfaces of the core particles (B). Whether the shell structure is formed depends on the physical properties of the organic solvent (M) contained in the core particle (B) forming solution, specifically the shell particles (A) and / or the core resin (b) with respect to the organic solvent (M). ).

  Specifically, if the organic solvent (M) that dissolves the core resin (b) but does not dissolve the shell particles (A) is selected, the shell particles (A) are attached to the surface of the core particles (B). .

  On the other hand, when an organic solvent (M) that dissolves both the shell particles (A) and the core resin (b) is selected, the shell particles (A) are melted in the organic solvent (M). ) Adheres to the surface. Therefore, when the organic solvent (M) is distilled off in a later step, the organic solvent (M) adhering to the surface of the core particle (B) is also distilled off. Particles (A) are formed into a film. Hereinafter, forming the shell particles (A) in the form of a film on the surface of the core particles (B) will be referred to as “film formation treatment”.

  In order to perform the film-forming treatment, it is preferable to select THF, toluene, acetone, methyl ethyl ketone, or ethyl acetate as the organic solvent (M), and it is more preferable to select acetone, ethyl acetate, or the like.

  When the coating treatment is performed, the content of the organic solvent (M) in the resin particle dispersion (X ′) is preferably 10% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass. It is. And when distilling off the organic solvent (M) after the film-forming treatment, the content of the organic solvent (M) in the resin particle dispersion (X ′) is preferably 1% by mass or less at a temperature of 40 ° C. or less. More preferably, the organic solvent (M) may be removed until the content becomes 0.5% by mass or less. Thereby, the shell layer consisting of the shell particles (A) dissolved in the organic solvent (M) is formed on the surface of the core layer composed of the core particles (B).

  When the film forming treatment is performed, an organic solvent used in the film forming treatment can be added to the resin particle dispersion (X ′). However, it is preferable to use the organic solvent (M) contained in the solution for forming the core particles (B) as the organic solvent for film formation treatment without removing after the formation of the core particles (B). Because the organic solvent (M) is contained in the core particle (B), the shell particle (A) can be easily dissolved in the organic solvent (M). It is because it becomes difficult to occur.

  When the shell particles (A) are dissolved in the organic solvent (M), the concentration of the organic solvent (M) in the resin particle dispersion (X ′) is preferably 3% by mass or more and 50% by mass or less, more preferably It is 10 mass% or more and 40 mass% or less, More preferably, it is 15 mass% or more and 30 mass% or less. In addition, it is preferable to stir the resin particle dispersion (X ′), for example, for 1 hour to 10 hours. Furthermore, the temperature at which the shell particles (A) are dissolved in the organic solvent (M) is preferably 15 ° C. or higher and 45 ° C. or lower, and more preferably 15 ° C. or higher and 30 ° C. or lower.

  When the shell particles (A) are dissolved in the organic solvent (M) and coated on the surface of the core particles (B), the solid content in the resin particle dispersion (X ′) (content of components other than the solvent) Is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. Further, the content of the organic solvent (M) at the time of molding the toner particles (C) is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less. is there. When the solid content in the resin particle dispersion (X ′) is high and when the content of the organic solvent (M) at the time of molding the toner particles (C) exceeds 2% by mass, the resin particle dispersion When the temperature of the liquid (X ′) is raised to 60 ° C. or higher, aggregates may be generated. Moreover, the melting method of the shell particles (A) is not particularly limited, and for example, preferably 40 ° C. or more and 100 ° C. or less, more preferably 60 ° C. or more and 90 ° C. or less, and further preferably 60 ° C. or more and 80 ° C. with stirring. In the following, a method of heating preferably 1 minute to 300 minutes is mentioned.

