JP2012116882A - Process for producing resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain resin particles having good heat-resistant storability and antistatic characteristics, and to provide a uniform particle diameter.SOLUTION: A process for producing resin particles (C) comprises a step of: mixing a solvent (S) solution (L) of a resin (b), fine particles (A), an additive (T) (a vegetable oil or the like) containing a compound represented by a specific formula, and a nonaqueous organic solvent (N) to form a nonaqueous dispersion (X) of resin particles (C1) in which the fine particles (A) are attached to the surface of resin particle (B1) containing the resin (b), the additive (T), the solvent (S); and further removing the solvent (S), the nonaqueous organic solvent (N) and, if necessary, the additive (T) from the nonaqueous dispersion (X).

Description

  The present invention relates to a method for producing resin particles using a non-aqueous organic solvent.

  As a method for producing resin particles, a resin solvent solution is dispersed in an aqueous medium to prepare a dispersion of resin particles containing a solvent, and then the solvent is removed from the resin particles to obtain particles having a uniform particle size. A method is known (see, for example, Patent Document 1). However, the resin particles obtained by this method have a hydrophilic group oriented on the outermost surface and are easy to absorb moisture. Therefore, plasticization of the resin occurs and the heat resistant storage stability of the resin particles decreases, and charge leakage due to water occurs. There was a problem that the charging characteristics of the particles deteriorated.

JP 2002-284881 A

  An object of the present invention is to obtain resin particles having good heat-resistant storage stability and charging characteristics and having a uniform particle size.

The present invention provides a solvent (S) solution (L) of resin (b), fine particles (A), an additive (T) containing a compound represented by the following general formula [1], and a non-aqueous organic solvent (N ) And a non-aqueous dispersion of resin particles (C1) in which fine particles (A) are adhered to the surfaces of resin particles (B1) containing resin (b), additive (T) and solvent (S) Of the resin particles (C) including the step of forming (X) and further removing the solvent (S), the non-aqueous organic solvent (N), and, if necessary, the additive (T) from the non-aqueous dispersion (X) Production method; and in the production method described above, the solvent (S) solution (L) of the resin (b) further contains a colorant (E) to obtain colored resin particles (C). A method for producing resin particles for an electrophotographic toner.
CH ₂ OR ¹
｜
CHOR ² [1]
｜
CH ₂ OR ³
[Wherein, R ¹ , R ² and R ³ are each independently a saturated fatty acid having 8 to 24 carbon atoms, an unsaturated fatty acid having 8 to 24 carbon atoms, or a derivative thereof, wherein OH of the —COOH group is removed. Represents a residue. ]

  According to the production method of the present invention, it is possible to obtain resin particles having a uniform particle size and good heat storage stability and charging characteristics.

The present invention is described in detail below.
In the production method of the present invention, a resin (b) solvent (S) solution (L), fine particles (A), an additive (T), and a non-aqueous organic solvent (N) are mixed to obtain a resin (b). And a non-aqueous dispersion (X) of resin particles (C1) in which fine particles (A) are adhered to the surface of resin particles (B1) containing the additive (T) and the solvent (S).
The fine particles (A) used in the production method of the present invention include at least one material (a) selected from the group consisting of a crystalline resin (a1), an amorphous resin (a2), and an inorganic compound (a3). The fine particle which becomes is mentioned. As the non-crystalline resin (a2), a cross-linkable non-crystalline resin is preferable.
Among these, the crystalline resin (a1) and the amorphous resin (a2) are preferable, and the crystalline resin (a1) is more preferable.

The melting point of the crystalline resin (a1) is preferably 40 to 110 ° C, more preferably 45 to 100 ° C, particularly preferably 50 to 90 ° C. If the melting point of the crystalline resin (a1) is 40 ° C. or higher, the resin particles (C) obtained by the production method of the present invention are difficult to block even during long-term storage. If it is 110 degrees C or less, low-temperature fixability is favorable.
The melting point in the present invention is measured by a differential scanning calorimeter (DSC) according to JIS K7122 (1987) “Method for measuring the transition heat of plastic”, and the temperature of the endothermic peak due to melting at the first temperature rise (° C.). Means.

  Number average molecular weight of crystalline resin (a1) [measured by gel permeation chromatography (GPC), hereinafter sometimes abbreviated as Mn. ] Is preferably 1000 or more, more preferably 1500 or more, particularly preferably 2000 or more, from the viewpoint of carrier contamination when used as an electrophotographic toner. From the viewpoint of melt viscosity, it is preferably 1000000 or less, more preferably 500000 or less, particularly preferably 300000 or less, and most preferably 100000 or less.

The composition of the crystalline resin (a1) is not particularly limited, but preferred specific examples include, for example, crystallinity having aliphatic or aromatic polyester, aliphatic polyurethane and / or polyurea, and alkyl (meth) acrylate as an essential constituent unit. Examples thereof include a vinyl resin, a crystalline vinyl resin (a14) having (meth) acrylonitrile and a crystalline vinyl monomer as essential constituent units, and a crystalline polyolefin (a15).
In the present invention, alkyl (meth) acrylate means alkyl acrylate and / or alkyl methacrylate, and the same description method is used hereinafter.

As the aliphatic or aromatic polyester, diol (11) and dicarboxylic acid (13) described later can be used, and in particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and 2 to 50 carbon atoms. And the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is 10 to 52, and if necessary, carbon. A crystalline polyester (a11) having an aromatic dicarboxylic acid of several 6 to 30 as a structural unit is preferable.
From the viewpoint of storage stability, the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. . Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

From the viewpoint of crystallinity, the number of carbon atoms in the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diol are 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol.
From the viewpoint of crystallinity, the number of carbon atoms in the alkylene chain of the linear aliphatic dicarboxylic acid having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic dicarboxylic acid are adipic acid, sebacic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid.
Moreover, 6-30 are preferable, as for carbon number of aromatic dicarboxylic acid from a viewpoint of the storage stability of aromatic polyester, More preferably, it is 8-24, Most preferably, it is 8-20. Preferred as the aromatic dicarboxylic acid having 6 to 30 carbon atoms are phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

  In the case of an aromatic polyester, from the viewpoint of resin strength, the dicarboxylic acid is preferably a combination of a linear aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and the aromatic with respect to the total of the linear aliphatic dicarboxylic acid and the aromatic dicarboxylic acid. The ratio of the dicarboxylic acid is preferably 90% or less, more preferably 1 to 85% by weight, and particularly preferably 3 to 80% by weight.

Examples of the aliphatic polyurethane and / or polyurea include a diol (11) described later, a diamine (a divalent one of polyamine (16) described later), and a diisocyanate (a divalent one of a polyisocyanate (15) described below). In particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and / or a linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms and an alkylene having 2 to 50 carbon atoms A crystalline polyurethane comprising a linear aliphatic diisocyanate having a chain as an essential constituent unit, and the total number of carbon atoms of the alkylene chain of the diol and / or diamine and the alkylene chain of the diisocyanate being 10 to 52 And / or polyurea (a12) is preferred.
A linear aliphatic diisocyanate having a polyester diol obtained by reacting a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms with a dicarboxylic acid (13) described later and an alkylene chain having 2 to 50 carbon atoms. The polyurethane obtained from (a12) is also included.
From the viewpoint of storage stability, aliphatic polyurethane and / or polyurea has a carbon number of alkylene chain of diol and / or diamine (when a mixture of diol and diamine is used, carbon of alkylene chain averaged by the weight ratio). Number) and the total number of carbon atoms of the alkylene chain of the diisocyanate is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

The preferred carbon number of the alkylene chain and preferred specific examples of the linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms are the same as those in the crystalline polyester (a11).
From the viewpoint of crystallinity, the number of carbon atoms in the alkylene chain of the linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diamine are tetramethylene diamine and hexamethylene diamine.
In addition, the number of carbon atoms in the alkylene chain of the linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more from the viewpoint of crystallinity. It is. From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diisocyanate are tetramethylene diisocyanate and hexamethylene diisocyanate.

As the crystalline vinyl resin having an alkyl (meth) acrylate as an essential constituent unit, a crystalline vinyl resin (a13) having an alkyl (meth) acrylate having an alkyl group having 12 to 50 carbon atoms as an essential constituent unit is preferable. From the viewpoint of storage stability, the alkyl group preferably has 12 or more carbon atoms, more preferably 14 or more, and particularly preferably 18 or more. From the viewpoint of fixability, it is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. From the viewpoint of storage stability, the alkyl group is preferably a straight chain. Preferred as the alkyl (meth) acrylate having an alkyl group with 12 to 50 carbon atoms are octadecyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl acrylate.
The crystalline vinyl resin containing alkyl (meth) acrylate as an essential constituent unit may be a homopolymer of alkyl (meth) acrylate or a copolymer with other monomers. As the other monomer, a vinyl monomer described later can be appropriately selected.
The content of the constituent unit of the alkyl (meth) acrylate having an alkyl group of 12 to 50 carbon atoms in the crystalline vinyl resin (a13) is preferably 40% by weight or more, more preferably 45% by weight or more, particularly preferably. Is 60% by weight or more.

As the crystalline vinyl resin (a14) having (meth) acrylonitrile and a crystalline vinyl monomer as essential structural units, the content of the structural unit of (meth) acrylonitrile is 0.01 to from the viewpoint of adhesion to resin particles. It is preferably 40% by weight, more preferably 0.05 to 35% by weight, and particularly preferably 0.1 to 30% by weight.
The crystalline vinyl monomer used in combination is not particularly limited as long as a crystalline vinyl resin can be formed, but alkyl (meth) acrylate having 12 to 50 carbon atoms in the above alkyl group, ethylene, and the like Can be mentioned.

  Examples of the crystalline polyolefin (a15) include polyethylene and polypropylene.

  Examples of the method for producing an aliphatic or aromatic polyester include a method of reacting a low molecular polyol and / or a polyalkylene ether diol having an Mn of 1000 or less and a polycarboxylic acid, a method by ring-opening polymerization of a lactone, a low molecular diol and a lower alcohol ( And a known production method such as a method of reacting with a carbonic acid diester such as methanol.

  Examples of the method for producing the aliphatic polyurethane and / or polyurea include known production methods such as a method of reacting a low molecular polyol (including the polyester polyol obtained by the above method) and / or a low molecular weight diamine and diisocyanate.

  Crystalline vinyl resins having an alkyl (meth) acrylate as an essential constituent unit, and crystalline vinyl resins having (meth) acrylonitrile and a crystalline vinyl monomer as essential constituent units include solution polymerization, bulk polymerization, and suspension. The polymerization method of well-known vinyl monomers, such as superposition | polymerization, is mentioned.