  When the coating treatment is performed, the resin particles dispersion (X ′) having an organic solvent (M) content of 2% by mass or less at the time of molding the toner particles (C) is heated to change the shell particles (A) into core particles. It is preferable to melt on the surface of (B). Thereby, toner particles (C) having a smoother surface can be obtained. The heating temperature at this time is preferably equal to or higher than Tg of the shell resin (a), and more preferably equal to or lower than 80 ° C. If the heating temperature is lower than the Tg of the shell resin, the effect obtained by heating (that is, the effect of further smoothing the surface of the toner particles) may not be obtained. On the other hand, when the heating temperature exceeds 80 ° C., the shell layer may be peeled off from the core layer.

  A preferable method for the coating treatment is a method of melting the shell particles (A) and a combination of a method of dissolving the shell particles (A) and a method of melting the shell particles (A).

<Process [IV]>
In step [IV], the organic solvent (M) contained in the core particle (B) forming solution is distilled off from the resin particle dispersion (X ′).

  The method for distilling off the organic solvent (M) from the resin particle dispersion (X ′) is not particularly limited. For example, under a reduced pressure of 0.02 MPa to 0.066 MPa, the organic solvent (M) The method of distilling off the said organic solvent (M) at the temperature below a boiling point etc. is mentioned.

  The content rate of the organic solvent (M) in the dispersion liquid after distilling off the organic solvent (M) is preferably 1% by mass or less, more preferably 0.5% by mass or less. A part of the insulating liquid (L) (for example, a low boiling point component in the insulating liquid (L)) may be distilled off together with the organic solvent (M).

  The shape of the toner particles (C) contained in the liquid developer (X) thus obtained and the smoothness of the surface of the toner particles (C) are determined by the SP of the shell resin (a) and the core resin (b). It is controlled by controlling at least one of the value difference and the molecular weight of the core resin (a). If the SP value difference is too small, it is easy to obtain toner particles having a distorted shape but a smooth surface. Conversely, when the SP value difference is too large, toner particles having a spherical shape but having a rough surface are likely to be obtained. When the molecular weight of the shell resin (a) is too large, toner particles having a rough surface are easily obtained, and when the molecular weight of the shell resin (a) is too small, toner particles having a smooth surface are easily obtained. Further, if the SP value difference is too small or too large, granulation is difficult. Moreover, even if the molecular weight of the shell resin (a) is too small, granulation is difficult. From the above, the SP value difference is preferably 0.01 or more and 5.0 or less, more preferably 0.1 or more and 3.0 or less, and further preferably 0.2 or more and 2.0 or less. is there. Moreover, Mw of shell resin (a) becomes like this. Preferably it is 100 or more and 1 million or less, More preferably, it is 1000 or more and 500000 or less, More preferably, it is 2000 or more and 200000 or less, Most preferably, it is 3000 or more and 100000 or less.

  In addition, when manufacturing the core-shell structure in this Embodiment, after manufacturing a core particle (B) according to the manufacturing method in any one of said [7]-[13], the said core particle (B) Shell particles (A) may be attached to or coated on the surface of these.

  Further, in the method for producing the liquid developer (X) according to the present embodiment, additives other than the colorant (for example, a filler, an antistatic agent, a release agent, a charge control agent, an ultraviolet absorber, an antioxidant) And at least one of a dispersion of shell particles (A), a solution for forming core particles (B), and a dispersion of a colorant is prepared by adding an anti-blocking agent, a heat stabilizer and a flame retardant. May be. Also in this case, the additive is added to the dispersion (W) of the shell particles (A) by adding a solution in which an additive other than the colorant is dissolved or dispersed to the dispersion (W) of the shell particles (A). Can be added. As a result, toner particles (C) in which additives other than the colorant are also contained in at least one of the core layer and the shell layer can be obtained.

<Process [V]>
The core particles (B) in the present embodiment preferably contain a core resin (b) and a colorant. The colorant may be obtained by dispersing the colorant in at least one of the dispersion (W) of the shell particles (A) and the solution for forming the core particles (B), or in a predetermined organic solvent. The dispersion may be mixed with at least one of the dispersion (W) of the shell particles (A) and the solution for forming the core particles (B).

  As the colorant, at least one of the pigments listed in the description of the colorant can be used. As the solution for dissolving or dispersing the colorant, for example, an organic solvent such as acetone can be used.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Production Example 1>
[Production of dispersion liquid (W) of shell particles (A)]
In the following production examples and examples, the types of shell particles (A) are described as, for example, shell particles (A1), shell particles (A2), and the like. Moreover, the dispersion liquid in which the shell particles (A1) are dispersed is referred to as a dispersion liquid (W1), for example.

<Production Example 1-1>
[Production of dispersion (W1) of shell particles (A1)]
195 parts by mass of THF was charged into a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, a dropping funnel, a solvent removal device, and a nitrogen introduction tube. In a glass beaker, 100 parts by mass of 2-decyltetradecyl acrylate, 30 parts by mass of methacrylic acid, 70 parts by mass of an equimolar reaction product of hydroxyethyl methacrylate and phenyl isocyanate, 0.5 wt. Of azobismethoxydimethylvaleronitrile A mixed solution consisting of part by mass was added, stirred and mixed at 20 ° C. to prepare a monomer solution, which was then added to a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 1 hour under hermetically sealed condition. Three hours after the completion of the dropping, a mixture of 0.05 part by mass of azobismethoxydimethylvaleronitrile and 5 parts by mass of THF was added, reacted at 70 ° C. for 3 hours, cooled to room temperature, and shell particles ( A copolymer solution of A1) was obtained. While stirring 400 parts by mass of the copolymer solution which is the shell particles (A1), 600 parts by mass of Isopar L (manufactured by ExxonMobil Co., Ltd.) is dropped, and THF is distilled off at 40 ° C. under a reduced pressure of 0.039 MPa. Thus, a dispersion liquid (W1) of shell particles (A1) was obtained. The volume average particle diameter of the shell particles (A1) contained in the dispersion liquid (W1) measured using “LA-920” was 0.12 μm.

<Production Example 1-2>
[Production of polyester resin]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, and a nitrogen introduction tube, 286 parts by mass of dodecanedioic acid, 190 parts by mass of 1,6-hexanediol, and a condensation catalyst 1 part by mass of titanium dihydroxybis (triethanolaminate) was added and reacted at 180 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water under a nitrogen stream, and further the reaction is carried out for 1 hour under a reduced pressure of 0.007 MPa or more and 0.026 MPa or less. Obtained. The polyester resin thus obtained had a melting point of 68 ° C., Mn of 4900, and Mw of 10,000.

[Production of dispersion (W2) of shell particles (A2)]
195 parts by mass of THF was charged into a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, a dropping funnel, a solvent removal device, and a nitrogen introduction tube. In a glass beaker, 80 parts by mass of 2-decyltetradecyl acrylate, 10 parts by mass of methyl methacrylate, 10 parts by mass of methacrylic acid, an isocyanate group-containing monomer (product name: Karenz MOI, Showa Denko Co., Ltd.) and the above A mixed solution consisting of 10 parts by weight of an equimolar reaction product of the obtained polyester resin and 0.5 parts by weight of azobismethoxydimethylvaleronitrile was added, stirred and mixed at 20 ° C. to prepare a monomer solution, It was put into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 1 hour under hermetically sealed condition. Three hours after the completion of the dropping, a mixture of 0.05 part by mass of azobismethoxydimethylvaleronitrile and 5 parts by mass of THF was added, reacted at 70 ° C. for 3 hours, cooled to room temperature, and shell particles ( A copolymer solution of A2) was obtained. 400 parts by mass of the copolymer solution as the shell particles (A2) was added dropwise to 600 parts by mass of Isopar L (manufactured by ExxonMobil) while stirring, and THF was distilled off at 40 ° C. under a reduced pressure of 0.039 MPa. Thus, a dispersion liquid (W2) of shell particles (A2) was obtained. The volume average particle diameter of the shell particles (A2) contained in the dispersion liquid (W2) measured using “LA-920” was 0.13 μm.