  Examples of the method for producing polyolefin include known polymerization methods such as addition polymerization.

  Of the crystalline resin (a1), particularly preferred are (a11), (a12), (a13), and (a14), and most preferred is (a13).

Examples of the amorphous resin (a2) include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide, polyimide, silicone resin, fluororesin, phenol resin, melamine resin, polycarbonate, cellulose, and a mixture thereof. . As the non-crystalline resin (a2), a cross-linkable non-crystalline resin is preferable.
The composition of (a2) is not limited to obtainment, and a commonly used resin may be used.
For example, as the crosslinkable vinyl resin, a copolymer of vinyl monomers including a vinyl monomer (divinylbenzene or the like) having two or more vinyl polymerizable functional groups can be used.
The crosslinkable polyester resin is a polycondensate of a polyol and a polycarboxylic acid, and at least a part of the polyol and / or polycarboxylic acid, a trivalent or higher polyol (12) described below and / or a trivalent or higher polyvalent acid is used. Examples thereof include a polyester resin obtained using the polycarboxylic acid (14).
Similarly, in the case of other resins, resins obtained using at least a part of the crosslinkable monomer are more preferable.
The monomer is selected from monomers used for the amorphous resin (b11) described later.

  As the fine particles (A), the crystalline resin (a1) and the amorphous resin (a2) may be used in combination. The melting point of the mixture of (a1) and (a2) is preferably 50 to 150 ° C. The content of (a2) is preferably 0 to 50% by weight with respect to the total weight of (a1) and (a2). Moreover, the microparticles | fine-particles which coat | covered the amorphous resin (a2) with the crystalline resin (a1) may be sufficient.

  The production method of the fine particles (A) containing the crystalline resin (a1) and / or the non-crystalline resin (a2) may be any production method. Specific examples thereof include a dry production method [fine particles (A). A method of dry pulverizing the material (a) comprising a known dry pulverizer such as a jet mill], a method of manufacturing by a wet method (dispersing the powder of (a) in an organic solvent, and a known method such as a bead mill or a roll mill) A method of wet-grinding with a wet disperser, a method of spray-drying the solvent (S) solution of (a) with a spray dryer or the like, a method of supersaturating the solvent (S) solution of (a) by adding a poor solvent or cooling and precipitating, (A) Solvent (S) solution dispersed in water or organic solvent, (a) precursor polymerized in water by emulsion polymerization method, soap-free emulsion polymerization method, seed polymerization method, suspension polymerization method, etc. How to make Method] and the like to be polymerized by dispersion polymerization or the like in an organic solvent a precursor of (a). Further, after the fine particles (A ′) of the amorphous resin (a2) are synthesized by the above method, the crystalline resin (a1) is applied to the surface (A ′) by a known coating method, seed polymerization method, mechanochemical method, or the like. It may be formed. Among these, from the viewpoint of easy production of the fine particles (A), a wet production method is preferable, and a precipitation method, an emulsion polymerization method, and a dispersion polymerization are more preferable.

  The fine particles (A) may be used as they are, or have an adsorptivity to the resin particles (B), or modify the powder characteristics and electrical characteristics of the resin particles (C) obtained by the production method of the present invention. Therefore, the surface may be modified by, for example, surface treatment with a coupling agent such as silane, titanate, or aluminate, surface treatment with various surfactants, coating treatment with a polymer, or the like. It is preferable that either one of the fine particles (A) and the resin particles (B) has an acidic functional group on at least its surface, and the other has at least a basic functional group on its surface.

  The fine particles (A) and the resin particles (B) may have an acidic functional group or a basic functional group therein. Examples of the acidic functional group include a carboxylic acid group and a sulfonic acid group. Examples of basic functional groups include primary amino groups, secondary amino groups, and tertiary amino groups.

  The fine particles (A) and the resin particles (B) have an acidic functional group or a basic functional group as the crystalline resin (a1) or the resin (b) in order to impart at least an acidic functional group or a basic functional group to the surface thereof. You may use the resin which has, and in order to provide these functional groups to microparticles | fine-particles (A) and resin particle (B), you may surface-treat.

  Examples of the crystalline resin (a1) having an acidic functional group include an aliphatic polyester having an acid value and a monomer having an acidic functional group (for example, a carboxyl group-containing vinyl monomer and a sulfone group-containing vinyl monomer described later). Examples thereof include polymerized vinyl resins.

  Examples of the crystalline resin (a1) having a basic functional group include a vinyl resin obtained by copolymerizing a monomer having a basic functional group (for example, an amino group-containing vinyl monomer described later).

  Examples of the inorganic compound (a3) include diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, and samarium oxide. , Metal oxides such as lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy carbonate Metal carbonates such as calcium, light calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalicite, metal sulfates such as calcium sulfate, barium sulfate, gypsum fiber, silica, calcium silicate (wollastonite, zonotlite), kaolin , Kure , Talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, glass flakes and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphates such as tricalcium phosphate Metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, gold, silver, and other inorganic particles. Among these, silica and metal carbonate are preferable.

  The particle diameter of the fine particles (A) used in the production method of the present invention is smaller than the particle diameters of the resin particles (B) and the resin particles (C) to be formed. The value of the particle size ratio [volume average particle size of fine particles (A)] / [volume average particle size of resin particles (C) obtained by the production method of the present invention] is preferably 0.001 to 0.2, Preferably it is 0.002-0.1, Most preferably, it is 0.01-0.08. Within the above range, (A) is efficiently adsorbed on the surface of (B), so that the particle size distribution of (C) obtained becomes narrow.

  The volume average particle diameter of the fine particles (A) can be appropriately adjusted within the above range of the particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (C) having a desired particle diameter. The volume average particle diameter of (A) is generally preferably 0.0005 to 30 μm. More preferably, it is 0.01-20 micrometers, Most preferably, it is 0.04-10 micrometers. However, for example, when it is desired to obtain a resin particle (C) having a volume average particle diameter of 1 μm, it is preferably 0.0005 to 0.3 μm, particularly preferably in the range of 0.001 to 0.2 μm, and 10 μm resin particles ( When it is desired to obtain C), preferably 0.005 to 3 μm, particularly preferably 0.05 to 2 μm, and 100 μm when resin particles (C) are desired, preferably 0.05 to 30 μm, particularly preferably Is 0.1-20 μm. The volume average particle size is determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba Seisakusho), a laser type particle size distribution measuring device (for example, LA-920: manufactured by Horiba Seisakusho), Multisizer III (Beckman).・ Measured by Coulter, Inc.

  When forming the non-aqueous dispersion (X) of the resin particles (C1), the fine particles (A) may be directly mixed with other components such as the solvent (S) solution (L) of the resin (b). From the viewpoint of dispersibility of (A), a fine particle dispersion (P) in which (A) is dispersed in (N) from at least a part of the non-aqueous organic solvent (N) and the fine particles (A). And (P) is preferably mixed with other components.

  The non-aqueous organic solvent (N) used in the present invention is a solvent that is not miscible with water at an arbitrary ratio in the standard state (23 ° C., 0.1 MPa), and is a solvent of the resin (a1) or (a2) in the standard state ( N) A solvent having an insoluble content of 50% by weight or more is preferred. When the solvent (N) insoluble content is 50% by weight or more, the particle size distribution of the resin particles (C) becomes narrow. From this point and the dispersibility of the fine particles (A), preferred specific examples of the solvent (N) include aliphatic hydrocarbon solvents (decane, hexane, heptane, etc.) and ester solvents (ethyl acetate, butyl acetate, etc.). It is done.

  Fine particle dispersion (P) in which fine particles (A) are dispersed in a non-aqueous organic solvent (N) [If necessary, a solvent (S) other than (N) may be contained. Is not particularly limited, but as a specific example, a method of producing by wet in the solvent (N) [powder of the material (a) constituting the fine particles (A) in the solvent (N) A method of dispersing and wet-grinding with a known wet disperser such as a bead mill or a roll mill, a method of spraying and drying the solvent (S) solution of (a) with a spray dryer or the like, and then dispersing in the solvent (N), (a) A method of adding a poor solvent out of the solvent (N) to the solvent (S) solution to cause supersaturation and precipitation, a method of dispersing the solvent (S) solution in the solvent (N) in the poor solvent of the solvent (N), (a ) In a solvent (N) by emulsion polymerization, dispersion polymerization or the like]. Further, after the dispersion (P) of the fine particles (A ′) of the amorphous resin (a2) is synthesized by the above method, the crystalline resin (a1) is obtained by a known coating method, seed polymerization method, mechanochemical method, or the like. (A ') You may form on the surface. Among these, from the viewpoint of easy production of the fine particle dispersion (P), there are a method of dispersing the solvent (S) solution of (a) in the solvent (N), a method of precipitation, an emulsion polymerization method, and a dispersion polymerization method. More preferred are a method of dispersing the solvent (S) solution of (a) in the solvent (N), an emulsion polymerization method, and a dispersion polymerization method.

  Examples of the solvent (S) include ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvents (acetate ester, Pyruvate, 2-hydroxyisobutyrate, lactate, etc.), amide solvent (dimethylformamide, etc.), alcohol solvent (methanol, ethanol, isopropanol, fluorine-containing alcohol, etc.), aromatic hydrocarbon solvent (toluene, xylene, etc.) And aliphatic hydrocarbon solvents (hexane, heptane, octane, decane, etc.). A mixed solvent of two or more of these solvents or a mixed solvent of these organic solvents and water can also be used.

  The weight ratio (% by weight) of the fine particles (A) and the non-aqueous organic solvent (N) in the fine particle dispersion (P) is not particularly limited, but the fine particles (A) are 60 or less with respect to the solvent (N). Is more preferable, and 0.1 to 50 is more preferable. Within this range, the fine particles (A) can be efficiently introduced into (N).

  In the production method of the present invention, as the resin (b), the thermoplastic resin (b1) or the resin (b2) obtained by finely crosslinking the thermoplastic resin, and the thermoplastic resin as a sea component and the cured resin as an island component are used. A polymer blend (b3) is mentioned, and 2 or more types may be used in combination. Examples of the thermoplastic resin (b1) include vinyl resins, polyurethane resins, epoxy resins, and polyester resins. Among these, a vinyl resin, a polyurethane resin, a polyester resin, and a combination thereof are preferable from the viewpoint that a dispersion of fine spherical resin particles is easily obtained. Further, (b1) may be an amorphous resin (b11) or a crystalline resin (b12).

When the thermoplastic resin (b1) is an amorphous resin (b11), the vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, α-olefins other than these; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7 -Octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as (di) cyclopentadiene; terpenes such as pinene.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, such as α-methylstyrene, 2,4-dimethylstyrene and the like; and vinylnaphthalene.
(2) Carboxyl group-containing vinyl monomers and salts thereof: unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides and monoalkyl (1 to 24 carbon atoms) esters thereof such as (meth) acrylic Acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, Carboxyl group-containing vinyl monomers such as cinnamic acid.
(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene Sulfonic acid and the like; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, and sulfuric acid ester or sulfonic acid group-containing vinyl monomer; and salts thereof.

(4) Phosphoric acid group-containing vinyl monomer and its salt: (meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoester, for example, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, ( (Meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2-acryloyloxyethylphosphonic acid. Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.
(5) Hydroxyl group-containing vinyl monomer: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, 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-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, etc.
(6-2) Amide group-containing vinyl monomer: (meth) acrylamide, N-methyl (meth) acrylamide, etc.
(6-3) Nitrile group-containing vinyl monomer: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc.
(6-4) Quaternary ammonium cation group-containing vinyl monomers: tertiary amines such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized products of group-containing vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate), etc.
(6-5) Nitro group-containing vinyl monomer: nitrostyrene and the like.
(7) Epoxy group-containing vinyl monomer: Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.
(8) Halogen element-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, 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 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or Alicyclic groups), dialkyl maleates (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes Monomers [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (Mn300) Mono (meth) acrylate, Polypropylene glycol (Mn500) monoacrylate Methyl alcohol ethylene oxide (hereinafter, ethylene oxide is referred to as EO) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [polyhydric alcohol Poly (meth) acrylates: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. ]etc,
(9-2) Vinyl (thio) ether, such as vinyl methyl ether,
(9-3) Vinyl ketones such as vinyl methyl ketone.
(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

  Examples of the vinyl monomer copolymer include polymers obtained by copolymerizing any of the above monomers (1) to (10) at an arbitrary ratio. For example, styrene- (meth) acrylate copolymer, styrene -Butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meta ) Acrylic acid-divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

Examples of polyester resins include polycondensates of polyols and polycarboxylic acids (including acid anhydrides and lower alkyl esters thereof). Examples of the polyol include a diol (11) and a trivalent or higher polyol (12), and examples of the polycarboxylic acid include a dicarboxylic acid (13) and a trivalent or higher polycarboxylic acid (14).
The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜1 / 1, particularly preferably 1.3 / 1 to 1.02 / 1.

  Diol (11) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) Alkylene oxide (hereinafter referred to as AO) [EO, propylene oxide (hereinafter referred to as PO), butylene oxide (hereinafter referred to as BO), etc. Additives; AO (EO, PO, BO, etc.) adducts of the above bisphenols; Other examples include polylactone diols (poly ε-caprolactone diols), polybutadiene diols, and the like. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and AO adducts of bisphenols, and particularly preferred are AO adducts of bisphenols and combinations thereof with alkylene glycols having 2 to 12 carbon atoms. It is.

  Examples of the trihydric or higher polyol (12) include 3 to 8 or higher polyhydric aliphatic alcohols (such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trisphenols (such as trisphenol PA) ) AO adducts; AO adducts of novolak resins (phenol novolac, cresol novolak, etc.), acrylic polyols [such as copolymers of hydroxyethyl (meth) acrylate and other vinyl monomers, etc.].

  Dicarboxylic acids (13) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.) Branched alkylene dicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl) Succinic acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher (3 to 6 or higher) polycarboxylic acid (14) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

  As the dicarboxylic acid (13) or the trivalent or higher polycarboxylic acid (14), acid anhydrides or lower alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  As the polyurethane resin, polyisocyanate (15) and active hydrogen group-containing compound (D) {water, polyol [the diol (11) and trivalent or higher polyol (12)], dicarboxylic acid (13), trivalent or higher Polycarboxylic acid (14), polyamine (16), polythiol (17) and the like} and the like.

As polyisocyanate (15), C6-C20 aromatic polyisocyanate, C2-C18 aliphatic polyisocyanate, C4-C15 alicyclic (excluding carbon in NCO group, the same shall apply hereinafter) Formula polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, Oxazolidone group-containing modified products) and mixtures of two or more thereof.
Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4′- and / or Or 4,4'-diphenylmethane diisocyanate (MDI) etc. are mentioned.
Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and the like. .
Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.
Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product. Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified polyisocyanates such as urethane-modified TDI, and mixtures of two or more of these [for example, modified MDI and urethane-modified TDI (Combined use with an isocyanate-containing prepolymer)] is included.
Of these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms, and alicyclic polyisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, hydrogenated MDI, and IPDI.

The following are mentioned as an example of a polyamine (16).
Aliphatic polyamines (C2 to C18):
[1] Aliphatic polyamine {C2-C6 alkylenediamine (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, etc.}}
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substituted products [dialkyl (C1-C3) aminopropylamine, etc.]
[3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (such as xylylenediamine, tetrachloro-p-xylylenediamine),
-Alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.

Aromatic polyamines (C6-C20):
[1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine and the like; nucleus-substituted alkyl group [C1-C4 alkyl such as methyl, ethyl, n- and i-propyl, butyl, etc.] Aromatic polyamines such as 2,4- and 2,6-tolylenediamine etc.), and mixtures of various proportions of these isomers [2] nuclear substituted electron withdrawing groups (Cl, Br, I, Aromatic polyamines having halogens such as F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc. [methylene bis-o-chloroaniline, etc.]
[3] Aromatic polyamine having a secondary amino group [Any or all of —NH ₂ of the aromatic polyamines (4) to (6) above is —NH—R ′ (R ′ is a lower group such as methyl, ethyl, etc.) Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Polyamide polyamine: low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylene diamine, polyalkylene polyamine, etc.)
-Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

  Examples of polythiol (17) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol and the like.

  Examples of the epoxy resin include a ring-opening polymer of polyepoxide (18), polyepoxide (18) and active hydrogen group-containing compound (D) {water, polyol [the diol (11) and a trivalent or higher valent polyol (12)], dicarboxylic acid. Acid (13), trivalent or higher polycarboxylic acid (14), polyamine (16), polythiol (17), etc.} polyaddition product, or polyepoxide (18) and dicarboxylic acid (13) or higher polyvalent polyvalent acid. Examples include cured products of carboxylic acid (14) with acid anhydrides.

  The polyepoxide (18) is not particularly limited as long as it has two or more epoxy groups in the molecule. What has preferable 2-6 epoxy groups in a molecule | numerator from a viewpoint of the mechanical property of hardened | cured material as a preferable polyepoxide (18). The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide (18) is preferably 65 to 1000, and more preferably 90 to 500. When the epoxy equivalent is 1000 or less, the crosslinked structure becomes dense and the physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved. On the other hand, those having an epoxy equivalent of 65 or more are synthesized. Easy.

  Examples of the polyepoxide (18) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Examples of the aromatic polyepoxy compounds include glycidyl ethers and glycidyl ethers of polyhydric phenols, glycidyl aromatic polyamines, and glycidylates of aminophenols. Examples of the glycidyl ether of polyhydric phenol include bisphenol F diglycidyl ether and bisphenol A diglycidyl ether. Examples of the glycidyl ester of polyhydric phenol include diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate. Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline, N, N, N ′, N′-tetraglycidylxylylenediamine, N, N, N ′, N′-tetraglycidyldiphenylmethanediamine and the like. Further, as the aromatic polyepoxy compound, triglycidyl ether of P-aminophenol, tolylene diisocyanate or diglycidyl urethane compound obtained by addition reaction of diphenylmethane diisocyanate and glycidol, obtained by reacting polyol with the reaction product. Also included are glycidyl group-containing polyurethane (pre) polymers and diglycidyl ethers of AO (EO or PO) adducts of bisphenol A. Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine. Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide. The alicyclic polyepoxy compound also includes a nuclear hydrogenated product of the aromatic polyepoxide compound. Examples of the aliphatic polyepoxy compound 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 and propylene glycol diglycidyl ether. Examples of polyglycidyl ester of polyvalent fatty acid include diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate and the like. Examples of the glycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine. The aliphatic polyepoxy compound also includes a (co) polymer of diglycidyl ether and glycidyl (meth) acrylate. Of these, preferred are aliphatic polyepoxy compounds and aromatic polyepoxy compounds. Two or more polyepoxides may be used in combination.

The thermoplastic resin (b1) may be a crystalline resin (b12) other than the amorphous resin (b11), and (b12) is preferred from the viewpoint of low-temperature fixability.
In the case of the crystalline resin (b12), the melting point is preferably in the range of 20 to 100 ° C, more preferably 40 to 70 ° C, from the viewpoint of heat resistant storage stability.

  As the crystalline resin (b12), a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin, a polyether resin, a vinyl resin and a composite resin thereof are preferable, and a linear polyester resin and a composite resin including the same are particularly preferable.

The crystalline polyester resin used as (b12) is preferably a polycondensed polyester resin synthesized from an alcohol (diol) component and an acid (dicarboxylic acid) component from the viewpoint of crystallinity. However, a tri- or higher functional alcohol component or acid component may be used as necessary.
As the crystalline polyester resin, in addition to the polycondensation polyester resin, a lactone ring-opening polymer and polyhydroxycarboxylic acid are also preferable.
Examples of the crystalline polyurethane resin include a polyurethane resin synthesized from an alcohol (diol) component and an isocyanate (diisocyanate) component. However, a tri- or higher functional alcohol component or isocyanate component may be used as necessary.
Examples of the crystalline polyamide resin include a polyamide resin synthesized from an amine (diamine) component and an acid (dicarboxylic acid) component. However, a trifunctional or higher functional amine component or acid component may be used as necessary.
Examples of the crystalline polyurea resin include a polyurea resin synthesized from an amine (diamine) component and an isocyanate (diisocyanate) component. However, a trifunctional or higher functional amine component or isocyanate component may be used as necessary.
In the following description, first, a diol component, a dicarboxylic acid component, a diisocyanate component, and a diamine component (each having three or more functional groups) used for the crystalline polycondensation polyester resin, the crystalline polyurethane resin, the crystalline polyamide resin, and the crystalline polyurea resin. Each of them).

The alcohol (diol) component is preferably an aliphatic diol and preferably having 2 to 36 carbon atoms. A linear aliphatic diol is more preferred.
When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that the storage stability and the low-temperature fixability may be deteriorated. On the other hand, when the number of carbon atoms exceeds 36, it may be difficult to obtain practical materials.