<Production Example 2>
[Production of Core Particle (B) Formation Solution of Core Resin (b)]
In the following production examples and examples, the types of the core resin (b) are described as, for example, the core resin (b-1) and the core resin (b-2). For example, the core particle (B) containing the core resin (b-1) is referred to as a core particle (B1). Further, for example, a core particle (B) forming solution in which the core resin (b-1) or its precursor is dissolved is referred to as a core particle (B1) forming solution.

<Production Example 2-1>
[Production of Core Particle (B1) Formation Solution for Core Resin (b-1)]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 961 parts by mass (5.2 parts by mol) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 1 part by mass of DMPA (0.05 mol part) and 38 parts by mass of IPDI (4.2 mol part) were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-1). A solution for forming particles (B1) was obtained. At this time, the core resin (b-1) is ([b1] + [b2]) / [b3] = 1.236 in the above formulas (1) and (2), and [b2] / ( [B1] + [b2]) = 0.01.

<Production Example 2-2>
[Production of Core Particle (B2) Formation Solution for Core Resin (b-2)]
Polyester (Mn = 2200) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 906 parts by mass (13.7 parts by mol) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 10 parts by weight (1.5 parts by weight) of DMPA and 84 parts by weight (14.2 parts by mole) of IPDI were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-2). A solution for forming particles (B2) was obtained. At this time, the core resin (b-2) is ([b1] + [b2]) / [b3] = 1.070 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.10.

<Production Example 2-3>
[Production of Core Particle (B3) Formation Solution for Core Resin (b-3)]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 971 parts by mass (2.2 parts by mol) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 2 parts by mass of DMPA (0.05 mol part) and 27 parts by mass of IPDI (1.3 mol part) were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-3). A solution for forming core particles (B3) was obtained. At this time, the core resin (b-3) is ([b1] + [b2]) / [b3] = 1.780 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.02.

<Production Example 2-4>
[Production of Core Particle (B4) Formation Solution for Core Resin (b-4)]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. 896 parts by mass (12.2 parts by mol) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. DMPA 20 parts by mass (3.0 parts by mol) and IPDI 84 parts by mass (14.2 parts by mol) were added to this solution and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-4). A solution for forming core particles (B4) was obtained. At this time, the core resin (b-4) is ([b1] + [b2]) / [b3] = 1.070 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.20.

<Production Example 2-5>
[Production of Core Particle (B5) Formation Solution for Core Resin (b-5)]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 953 parts by mass (1.8 mol parts) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 20 parts by mass (0.5 parts by mol) of DMPA and 27 parts by mass (1.3 parts by mol) of IPDI were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-5). A solution for forming particles (B5) was obtained. At this time, the core resin (b-5) is ([b1] + [b2]) / [b3] = 1.780 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.20.

<Production Example 2-6>
[Production of Core Particle (B6) Formation Solution for Core Resin (b-6)]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 973 parts by mass (2.3 mol parts) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. 27 parts by mass (1.3 mol parts) of IPDI was added to this solution and reacted at 80 ° C. for 6 hours to obtain a solution for forming core particles (B6) in which the core resin (b-6) was dissolved. At this time, the core resin (b-6) is ([b1] + [b2]) / [b3] = 1.780 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.

<Production Example 2-7>
[Production of Core Particle (B7) Formation Solution for Core Resin (b-7)]
Polyester (Mn = 2200) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 885 parts by mass (2.0 mol parts) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 98 parts by mass of DMPA (0.2 mol part) and 17 parts by mass of IPDI (1.2 mol part) were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-7). A solution for forming core particles (B7) was obtained. At this time, the core resin (b-7) is ([b1] + [b2]) / [b3] = 1.850 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.10.