  The content of the linear aliphatic diol in the diol component is preferably 80 mol% or more of the diol component used, and more preferably 90 mol% or more. If it is 80 mol% or more, the crystallinity of the polyester resin is improved and the melting point is increased, so that the storage stability and the low-temperature fixability are improved.

  Specific examples of the linear aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

Other diols used as necessary include those other than those described above as the diol (11).
Furthermore, you may use the diol which has another functional group. Examples of the diol having a functional group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Diols having a carboxyl group include dialkylol alkanoic acids [things of C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethylol octanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or PO). AO addition mole number 1 to 6): for example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2 -Hydroxyethyl) phosphate and the like.
Examples of the neutralizing base of the diol having these neutralizing bases include tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

Examples of the trivalent or higher polyol used as necessary include those similar to the above trivalent or higher polyol (12).
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

Among the acid (dicarboxylic acid) components, examples of the dicarboxylic acid include those similar to the dicarboxylic acid (13).
Examples of the trivalent or higher polycarboxylic acid used as necessary include the same as the trivalent or higher polycarboxylic acid (14).

Among these acid (dicarboxylic acid) components, aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and the aliphatic dicarboxylic acids are more preferably linear carboxylic acids. It is particularly preferred to use an aliphatic dicarboxylic acid (especially a straight-chain carboxylic acid) alone, but an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid, and lower thereof) together with the aliphatic dicarboxylic acid. Alkyl esters are preferred, and those obtained by copolymerization are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.
Examples of the dicarboxylic acid component include, but are not limited to, the above carboxylic acids. Of these, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid are preferable in consideration of crystallinity and availability.

Examples of the isocyanate (diisocyanate) component include those similar to the polyisocyanate (15).
Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are TDI, MDI, HDI, water. Attached MDI and IPDI.

  Examples of the amine (diamine) component include those similar to the polyamine (16).

Among the polyester resins used as the crystalline resin (b12), the lactone ring-opening polymer is, for example, a monolactone having 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. A lactone such as (one ester group in the ring) can be obtained by ring-opening polymerization using a catalyst such as a metal oxide or an organometallic compound. Of these, preferred lactone is ε-caprolactone from the viewpoint of crystallinity.
When glycol is used as the initiator, a lactone ring-opening polymer having a hydroxyl group at the terminal is obtained. For example, it can be obtained by reacting the lactone with the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, and the like are common, added at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C., preferably in an inert atmosphere. By polymerizing, a lactone ring-opening polymer can be obtained. The lactone ring-opening polymer may be modified at its terminal so as to be, for example, a carboxyl group. The lactone ring-opening polymer is a thermoplastic aliphatic polyester resin having high crystallinity. A commercially available product may be used as the lactone ring-opening polymer, for example, H1P, H4, H5, H7 of Daicel Corporation's PLACEL series (all melting points = about 60 ° C., glass transition temperature (Tg) = High crystalline polycaprolactone at about −60 ° C.).

Among crystalline polyester resins, polyhydroxycarboxylic acid can be obtained by directly dehydrating and condensing hydroxycarboxylic acid such as glycolic acid and lactic acid (L-form, D-form, racemic form), but glycolide, lactide (L-form, A cyclic ester having 4 to 12 carbon atoms (2 to 3 ester groups in the ring) corresponding to a dehydration condensate between two or three molecules of a hydroxycarboxylic acid such as D-form or racemate) as a metal oxide or organic Ring-opening polymerization using a catalyst such as a metal compound is preferable from the viewpoint of adjusting the molecular weight. Among these, preferred cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity.
When glycol is used as an initiator, a polyhydroxycarboxylic acid skeleton having a hydroxyl group at the terminal is obtained. For example, the cyclic ester can be obtained by reacting the diol component such as ethylene glycol or diethylene glycol in the presence of a catalyst. As the catalyst, an organic tin compound, an organic titanium compound, an organic tin halide compound, and the like are common, added at a rate of about 0.1 to 5000 ppm, and preferably at 100 to 230 ° C., preferably in an inert atmosphere. A polyhydroxycarboxylic acid can be obtained by polymerization. The polyhydroxycarboxylic acid may have a terminal modified so as to be, for example, a carboxyl group.

Among the crystalline resins (b12), examples of the polyether resins include crystalline polyoxyalkylene polyols.
The method for producing the crystalline polyoxyalkylene polyol is not particularly limited, and any conventionally known method may be used.
For example, a method of ring-opening polymerization of a chiral AO with a catalyst usually used in polymerization of AO (for example, Journal of the American Chemical Society, 1956, Vol. 78, No. 18, p. 4787-4792) And a method of ring-opening polymerization of inexpensive racemic AO using a sterically bulky complex having a special chemical structure as a catalyst.
As a method using a special complex, a method in which a compound obtained by contacting a lanthanoid complex and an organoaluminum is used as a catalyst (for example, described in JP-A No. 11-12353), or bimetal μ-oxoalkoxide and a hydroxyl compound are previously used. A reaction method (for example, described in JP-T-2001-521957) is known.
Further, as a method for obtaining a polyoxyalkylene polyol having a very high isotacticity, a method using a salen complex as a catalyst (for example, Journal of the American Chemical Society, 2005, Vol. 127, No. 33, p. 11566-). 11567) is known.

For example, when a chiral AO is used and glycol or water is used as an initiator during the ring-opening polymerization, a polyoxyalkylene glycol having a hydroxyl group at the terminal and having an isotacticity of 50% or more is obtained. The polyoxyalkylene glycol having an isotacticity of 50% or more may be modified such that its terminal is, for example, a carboxyl group. If the isotacticity is 50% or more, the crystallinity is usually obtained.
Examples of the glycol include the diol component, and examples of the carboxylic acid used for carboxy modification include the dicarboxylic acid component.

As AO used for manufacture of crystalline polyoxyalkylene polyol, a C3-C9 thing is mentioned, For example, the following compounds are mentioned.
C3 AO [PO, 1-chlorooxetane, 2-chlorooxetane, 1,2-dichlorooxetane, epichlorohydrin, epibromohydrin]; C4 AO [1,2-BO, methylglycidyl ether]; C5 AO [1,2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide]; C6 AO [cyclohexene oxide, 1,2-hexylene oxide , 3-methyl-1,2-pentylene oxide, 2,3-hexylene oxide, 4-methyl-2,3-pentylene oxide, allyl glycidyl ether]; AO [1,2-heptyl having 7 carbon atoms] Ren oxide]; AO having 8 carbon atoms [styrene oxide]; AO having 9 carbon atoms [phenyl glycidyl ether] and the like.

Of these AOs, PO, 1,2-BO, styrene oxide and cyclohexene oxide are preferred. More preferred are PO, 1,2-BO and cyclohexene oxide. From the viewpoint of the polymerization rate, PO is most preferable.
These AOs can be used alone or in combination of two or more.

  The isotacticity of the crystalline polyoxyalkylene polyol is preferably 70% or more, more preferably 80% or more, more preferably 90% or more from the viewpoint of high sharp melt property and blocking resistance of the obtained crystalline polyether resin. Most preferably, it is 95% or more.

Isotacticity is described in Macromolecules, vol. 35, no. 6, 2389-2392 (2002), and can be calculated as follows.
About 30 mg of a measurement sample is weighed into a ¹³ C-NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved to obtain an analysis sample. Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent capable of dissolving the sample is appropriately selected.

¹³ C-NMR signals derived from three types of methine groups are syndiotactic value (S) around 75.1 ppm, heterotactic value (H) around 75.3 ppm, and isotactic value (I) 75.5 ppm, respectively. Observed nearby. Isotacticity is calculated by the following calculation formula (1).
Isotacticity (%) = [I / (I + S + H)] × 100 (1)
Where I is the integrated value of the isotactic signal; S is the integrated value of the syndiotactic signal; and H is the integrated value of the heterotactic signal.

  Among the crystalline resins (b12), as the vinyl resin, those having a vinyl monomer (m) having a crystalline group and, if necessary, a vinyl monomer (n) having no crystalline group as structural units are preferable.

As the vinyl monomer (m), a linear alkyl (meth) acrylate (m1) having 12 to 50 carbon atoms in the alkyl group (the linear alkyl group having 12 to 50 carbon atoms is a crystalline group), and a vinyl resin And vinyl monomer (m2) having a unit of the crystalline resin (b12) other than the above.
As a crystalline vinyl resin, what contains linear alkyl (meth) acrylate (m1) whose carbon number of an alkyl group is 12-50 (preferably 16-30) as a vinyl monomer (m) is further more preferable.
Examples of (m1) include linear lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate, each of which is linear. It is done.

  In the vinyl monomer (m2) having a unit of the crystalline resin (b12), the method of introducing the unit of the crystalline resin (b12) into the vinyl monomer takes into account the reactivity of each terminal functional group and the binder ( (Coupling agent) is used or not, and when it is used, the binder suitable for the terminal functional group is selected, the crystalline resin (b12) and the vinyl monomer are bonded, and the unit of (b12) The vinyl monomer (m2) having

  When a binder is not used when preparing the vinyl monomer (m2) having a unit of the crystalline resin (b12), the terminal functional group of the crystalline resin (b12) and the terminal functional group of the vinyl monomer are heated and reduced in pressure as necessary. Advance the reaction. Especially when the terminal functional group is a reaction between a carboxyl group and a hydroxyl group, or a reaction between a carboxyl group and an amino group, if the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high, Progresses smoothly. The reaction temperature is preferably 180 ° C to 230 ° C.

When using a binder, various binders can be used according to the kind of the functional group at the terminal.
Specific examples of the binder and a method for producing the vinyl monomer (m2) using the binder include the same methods as the block resin production method described later.

  The vinyl monomer (n) having no crystalline group is not particularly limited, and a vinyl monomer (n1) having a molecular weight of 1000 or less, which is usually used for producing a vinyl resin, other than the vinyl monomer (m) having a crystalline group. And a vinyl monomer (n2) having a unit of the non-crystalline resin (b11).

  Examples of the vinyl monomer (n1) include styrenes, (meth) acrylic monomers, carboxyl group-containing vinyl monomers, other vinyl ester monomers, and aliphatic hydrocarbon vinyl monomers. Also good.

  Examples of styrenes include styrene and alkyl styrene having an alkyl group having 1 to 3 carbon atoms [for example, α-methyl styrene, p-methyl styrene], and styrene is preferable.