<Production Example 2-8>
[Production of core resin (b-8) core particle (B8) forming solution]
Polyester (Mn = 4500) obtained from sebacic acid, adipic acid and ethylene glycol (molar ratio 0.8: 0.2: 1) in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer. ) 815 parts by mass (30.4 mol parts) and 300 parts by mass of acetone were added and stirred to dissolve uniformly. To this solution, 91 parts by mass of DMPA (3.4 parts by mol) and 94 parts by mass of IPDI (32.8 parts by mol) were added and reacted at 80 ° C. for 6 hours to dissolve the core resin (b-8). A solution for forming particles (B8) was obtained. At this time, the core resin (b-8) is ([b1] + [b2]) / [b3] = 1.030 in the above formulas (1) and (2), and [b2] / ([b1 ] + [B2]) = 0.10.

<Production Example 3>
[Production of urethane prepolymer]
Polycaprolactone diol having a hydroxyl value of 56 (product name: “Placcel L220AL”, manufactured by Daicel Chemical Industries, Ltd.) 2000 in a reaction vessel equipped with a stirrer, a heating / cooling device, a dehydrating device, and a thermometer. A part by mass was added, heated to 110 ° C., and dehydrated under a reduced pressure of 0.026 MPa for 1 hour. Next, 457 parts by mass of IPDI was added and reacted at 110 ° C. for 10 hours to obtain a urethane prepolymer having an isocyanate group at the terminal. The NCO content of the urethane prepolymer was 3.6% by mass.

<Production Example 4>
[Manufacture of curing agent]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, 50 parts by mass of ethylenediamine and 300 parts by mass of methyl isobutyl ketone are charged, and the reaction is performed at 50 ° C. for 5 hours. A curing agent was obtained.

<Production Example 5>
[Production of colorant dispersion]
In a beaker, 25 parts by mass of copper phthalocyanine, 4 parts by mass of a colorant dispersant (product name: “Ajisper PB-821”, manufactured by Ajinomoto Fine Techno Co., Ltd.) and 75 parts by mass of acetone are added and stirred. After uniformly dispersing, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle size of the colorant contained in the colorant dispersion was 0.2 μm.

  In the description of the following examples, for example, the liquid developer of Example 1 is referred to as liquid developer (X-1), the liquid developer of Example 2 is referred to as liquid developer (X-2), and the like. Similarly, in the comparative example, for example, the liquid developer of Comparative Example 1 is referred to as a liquid developer (Z-1).

<Example 1>
In a beaker, 45 parts by mass of the solution for forming the core particles (B1) obtained in Production Example 2-1 and 15 parts by mass of the colorant dispersion obtained in Production Example 4 were added, and a TK auto homomixer at 25 ° C. (Product name, manufactured by Tokushu Kika Kogyo Co., Ltd.) was stirred at 8000 rpm and dispersed uniformly to obtain a mixed solution of the core particle (B1) forming solution and the colorant dispersion.

  In another beaker, 67 parts by mass of liquid paraffin and 6 parts by mass of the dispersion liquid (W1) obtained in Production Example 1-1 were charged and uniformly dispersed. Next, while stirring at 10000 rpm using a TK auto homomixer at 25 ° C., 60 parts by mass of the mixed solution of the core particle (B1) forming solution and the colorant dispersion was added and stirred for 2 minutes. Next, this mixed solution was put into a reaction vessel equipped with a stirring device, a heating / cooling device, a thermometer, and a solvent removal device, heated to 35 ° C., and then at the same temperature under a reduced pressure of 0.039 MPa, Acetone was distilled off until the acetone concentration reached 0.5% by mass or less to obtain a liquid developer (X-1). The concentration of acetone in the liquid developer (X-1) is quantitatively determined by gas chromatography (product name: “GC2010”, manufactured by Shimadzu Corporation) using a flame ion detection method (hereinafter also referred to as FID method). did.

  The solubility of the shell resin (a) in the liquid developer (X-1) obtained as described above in the insulating liquid (L) at 25 ° C. was measured as follows.