(Meth) acrylic monomers include alkyl (meth) acrylates having 1 to 11 carbon atoms in the alkyl group and branched alkyl (meth) acrylates having 12 to 18 carbon atoms in the alkyl group [for example, methyl (meth) acrylate, ethyl (Meth) acrylates, butyl (meth) acrylates, 2-ethylhexyl (meth) acrylates], alkyl groups having 1 to 11 carbon atoms hydroxylalkyl (meth) acrylates [for example, hydroxylethyl (meth) acrylates], alkyl group carbons Alkylamino group-containing (meth) acrylates having a number of 1 to 11 [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate], and nitrile group-containing vinyl monomers [for example, acrylonitrile, methacrylonitrile And the like.
Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids [having 3 to 15 carbon atoms such as (meth) acrylic acid, crotonic acid and cinnamic acid], dicarboxylic acids [having 4 to 15 carbon atoms such as (anhydrous) maleic acid, Fumaric acid, itaconic acid, citraconic acid], dicarboxylic acid monoester [monoalkyl (carbon number 1 to 18) ester of the above dicarboxylic acid, for example, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, Citraconic acid monoalkyl ester] and the like.

Other vinyl ester monomers include aliphatic vinyl esters [4 to 15 carbon atoms, such as vinyl acetate, vinyl propionate, isopropenyl acetate], unsaturated carboxylic acid polyvalent (2 to 3 or more) alcohol esters [ C8-50, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6 hexanediol diacrylate, Polyethylene glycol di (meth) acrylate], aromatic vinyl ester [carbon number 9 to 15, for example, methyl-4-vinylbenzoate] and the like.
Aliphatic hydrocarbon vinyl monomers include olefins [2-10 carbon atoms such as ethylene, propylene, butene, octene], dienes (4-10 carbon atoms such as butadiene, isoprene, 1,6-hexadiene) and the like. Can be mentioned.
Of these (n1), (meth) acrylic monomers and carboxyl group-containing vinyl monomers are preferred.

  In the vinyl monomer (n2) having the unit of the amorphous resin (b11), the method of introducing the unit of the amorphous resin (b11) into the vinyl monomer is the vinyl monomer having the unit of the crystalline resin (b12). In (m2), the same method as the method of introducing the unit (b12) into the vinyl monomer can be used.

The proportion of the structural unit of the vinyl monomer (m) having a crystalline group in the crystalline vinyl resin is preferably 30% by weight or more, more preferably 35 to 95% by weight, particularly preferably 40 to 90% by weight. It is. Within this range, the crystallinity of the vinyl resin is not impaired and the heat resistant storage stability is good. The content of the linear alkyl (meth) acrylate (m1) having 12 to 50 carbon atoms in the alkyl group in (m) is preferably 30 to 100% by weight, more preferably 40 to 80% by weight.
A crystalline vinyl resin is obtained by polymerizing these vinyl monomers by a known method.

  Further, the crystalline resin (b12) is composed of one or more crystalline parts (p) made of the crystalline resin (b12) and one or more amorphous parts (q) made of the amorphous resin (b11). It may be a block resin having

For the block resin composed of the crystalline part (p) and the non-crystalline part (q), the use or non-use of the binder is selected in consideration of the reactivity of each terminal functional group. Can select a binder type suitable for the terminal functional group and bond (p) and (q) to form a block resin.
When the binder is not used, the reaction between the terminal functional group of the resin forming (p) and the terminal functional group of the resin forming (q) is advanced while heating and decompressing as necessary. In particular, in the case of a reaction between an acid and an alcohol or a reaction between an acid and an amine, the reaction proceeds smoothly when the acid value of one resin is high and the hydroxyl value or amine value of the other resin is high. The reaction temperature is preferably 180 ° C to 230 ° C.
When a binder is used, various binders can be used. It can be obtained by performing a dehydration reaction or an addition reaction using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, acid anhydride or the like.
Examples of the polyvalent carboxylic acid and acid anhydride include those similar to the dicarboxylic acid component. Examples of the polyhydric alcohol include those similar to the diol component. Examples of the polyvalent isocyanate include those similar to the diisocyanate component. As the polyfunctional epoxy, bisphenol A type and -F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, diglycidyl ethers of AO adducts of bisphenol A or -F, Diglycidyl ether and triol of diglycidyl ether and diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) of AO adduct of hydrogenated bisphenol A Propane di and / or triglycidyl ether, pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta And / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol-added glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, polybutadiene diglycidyl ether, etc. Is mentioned.

Among the methods for bonding (p) and (q), as examples of dehydration reaction, both the crystalline part (p) and the non-crystalline part (q) are alcohol resins at both ends, and these are combined with a binder (for example, polyvalent). Reaction which couple | bonds with carboxylic acid) is mentioned. In this case, for example, the reaction is performed at a reaction temperature of 180 ° C. to 230 ° C. in the absence of a solvent to obtain a block resin.
Examples of the addition reaction include a resin having a hydroxyl group at both ends of the crystalline part (p) and the non-crystalline part (q), a reaction in which these are bonded with a binder (for example, a polyvalent isocyanate), and crystalline In the case where one of the part (p) and the non-crystalline part (q) is a resin having a hydroxyl group at the terminal and the other is a resin having an isocyanate group at the terminal, there is a reaction of bonding them without using a binder. . In this case, for example, both the crystalline part (p) and the non-crystalline part (q) are dissolved in a soluble solvent (S), and if necessary, a binder is added, and the reaction temperature is 80 ° C. to 150 ° C. To give a block resin.

  When the crystalline resin (b12) is a block resin composed of a crystalline part (p) and an amorphous part (q), the proportion of the crystalline part (p) in (b12) is 50 % By weight or more is preferable, more preferably 55 to 96% by weight, and still more preferably 60 to 90% by weight. When the proportion of (p) is 50% by weight or more, the crystallinity of (b12) is not impaired, and the low-temperature fixability is better.

  The resin (b2) obtained by microcrosslinking a thermoplastic resin refers to a resin in which a crosslinked structure is introduced and the Tg of the resin (b) is 20 to 200 ° C. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. As a specific example, for example, when a polyester is selected as the resin (b2), a crosslinked structure is introduced by using a polyol or polycarboxylic acid at the time of polymerization, or a compound having a functional group number of 3 or more in both. be able to. When a vinyl resin is selected as the resin (b2), a crosslinked structure can be introduced by adding a monomer having two or more double bonds during polymerization.

  The polymer blend (b3) having a thermoplastic resin as a sea component and a cured resin as an island component has a Tg of 20 to 200 ° C. and a softening start temperature of 40 to 220 ° C., specifically vinyl resin and polyester Resins, polyurethane resins, epoxy resins and mixtures thereof.

The number average molecular weight (Mn) by GPC of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000, solubility parameter [SP value, (cal / cm ³ ) ^1/2 ]. Is preferably 7-18, more preferably 8-14. Moreover, when it is desired to modify the thermal characteristics of the resin particles (C) obtained by the production method of the present invention, the resin (b2) or the resin (b3) may be used.
The SP value is represented by the square root of the ratio between the cohesive energy density and the molecular volume, as shown below.
SP = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

  The glass transition temperature (Tg) when the resin (b) is other than the crystalline resin (b12) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 150 ° C. Above 20 ° C, the storage stability of the particles is good. In addition, Tg in this invention is a value calculated | required from DSC measurement.

  The softening start temperature of the resin (b) is preferably 40 ° C to 220 ° C, more preferably 50 ° C to 200 ° C. Above 40 ° C, long-term storage is good. Below 220 ° C., the fixing temperature does not increase and there is no problem. In addition, the softening start temperature in this invention is a value calculated | required from a flow tester measurement.

In the present invention, the solvent solution of the precursor (b0) of the resin (b) is used alone in addition to the method of using the solvent solution of the resin (b) alone as the solvent (S) solution (L) of the resin (b). Or a method using a mixture of the above two. The solvent (S) solution of the precursor (b0) of the resin (b) can be suitably used particularly when it is desired to introduce a crosslinking component or a high cohesion force component into the resin particles (C).
In the present invention, the resin (b) is used in a sense including the precursor (b0) of the resin (b).

  The precursor (b0) is not particularly limited as long as it can be converted into the resin (b) by a chemical reaction. For example, when the resin (b) is a vinyl resin, (b0) is the vinyl monomer described above. When the resin (b) is a condensation resin (for example, polyurethane resin, epoxy resin, polyester resin) (b0) is a reactive group. A combination of the prepolymer (α) and the curing agent (β) is exemplified.

As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). The following (1), (2), etc. are mentioned as a combination of the reactive group which a reactive group containing prepolymer ((alpha)) and a hardening | curing agent ((beta)).
(1): The reactive group of the reactive group-containing 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). There is a combination.
(2) The reactive group-containing prepolymer (α) has an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. combination.
In the combination (1), the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]; aliphatic alcohols having 1 to 20 carbon atoms [ethanol, methanol, octanol, etc.]; phenols [phenol, m-cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] Etc.]; basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]; and mixtures of two or more thereof. That. Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Among these, (αx), (αy) and (αz) are preferable, and (αx) and (αz) are particularly preferable. Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like. Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ring-opening polymerization products of ε-caprolactone), and the like. Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin. Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

  As a method of incorporating a reactive group into polyester (αx), epoxy resin (αy), polyurethane (αz), etc., (1): by using one of two or more components in excess, A method of leaving a functional group at the end, (2): by using one of two or more constituent components in excess, the functional group of the constituent component can be left at the end and further reacted with the remaining functional group Examples include a method of reacting a compound containing a functional group and a reactive group. In the above method (1), a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of the polyol (1) and the polycarboxylic acid (2) is the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ] Is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed. In the said method (2), an isocyanate group containing prepolymer is obtained by making polyisocyanate react with the preprimer obtained by the said method (1), and blocked isocyanate group containing prepolymer is made to react with blocked polyisocyanate. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride. The amount of the compound containing a functional group and a reactive group is, for example, when an isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The molar ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight (measured by GPC, hereinafter abbreviated as Mw) of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 4,000. ~ 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that a resin particle (C) having a sharp particle size distribution can be obtained.

  Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are (β1a), (β1b) and (β1d), more preferred are (β1a) and (β1d), and particularly preferred are blocked polyamines and (β1d ). (Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and mixtures thereof.

  An example of the case where (β1a) is a polyamine blocked with a detachable compound is obtained from the polyamine (16) and a ketone having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Examples include ketimine compounds, aldimine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde), enamine compounds, and oxazolidine compounds.