  10 g of the liquid developer (X-1) was centrifuged at 10000 rpm for 30 minutes at 25 ° C., and the entire supernatant was recovered. 10 ml of the insulating liquid (L) was added to the remaining solid content, and the toner particles (C) were dispersed again. Then, it centrifuged at 25 degreeC and 10000 ppm for 30 minutes, and collect | recovered all the supernatant liquids. This operation was further repeated, and the supernatant was collected 3 times in total. The supernatant liquid was dried with a vacuum dryer at a temperature equal to the boiling point of the insulating liquid (L) for 1 hour under a reduced pressure of 20 mmHg, and the mass of the residue was weighed. The residue mass Y (g) and the mass y (g) of the shell resin (a) in 10 g of the liquid developer are substituted into the following formula (7) to insulate the liquid developer (X-1). The solubility (25 ° C.) of the shell resin (a) in the functional liquid (L) was calculated.

Solubility (% by weight) = (Y / y) × 100 (7)
As a result of the measurement as described above, the solubility of the shell resin (a) in the liquid developer (X-1) in (L) at 25 ° C. was 3% by mass. The results are shown in Table 1.

<Examples 2-5 and Comparative Examples 1-5>
In the same manner as in Example 1, except that the core particle (B) forming solution, urethane prepolymer, curing agent, colorant dispersion, liquid paraffin, and dispersion shown in Table 1 are used. Liquid developers (X-2) to (X-5) and liquid developers (Z-1) to (Z-5) of comparative examples were obtained.

  In Table 1, the column for the dispersion (W) of the shell particles (A) indicates the type of the dispersion used. For example, “W1” indicates that the dispersion liquid (W1) of the shell particles (A1) described in Production Example 1 is used.

  The column of the type of the core particle (B) forming solution indicates the type of the core particle forming solution used. For example, “B1” indicates that the core particle (B1) forming solution described in Production Example 2 is used.

  The numerical values in the columns of urethane prepolymer, curing agent, colorant dispersion, and liquid paraffin all indicate the amount used (parts by mass).

  The liquid developers (X-1) to (X-5) and (Z-1) to (Z-5) obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were each converted into liquid paraffin. After dilution, the volume average particle diameter and the coefficient of variation of volume distribution of the toner particles (C) were measured using “LA-920”. Further, the state of the shell particles (A) in the toner particles (C) was observed by the following method. Then, the surface coverage of the core particles (B) with the shell particles (A) in the toner particles (C) was measured by the above method. Further, the fixability and heat resistance stability of the liquid developer were evaluated by the following methods. The results are shown in Table 1.

<Evaluation of the state of the shell particles (A) in the toner particles (C)>
The surface of 50 toner particles (C) was observed with a scanning electron microscope (SEM) to determine whether the shell particles (A) were attached to the surface of the core particles (B) or formed into a film.

<Image forming apparatus>
FIG. 1 is a schematic conceptual diagram of an electrophotographic image forming apparatus used for evaluating the fixability of a liquid developer according to this embodiment. In the image forming apparatus 1, the liquid developer 2 is pumped up by the supply roller 3 and rubbed off by the regulating blade 4, so that a thin layer of the liquid developer 2 having a predetermined thickness is formed on the supply roller 3. . In the case of an anilox roller, the engraving of the roller is filled with a liquid developer, and the prescribed amount is measured by the regulating roller. Next, a thin layer of the liquid developer 2 moves from the supply roller 3 onto the developing roller 5, and a toner image is formed on the photosensitive member 6 with toner particles by the nip between the developing roller 5 and the photosensitive member 6. Thereafter, the toner image is transferred onto the recording material 11 by the nip between the photoreceptor 6 and the backup roller 10, and the image is fixed by the heat roller 12. In addition to the above, the image forming apparatus 1 includes a developing roller cleaning blade 8 and a charging device 9.

<Fixing strength evaluation>
Using the image forming apparatus shown in FIG. 1, a solid pattern (10 cm × 10 cm, adhesion amount: 2 mg / m ² ) of each liquid developer in Examples and Comparative Examples was coated with 128 g / cm ² high-quality paper (product name: It was formed on “Kinryo 128 g / cm ² ” (Mitsubishi Paper) and fixed with a heat roller (180 ° C. × nip time 30 msec).

Thereafter, an eraser (trade name: sand eraser “LION 26111”, manufactured by Lion Corporation) was rubbed twice with a pressing load of 1 kgf, and the residual ratio of image density was measured by a reflection densitometer (product name: “X-Rite model 404”, X-Rite Co.) and the following three ranks were evaluated. The results are shown in the column of fixing strength in Table 1.
Fixing strength A: Image density remaining rate is 90% or more Fixing strength B: Image density remaining rate is 80% or more and less than 90% Fixing strength C: Image density remaining rate is less than 80% In Table 1, fixing strength A is the most fixable. The fixing strength B is excellent, and the fixing strength C indicates that the fixing property is inferior.

<High temperature offset evaluation>
At the same time, roller contamination (high temperature offset) was measured. For high temperature offset, high quality paper was passed through the image forming apparatus, and immediately after the image was formed on the high quality paper, white paper was passed through and the stain on the white paper was visually evaluated. “B” indicates that the toner stain is confirmed on the white paper, and “A” indicates that the toner is not confirmed. The results are shown in the high temperature offset column of Table 1.

  In Table 1, "A" has good high temperature offset performance.

  As is clear from Table 1, the liquid developer of the present embodiment is a liquid developer (X) in which toner particles (C) are dispersed in an insulating liquid (L), and the toner particles (C ) Has a core-shell structure in which the shell particles (A) containing the shell resin (a) are attached to or coated on the surfaces of the core particles (B) containing the core resin (b). ) Is a resin containing a structural unit derived from the diol (b1), a structural unit derived from the carboxyl group-containing diol (b2), and a structural unit derived from the diisocyanate (b3), and the above formulas (1) and ( 2), the diol (b1) has a number average molecular weight of 2000 or more and 12000 or less, and the carboxyl group-containing diol (b2) has an excellent number average molecular weight of 90 or more and 500 or less. Show good fixability, It is fixable in a wide temperature range was confirmed.

  Although the embodiments and examples of the present invention have been described as described above, it is also planned from the beginning to appropriately combine the configurations of the above-described embodiments and examples.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The liquid developer (X) of the present invention is extremely useful in applications such as paints, electrophotographic liquid developers, electrostatic recording liquid developers, oil-based inks for inkjet printers, and inks for electronic paper. Further, as other applications, it has high utility value in applications such as cosmetics, spacers for manufacturing electronic components, and electrorheological fluids.

  DESCRIPTION OF SYMBOLS 1 Image forming apparatus, 2 Liquid developer, 3 Supply roller, 4 Regulating blade, 5 Developing roller, 6 Photoconductor, 7, 8 Cleaning blade, 9 Charging device, 10 Backup roller, 11 Recording material, 12 Heat roller

Claims (13)