  Examples of the polyol (β1b) are the same as the diol (11) and the polyol (12). Diol (11) alone or a mixture of diol (11) and a small amount of polyol (12) is preferred. 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 a reaction terminator in combination with (β1) at a certain ratio, it is possible to adjust (b) to a predetermined molecular weight. As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) And phenol; monomercaptan (such as butyl mercaptan and lauryl mercaptan); monoisocyanate (such as lauryl isocyanate and phenyl isocyanate); monoepoxide (such as butyl glycidyl ether) and the like.

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination (2), an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred. Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with an active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polyanhydride (β2d), and polyacid halide (β2e). It is done. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

  Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same. Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (18), and preferred ones are also the same.

  Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred. Examples of the dicarboxylic acid (β2c-1) include the same dicarboxylic acid (13), and examples of the polycarboxylic acid include those similar to the polycarboxylic acid (14), and preferable ones are also the same.

  Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride. Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide, acid iodide) of the above (β2c). Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.

  When a combination of a prepolymer (α) having a reactive group and a curing agent (β) is used as the precursor (b0), (b0) is reacted during the production of the non-aqueous dispersion (X) of the resin particles (C1). The method for preparing the resin (b) is not particularly limited, but (α) and (β) are mixed immediately before mixing the non-aqueous organic solvent (N) and the solvent (S) solution (L) of (b0). The method of reacting simultaneously with mixing is preferred. Although reaction time is selected by the reactivity by the structure of the reactive group which prepolymer ((alpha)) has, and the hardening | curing agent ((beta)) combination, Preferably it is 5 minutes-24 hours. The reaction may be completed in (X) before depressurization, or may be allowed to react to some extent in (X), depressurized and (C) is taken out, and then aged in a thermostatic bath or the like. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate in the case of reaction of an isocyanate and an active hydrogen compound. The reaction temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

  The resin (b) obtained by reacting the precursor (b0) composed of the reactive group-containing prepolymer (α) and the curing agent (β) is a constituent component of the resin particles (B) and the resin particles (C). The Mw of the resin (b) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3,000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000 to 5,000. One million.

  In addition, a reactive group-containing prepolymer (α) and a polymer that does not react with the curing agent (β) during reaction of the reactive group-containing prepolymer (α) with the curing agent (β) [so-called dead polymer] It can also be contained. In this case, (b) is a mixture of a resin obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) and an unreacted resin (dead polymer).

  The resin (b) may use any number of the above-mentioned resins, but from the viewpoint of productivity and low-temperature fixability, it is preferable that the crystalline resin (b12) is included as at least one kind in (b). . When the solvent (S) is removed from the resin particles (C1) by using the crystalline resin, the solvent (S) can be easily removed more efficiently. When the crystalline resin (b12) is contained in the resin (b), sharp melting will improve the low-temperature fixability, and after fixing when used in an electrophotographic toner, the melting point of the crystalline resin (b12) or less. The image stability at this temperature is improved.

Examples of the solvent (S) used in the solution (L) in which the resin (b) is dissolved include those described above.
Among them, from the viewpoint of ease of particle formation, as a single solvent, cyclic ether, pyruvate ester, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, 2-hydroxyisobutyrate ester, lactate ester, and fluorine Containing alcohols and mixed solvents are preferred.
More preferably, from the viewpoint of solvent removal, a mixed solvent (especially, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, and a mixed solvent of acetone and water) is preferable.

In the present invention, a solvent (S) solution (L) of the resin (b) is used. In this solvent (S), the solvent (S1) of the resin (b) in the standard state (23 ° C., 0.1 MPa). It is preferable to use a solvent (S1) having an insoluble content of 20% by weight or less. The solvent (S1) is a good solvent for the resin (b). When the (S1) insoluble content of (b) is 20% by weight or less, the particle size distribution of the resin particles (C) becomes sharp. The insoluble content of the solvent (S1) is preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 0% by weight.
In addition, the preferable range of the insoluble part with respect to the whole solvent (S) of resin (b) is the same as that of the said (S1) insoluble part.

The solvent (S) insoluble content of the resin (b) in the standard state (23 ° C., 0.1 MPa) is the weight of the insoluble content of the resin (b) with respect to the solvent (S) measured by the following method. Defined by weight percent divided by the sample weight of b).
About 0.5 g of resin (b) sample is precisely weighed into a 200 ml stoppered Meyer flask, 50 ml of solvent (S) is added, and the mixture is stirred and refluxed for 3 hours. Filter. The weight of the insoluble matter in the solvent (S) is the weight after the resin content on the filter is dried under reduced pressure at 80 ° C. for 3 hours.
In the case where the precursor (b0) of the resin (b) is a liquid, the weight of the insoluble component in the solvent (S) is calculated by the following method.
Add 50 ml of solvent (S) to the flask and stir with a magnetic stirrer. When the precursor (b0) of the resin (b) is dropped therein and the addition amount when the transmittance becomes 50% or less is W, the weight of the insoluble matter with respect to the solvent (S) is (0.5-W). ).

Specifically, the solvent (S1) is appropriately selected depending on the composition of the resin (b), and examples thereof include the following.
When the resin (b) is a polyester resin or a modified polyester resin, a ketone solvent (acetone, methyl ethyl ketone, etc.), an ester solvent (ethyl acetate, butyl acetate, etc.), an ether solvent (tetrahydrofuran, diethyl ether, etc.), an amide type Examples include solvents (dimethylformamide, dimethylacetamide, etc.) and aromatic hydrocarbon solvents (toluene, xylene, etc.).
When the resin (b) is a polyurethane resin or a modified polyurethane resin, examples include amide solvents (dimethylformamide, dimethylacetamide, etc.), ether solvents (tetrahydrofuran, diethyl ether, etc.), and ketone solvents (acetone, methyl ethyl ketone, etc.). .
When the resin (b) is an epoxy resin or a modified epoxy resin, ketone solvents (acetone, methyl ethyl ketone, etc.) and amide solvents (dimethylformamide, dimethylacetamide, etc.) can be mentioned.
When the resin (b) is a vinyl resin or a modified vinyl resin, a ketone solvent (acetone, methyl ethyl ketone, etc.), an ester solvent (ethyl acetate, butyl acetate, etc.), an ether solvent (tetrahydrofuran, diethyl ether, etc.), an amide type Examples include solvents (dimethylformamide, dimethylacetamide, etc.) and aromatic hydrocarbon solvents (toluene, xylene, etc.).

Solvent (S) used as the solvent (S) solution (L) of the resin (b) As a solvent (S2), the solvent (S2) is a poor solvent for the resin (b) as long as the resin (b) is not precipitated. Is preferable because resin particles (C) having a sharper particle size distribution can be obtained.
The content of the solvent (S2) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, based on the weight of the solvent (S1).

The solvent (S2) has a solvent (S2) insoluble content of the resin (b) in a standard state (23 ° C., 0.1 MPa) of 80% by weight or more. The solvent (S2) is preferably a solvent having an SP value larger than that of the solvent (S1) and an SP value of 10 to 25.
Specific examples of the solvent (S2) include water, alcohol (methanol, ethanol), dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, and the like. At least one solvent selected from the group consisting of water, methanol and ethanol is preferred from the viewpoint of ease of removal after the production of the resin particles.

The SP value of the solvent (S) is preferably 8.5 to 20, more preferably 8.7 to 14, and more preferably 9 to 12 from the viewpoint of the particle size distribution of the resin particles (C). The solubility parameter of the mixed solvent is calculated as an average value of the mixing weight ratio of the solubility parameter of each component.
The difference in solubility parameter between the resin (b) and the solvent (S) is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

When only the poor solvent (S2) of the resin (b) is used as the solvent (S) of the resin (b), the fine particles (A) are dispersed in the non-aqueous organic solvent (N) and, if necessary, the solvent (S). It is difficult to continuously mix and disperse the fine particle dispersion (P) and the solution (L), and a batch operation must be selected, but if a good solvent (S1) of the resin (b) is used, It is easy to continuously mix the solvent (S) solution (L) and (P) of the resin (b), and continuous operation is possible.
When the solvent (S) is composed of a good solvent (S1) and a poor solvent (S2), the good solvent (S1) generally has an SP value with the non-aqueous organic solvent (N) as compared with the poor solvent (S2). Since the difference is small, (S1) is more easily extracted from the resin particles (C1) than (S2). Therefore, since the concentration of (S2) in the solvent (S) remaining in (C1) is increased, it becomes difficult for the resin particles (C) to be combined.

As a specific example of the combination of (S1) and (S2), for example, when a polyester resin or a composite resin of a polyester resin and another resin (particularly a polyurethane resin) is selected as the resin (b), the following (1), ( 2).
(1) (S1) is ketone (acetone or methyl ethyl ketone), (S2) is water or methanol, and weight ratio (S1) :( S2) is 95: 5 to 70:30.
(2) (S1) is ketone (acetone or methyl ethyl ketone), (S2) is water: methanol (weight ratio 1: 2 to 1:10), and weight ratio (S1) :( S2) is 95: 5 to 50 : 50.

  The ratio (concentration) of the weight of the resin (b) to the weight of the solution (L) in the solvent (S) solution (L) of the resin (b) is determined by mixing the solution (L) with the non-aqueous organic solvent (N). In order to obtain a suitable viscosity, it is preferable to set appropriately, and a preferable range is 10 to 90% by weight, and further preferably 20 to 80% by weight.

Since the solvent (S) solution (L) of the resin (b) is mixed with (N), it is preferable to have an appropriate viscosity. From the viewpoint of particle size distribution, the operating temperature is preferably 100 Pa · s or less. The pressure is preferably 10 Pa · s or less.
When the viscosity of the solution (L) is higher than the above range, heating is preferably performed within a range where the resin (b) is not denatured or within a range where the precursor (b0) of the resin (b) does not react.

  Further, the solubility of the resin (b) in the non-aqueous organic solvent (N) is preferably 3% or less, more preferably 1% or less.