A liquid developer (X) in which toner particles (C) are dispersed in an insulating liquid (L),
The toner particles (C) have a core-shell structure in which the shell particles (A) containing the shell resin (a) are attached to or coated on the surfaces of the core particles (B) containing the core resin (b),
The core resin (b) is a resin including a structural unit derived from the diol (b1), a structural unit derived from the carboxyl group-containing diol (b2), and a structural unit derived from the diisocyanate (b3), and the following formula Satisfy (1) and (2)
The diol (b1) has a number average molecular weight of 2000 or more and 12000 or less,
The carboxyl group-containing diol (b2) is a liquid developer (X) having a number average molecular weight of 90 or more and 500 or less.
1.060 ≦ ([b1] + [b2]) / [b3] ≦ 1.800 (1)
0.01 ≦ [b2] / ([b1] + [b2]) ≦ 0.15 (2)
(In the formulas (1) and (2), [b1] indicates the molar ratio of the structural unit derived from the diol (b1) to the core resin (b), and [b2] is derived from the carboxyl group-containing diol (b2). (B3) indicates the molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b). The volume average particle diameter of the toner particles (C) is 0.01 μm or more and 100 μm or less,
2. The liquid developer (X) according to claim 1, wherein a coefficient of variation of the volume distribution of the toner particles (C) is 1% or more and 100% or less.   3. The liquid developer (X) according to claim 1, wherein an average value of the circularity of the toner particles (C) is 0.92 or more and 1.0 or less.   The liquid developer (X) according to any one of claims 1 to 3, wherein the shell resin (a) is at least one selected from the group consisting of a vinyl resin, a polyester resin, a polyurethane resin, and an epoxy resin.   The liquid according to claim 1, wherein the shell resin (a) is a vinyl resin and is a homopolymer or a copolymer including a structural unit derived from a monomer having a polymerizable double bond. Developer (X).   The liquid developer (X) according to claim 5, wherein the monomer having a polymerizable double bond is a vinyl monomer (m) having a molecular chain (k).   The vinyl monomer (m) includes a vinyl monomer (m1) having a linear hydrocarbon chain having 12 to 27 carbon atoms, a vinyl monomer (m2) having a branched hydrocarbon chain having 12 to 27 carbon atoms, carbon The liquid developer according to claim 6, which is at least one selected from the group consisting of a vinyl monomer (m3) having 4 to 20 fluoroalkyl chains and a vinyl monomer (m4) having a polydimethylsiloxane chain. X).   The liquid developer (1) according to any one of claims 1 to 7, wherein the core particle (B) contains at least one of a wax (c) and a modified wax (d) in which a vinyl polymer chain is graft-polymerized to the wax. X).   The liquid developer (X) according to any one of claims 1 to 8, wherein in the toner particles (C), the surface coverage of the core particles (B) by the shell particles (A) is 50% or more. .   10. The liquid developer (X) according to claim 1, wherein the liquid developer (X) is a paint, an electrophotographic liquid developer, an electrostatic recording liquid developer, an oil-based ink for an inkjet printer, or an ink for electronic paper. Liquid developer (X).   The liquid developer (X) according to any one of claims 1 to 10, wherein the core particle (B) contains the core resin (b) and a colorant. Preparing a dispersion (W) of shell particles (A) in which shell particles (A) containing the shell resin (a) are dispersed in the insulating liquid (L);
Preparing a solution for forming core particles (B) in which the core resin (b) or the precursor (b0) of the core resin (b) is dissolved in the organic solvent (M);
The core particle (B) containing the core resin (b) in the dispersion (W) is obtained by dispersing the core particle (B) forming solution in the dispersion (W) of the shell particles (A). And forming toner particles (C) having a core-shell structure in which the shell particles (A) are attached to or coated on the surfaces of the core particles (B);
A step of obtaining a liquid developer (X) by distilling off the organic solvent (M) after the step of obtaining the toner particles (C),
The core resin (b) contained in the liquid developer (X) includes a structural unit derived from the diol (b1), a structural unit derived from the carboxyl group-containing diol (b2), and a structural unit derived from the diisocyanate (b3). And satisfying the following formulas (1) and (2),
The diol (b1) has a number average molecular weight of 2000 or more and 12000 or less,
The carboxyl group-containing diol (b2) is a method for producing a liquid developer (X) having a number average molecular weight of 90 or more and 500 or less.
1.060 ≦ ([b1] + [b2]) / [b3] ≦ 1.800 (1)
0.01 ≦ [b2] / ([b1] + [b2]) ≦ 0.15 (2)
(In the formulas (1) and (2), [b1] indicates the molar ratio of the structural unit derived from the diol (b1) to the core resin (b), and [b2] is derived from the carboxyl group-containing diol (b2). (B3) indicates the molar ratio of the structural unit derived from the diisocyanate (b3) to the core resin (b). Solubility parameter of the organic solvent (M) is ^{8.5~20 (cal / cm 3) 1/2} , the liquid developer producing method of claim 12 (X).

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