In the present invention, an additive (T) containing a compound represented by the following general formula [1] is mixed with a nonaqueous organic solvent (N) together with a solvent (S) solution (L) and fine particles (A) of the resin (b). ). By using (T), the particle size distribution of the obtained resin particles (C) becomes sharper, and the control of the particle size (especially when making the particle size small) becomes easy.
CH ₂ OR ¹
｜
CHOR ² [1]
｜
CH ₂ OR ³
[Wherein, R ¹ , R ² and R ³ are each independently a saturated fatty acid having 8 to 24 carbon atoms, an unsaturated fatty acid having 8 to 24 carbon atoms, or a derivative thereof, wherein OH of the —COOH group is removed. Represents a residue. ]

In the general formula [1], examples of the saturated fatty acid having 8 to 24 carbon atoms include caprylic acid, lauric acid, mytilic acid, margaric acid, stearic acid, behenic acid, and lignoceric acid. Examples of the unsaturated fatty acid having 8 to 24 carbon atoms include palmitoyl acid, oleic acid, linoleic acid, and arachidonic acid.
Examples of fatty acid derivatives include those in which hydrogen of the fatty acid is substituted with a substituent selected from a methyl group, a hydroxyl group, a carboxyl group, and an amino group.
Specific examples of those containing the compound represented by the general formula [1] include castor oil, rapeseed oil, soybean oil, corn oil, rice bran oil, safflower oil, sesame oil, cottonseed oil, palm oil, coconut oil, linseed oil, And vegetable oils such as tung oil and derivatives thereof. Of these, rapeseed oil and castor oil are preferred, and rapeseed oil is more preferred.
The amount of the additive (T) used is preferably 0.1 to 50% by weight and preferably 1 to 40% by weight with respect to the weight of the solvent (S) solution (L) of the resin (b). More preferred is 3 to 30% by weight.

  In the solvent (S) solution (L) of the resin (b) used in the present invention, additives other than (T) (colorant (E), mold release agent, charge control agent, antioxidant, blocking) An inhibitor, a heat stabilizer, a fluidizing agent, etc.), and an additive can be contained in the resulting resin particles (C).

Known dyes, pigments and magnetic powders can be used as the colorant (E). Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Examples include rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, prilliant green, phthalocyanine green, oil yellow GG, kayaset YG, orazol brown B, oil pink OP, magnetite, iron black and the like.
The amount of the colorant (E) used is preferably 0.5 to 15% by weight based on the weight of the resin (b) when a dye or pigment is used, and preferably when a magnetic powder is used. Is 20 to 150% by weight.

  As the release agent, waxes having a softening point of 50 to 170 ° C. are used. Waxes include polyolefin resins [polyethylene, polypropylene, ethylene-α olefin (3 to 8 carbon atoms) copolymer, Fischer-Tropsch wax, polymethylene, etc.], paraffins (n-paraffin, isoparaffin, etc.), ester waxes (Carnauba wax, montan wax, rice wax, etc.), aliphatic alcohols having 30 or more carbon atoms, fatty acids having 30 or more carbon atoms, and mixtures thereof. The amount of the release agent is preferably 0 to 30% by weight, more preferably 1 to 20% by weight, based on the weight of the resin (b).

  Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts). ), Alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfo group, a carboxyl group, and a quaternary ammonium salt. The amount of the charge control agent used is preferably 0 to 5% by weight based on the weight of the resin (b).

  As a method of mixing the resin (b) and other additives, a resin solution (b) selected in advance from a solvent solution of the resin (b), a solvent solution of the precursor (b0) of the resin (b), and a mixture thereof. It is preferable that after mixing the solvent (S) solution (L) and the additive, the non-aqueous organic solvent (N) and the mixture thereof are mixed and dispersed. A known method can be applied to the method of mixing the additive with the solvent (S) solution (L) of the resin (b). For example, a method of mixing using a disperser, a pulverizer, a kneader or the like can be used. Can be mentioned.

In the present invention, the solvent (S) solution (L) of the resin (b), the fine particles (A), the additive (T) containing the compound represented by the general formula [1], and the non-aqueous organic solvent (N ) May be mixed in any order and method, but as described above, the fine particle dispersion (P) is previously prepared from at least a part of (N) and (A). It is preferable to create and use it.
For example, a solution (L), a fine particle dispersion (P) in which (A) is dispersed in a fine particle (A) or a non-aqueous organic solvent (N), and an additive (T) are charged in a container and stirred. Originally, a method of further introducing the non-aqueous organic solvent (N) into the container; and a fine particle dispersion in which the fine particles (A) are dispersed in the non-aqueous organic solvent (N) and, if necessary, the solvent (S) ( P) is a method in which the solution (L) and the additive (T) are mixed and dispersed. Of these, the latter method is preferred.

  In this way, the solvent (S) solution (L) of resin (b), fine particles (A), additive (T), and non-aqueous organic solvent (N) are mixed, and the non-aqueous organic solvent (N) and The resin (b) is dispersed in the non-aqueous dispersion (X) containing the solvent (S), and the resin (b) is grown on the surface while the fine particles (A) are adsorbed on the surface. Resin particles (C1) in which fine particles (A) are adhered to the surface of resin particles (B1) containing (b), additive (T) and solvent (S) are formed. A non-aqueous dispersion (X) is obtained by dispersing (C1) in (N) and (S).

  The temperature at which the non-aqueous dispersion (X) is formed is preferably 10 ° C. or higher from the viewpoint of the dispersibility of the resin particles (C1), and the fine particles (A), resin particles (B), and resin particles (C ) Is preferably 80 ° C. or lower. More preferably, it is 20-60 degreeC.

  Use amount of fine particle dispersion (P) in which fine particles (A) are dispersed in non-aqueous organic solvent (N) with respect to 100 parts by weight of resin (b) [(A) and (N) when (P) is not used The total amount] is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (b) is good, and if it is 2,000 parts by weight or less, it is economical.

When the solvent (S) solution (L) of resin (b), fine particles (A), additive (T), and non-aqueous organic solvent (N) are mixed to form a non-aqueous dispersion (X). A dispersion device can be used.
The dispersion apparatus is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser, and specific examples include those described in JP-A-2002-284881.

  In the production method of the present invention, the solvent (S), the non-aqueous organic solvent (N), and, if necessary, the additive (T) are removed from the non-aqueous dispersion (X) formed by the above method.

As a method of removing the solvent (S) and the non-aqueous organic solvent (N) from the non-aqueous dispersion (X) liquid of the resin particles (C1) to obtain the resin particles (C),
[1] Solvent (S) and non-aqueous organic solvent (N) are desolvated under reduced pressure or normal pressure, and the resulting powder is dried. [2] Solid-liquid using a centrifuge, spacula filter, filter press, etc. Method of separating and drying the resulting powder [3] Method of freezing and drying solvent (S) and non-aqueous organic solvent (N) (so-called lyophilization)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.

In addition, when the additive (T) is contained in the resin particles (C), depending on the use (when used as resin particles for electrophotographic toners, etc.), the performance of the resin particles is adversely affected. It is desirable to remove.
The compound used as the additive (T) is generally known to have a high boiling point, and tends to remain in the resin particles (C). Examples of the method for removing the additive (T) from the resin particles (C) include a method for removing by filtration or centrifugation. At that time, a good solvent of the additive (T) having a low boiling point, for example, an aliphatic hydrocarbon solvent such as normal pentane, normal hexane, etc. is added to the resin particles (C) [solvent (S) and non-aqueous organic solvent (N) It may not be completely removed. It is desirable to extract and dissolve the additive (T) from the resin particles (C) in the good solvent, and then filter or centrifuge.
The amount of the good solvent to be added (T) is not particularly limited as long as it can extract (T), but is preferably 1 to 10 times the weight of the obtained resin particles (C).

In the resin particles (C) obtained by the production method of the present invention, fine particles (A) are once attached to the surfaces of the resin particles (B1). For example, when the crystalline resin (a1) is used as (A), etc. Depending on the composition of the material (a) and the resin (b) constituting the fine particles (A) and the type of the solvent (S), the fine particles (A) are formed into a film during the production process such as the desolvation process, A film in which (A) is formed into a film may be formed on the surface of B).
The resin particles (C) are those in which fine particles (A) are attached to the surface of the resin particles (B), in which a film derived from (A) is formed, and in which a part of (A) is formed into a film Either may be sufficient.
The surface state and shape of the resin particles (C) can be observed by, for example, a photograph obtained by enlarging the surface of the resin particles 10,000 times or 30,000 times using a scanning electron microscope (SEM).

The volume average particle diameter of the resin particles (C) obtained by the production method of the present invention is preferably 0.01 to 300 μm, more preferably 0.1 to 100 μm, particularly preferably 0.5 to 50 μm. When it is 0.01 μm or more, the handling property as a powder is good. A particle size distribution is more favorable in it being 300 micrometers or less.
The ratio DVc / DNc of the volume average particle diameter DVc of (C) and the number average particle diameter DNc of (C) is preferably 1.0 to 1.5, more preferably 1.0 to 1.4, particularly preferably. 1.0 to 1.3. When it is 1.5 or less, powder characteristics (fluidity, charging uniformity, etc.) are remarkably improved.

From the viewpoints of particle size uniformity, powder fluidity, storage stability, etc., 5% or more of the surface of the resin particles (B) is a film derived from the fine particles (A) or (A). It is preferably covered, more preferably 30% or more. The surface coverage can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = 100 × [surface area of (B) of the portion covered with the film derived from (A) or (A)] / [covered with the film derived from (A) or (A) (B) surface area of the portion + area of the portion where the surface of (B) is exposed]

In the resin particles (C) obtained by the production method of the present invention, the weight ratio of the material (a) constituting the fine particles (A) and the resin (b) constituting the resin particles (B) is preferably (0.1 : 99.9) to (30:70), and more preferably (0.2: 99.8) to (20:80). It is preferable that the weight ratio of the material (a) and the resin (b) is within this range because both low-temperature fixability and long-term storage stability are compatible.
When (a) in the resin particle (C) is the crystalline resin (a1), the weight ratio of the crystalline resin (a1) is determined from the endothermic amount of the endothermic peak unique to (a1) by a known method, for example, DSC. It can be measured by the calculation method.

The resin particles (C) obtained by the production method of the present invention are obtained by changing the particle diameters of the fine particles (A) and the resin particles (B) and the coverage of the resin particles (B) by the fine particles (A). Desirable irregularities can be imparted to the surface.
When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area in the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). . Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, the fine particles (A) and the resin particles (B) are also preferably spherical. In (C), Wadell's practical sphericity is preferably 0.85 to 1.00. The Wadell practical sphericity is obtained from a ratio of a diameter of a circle having an area equal to the projected area of the particle and a diameter of a circle having a minimum area circumscribing the projected image of the particle. The projected image of the particles can be taken with, for example, a scanning electron microscope (SEM).

The resin particles (C) obtained from the production method of the present invention are particularly useful as resin particles for electrophotographic toners. As a method for producing resin particles for an electrophotographic toner, in the method for producing resin particles (C), a colorant (E) is further contained in the solvent (s) solution (L) of the resin (b) and colored. The method of obtaining the obtained resin particle (C) is mentioned.
As the colorant (E), the above-mentioned colorant (E) can be appropriately used. In addition, the above-described charge adjusting agent may be used to control the charging property, and the above-described releasing agent may be used to control the releasing property at the time of fixing.
When the resin particles (C) obtained by the production method of the present invention are used as resin particles for an electrophotographic toner, the volume average particle diameter of the resin particles (C) is preferably 1 to 10 μm, more preferably 1.5 to It is 8 μm, particularly preferably 2 to 6 μm. The ratio DVc / DNc of the volume average particle diameter DVc of (C) and the number average particle diameter DNc of (C) is preferably 1.0 to 1.3, more preferably 1.0 to 1.2.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” means parts by weight, and “%” means% by weight unless otherwise specified.

The following crystallinity, melting point, glass transition temperature (Tg), number average molecular weight (Mn), weight average molecular weight (Mw), and volume average particle diameter were measured by the following methods.
<Measurement method of crystallinity>
A sample (5 mg) was collected and placed in an aluminum pan, and the temperature was increased from room temperature to a temperature increase rate of 20 ° C./min using DSC (differential scanning calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.). The amount of heat of fusion (ΔHm (J / g)) determined from the area of the endothermic peak was determined while changing. Based on the measured ΔHm, the degree of crystallinity (%) was calculated by the following formula.
Crystallinity = (Heat of fusion / a) × 100
In the above formula, a is measured as follows.
Measurement method according to JISK0131 (1996) (X-ray diffraction analysis general rule 13 crystallinity measurement (2) absolute method) by measuring the heat of fusion of a resin having the same composition as the resin to be measured by DSC The crystallinity was measured at When the heat of fusion is plotted on the vertical axis and the crystallinity is plotted on the horizontal axis, the standard data is plotted, and a straight line is drawn from the two points of that point and the origin, and extrapolated so that the crystallinity is 100% The value obtained by calculating the amount of heat of fusion is a.

<Measuring method of melting point>
A sample (5 mg) is collected and placed in an aluminum pan, and the DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII NanoTechnology Co., Ltd.) is used to absorb heat by crystal melting at a heating rate of 10 ° C./min. The peak temperature (° C.) was determined.
<Measuring method of glass transition temperature (Tg)>
5 mg of each sample was weighed, and the glass transition temperature was measured at a heating rate of 10 ° C. per minute by DSC (Differential Scanning Calorimetry) (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.).
<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
Each sample was dissolved in tetrahydrofuran at a concentration of 2.5 g / L and measured by GPC.
GPC model: HLC-8120GPC, manufactured by Tosoh Corporation Column: TSKgel GMHXL) 2 + TSKgel Multipore
HXL-M (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C
Solution injection volume: 100 μl
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSYRENE) manufactured by Tosoh (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)
<Measurement method of volume average particle diameter>
After 5 mg of the sample was dispersed in 10 g of ion-exchanged water, measurement was performed with Multisizer III (manufactured by Coulter).

Production Example 1 <Preparation of Resin (b-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 831 parts of 1.2-propylene glycol (hereinafter referred to as propylene glycol), 703 parts of terephthalic acid, 47 parts of adipic acid, and tetrabutoxy as a condensation catalyst 0.5 parts of titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 87 ° C. After cooling to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain an amorphous polyester resin (b-1). This resin had Mn of 1900 and Tg of 45 ° C.

Production Example 2 <Preparation of Resin (b-2)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 729 parts of propylene glycol, 683 parts of terephthalic acid, 67 parts of adipic acid, 38 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate as a condensation catalyst The mixture was allowed to react for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 172 parts. When the softening point reached 160 ° C., it was taken out, cooled to room temperature, pulverized and granulated to obtain an amorphous polyester resin (b-2). This resin had Mn of 5700 and Tg of 63 ° C.

Production Example 3 <Preparation of Resin (b-3)>
Into an autoclave equipped with a stir bar and a thermometer, 24 parts of xylene were added, and mixed monomer 2 of butyl acrylate / methyl methacrylate / styrene / 2-ethylhexyl acrylate (25% / 33% / 40% / 2%) 1,000 parts of the polymerization catalyst and 1 part of a polymerization catalyst azobismethoxydimethylvaleronitrile were dropped at 170 ° C. for 3 hours. Volatilization was performed at normal pressure while raising the temperature to 180 ° C., and when the temperature reached 180 ° C., the pressure was switched to reduced pressure, and devolatilization was performed over 2 hours to obtain an amorphous vinyl resin (b-3). The resin had a Mn of 10500 and a Tg of 62 ° C.

Production Example 4 <Adjustment of Crystalline Part (p-1)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 159 parts of sebacic acid, 11 parts of adipic acid and 108 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 0. 5 parts were added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the generated water. Next, while gradually raising the temperature to 225 ° C., the reaction is carried out for 4 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it became 10,000, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part (p-1)]. The melting point of [crystalline part (p-1)] was 57 ° C., Mn was 5000, Mw was 11000, and the hydroxyl value was 30.

Production Example 5 <Adjustment of Crystalline Part (p-2)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 121 parts of sebacic acid, 118 parts of dimethylterephthalic acid and 124 parts of 1,6-hexanediol and titanium dihydroxybis (triethanolaminate) 1 as a condensation catalyst The reaction was allowed to proceed for 8 hours while distilling off the water produced under a nitrogen stream at 180 ° C. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the generated water and 1,6-hexanediol under a nitrogen stream, and the reaction is further carried out under a reduced pressure of 5 to 20 mmHg. When it became, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polycondensed polyester resin [crystalline part (p-2)]. The melting point of [crystalline part (p-2)] was 53 ° C., Mw was 8000, and the hydroxyl value was 46.

Production Example 6 <Adjustment of Crystalline Part (p-3)>
In a reaction vessel equipped with a stirrer and a dehydrator, 2 parts of 1,4-butanediol, 650 parts of ε-caprolactone, and 2 parts of dibutyltin oxide are added, and the reaction is carried out at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere. went. Further, the obtained resin was cooled to room temperature and then pulverized to form particles, whereby a crystalline polyester resin [crystalline part (p-3)], which was a lactone ring-opening polymer, was obtained. The melting point of [crystalline part (p-3)] was 60 ° C., Mw was 9800, and the hydroxyl value was 14.

Production Example 7 <Preparation of Resin (b-4)>
A reaction vessel equipped with a stir bar and a thermometer was charged with 44 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 32 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, this amorphous polyurethane resin (q-1) solution was added to a solution in which 140 parts of [crystalline part (p-1)] were dissolved in 140 parts of MEK and reacted at 80 ° C. for 4 hours to obtain crystallinity. An MEK solution of the block resin (b-4) was obtained. The melting point of the crystalline block resin (b-4) after removing the solvent was 56 ° C., Mn was 14,000, and Mw was 28000.

Production Example 8 <Preparation of Resin (b-5)>
A reaction vessel equipped with a stir bar and a thermometer was charged with 42 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 31 parts of cyclohexanedimethanol and allowed to react at 80 ° C. for 2 hours. Next, this amorphous polyurethane resin (q-2) solution was added to a solution in which 126 parts of [crystalline part (p-2)] were dissolved in 140 parts of MEK, and reacted at 80 ° C. for 4 hours to obtain crystallinity. A MEK solution of the block resin (b-5) was obtained. The melting point of the crystalline block resin (b-5) after removing the solvent was 53 ° C., Mn was 10,000, and Mw was 22,000.

Production Example 9 <Preparation of Resin (b-6)>
A reaction vessel equipped with a stir bar and a thermometer was charged with 44 parts of tolylene diisocyanate and 100 parts of MEK. This solution was charged with 32 parts of cyclohexanedimethanol and reacted at 80 ° C. for 2 hours. Next, this amorphous polyurethane resin (q-1) solution was added to a solution in which 250 parts of [crystalline part (p-3)] were dissolved in 250 parts of MEK and reacted at 80 ° C. for 4 hours to obtain crystallinity. A MEK solution of the block resin (b-6) was obtained. The melting point of the crystalline block resin (b-6) after removing the solvent was 60 ° C., Mn was 10,000, and Mw was 22000.

Production Example 10 <Preparation of Resin Solution (L-1)>
In a container equipped with a stirrer, 228 parts of resin (b-1) obtained in Production Example 1 and Production Example 2 were added to solvent (S-1) which is a mixed solvent consisting of 450 parts of acetone and 50 parts of ion-exchanged water. The resin (b-2) 57 parts and carbon black 15 parts obtained in the above were charged and stirred until the resins (b-1) and (b-2) were completely dissolved to obtain a resin solution (L-1). It was. Resin (b-1) and resin (b-2) in the standard state had a solvent (S-1) insoluble content of 0.1% or less, and the solvent (S-1) had an SP value of 10.5.

Production Example 11 <Preparation of Resin Solution (L-2)>
In a container equipped with a stirring device, 280 parts of resin (b-3) obtained in Production Example 3 and 15 parts of carbon black were added to solvent (S-2), which is a mixed solvent consisting of 490 parts of acetone and 210 parts of methanol. Was stirred until the resin (b-3) was completely dissolved to obtain a resin solution (L-2). The resin (b-3) insoluble in the solvent (S-2) in the standard state was 0.1% or less, and the SP value of the solvent (S-2) was 10.9.

Production Example 12 <Preparation of Resin Solution (L-3)>
In a container equipped with a stirrer, 450 parts of acetone and 50 parts of ion-exchanged water, solvent (S-1) which is a mixed solvent, 285 parts of resin (b-4) obtained in Production Example 7, and carbon black 15 parts were charged and stirred until the resin (b-4) was completely dissolved to obtain a resin solution (L-3). The solvent (S-1) insoluble content of the resin (b-4) in the standard state was 0.1% or less.

Production Example 13 <Preparation of Resin Solution (L-4)>
In a container with a stirrer, 450 parts of acetone and 50 parts of ion-exchanged water, a solvent (S-1) that is a mixed solvent, 285 parts of the resin (b-5) obtained in Production Example 8, and carbon black 15 parts were charged and stirred until the resin (b-5) was completely dissolved to obtain a resin solution (L-4). The solvent (S-1) insoluble content of the resin (b-5) in the standard state was 0.1% or less.

Production Example 14 <Preparation of Resin Solution (L-5)>
In a container equipped with a stirrer, 450 parts of acetone and 50 parts of ion-exchanged water, a solvent (S-1) that is a mixed solvent, 285 parts of the resin (b-6) obtained in Production Example 9, and carbon black 15 parts were charged and stirred until the resin (b-6) was completely dissolved to obtain a resin solution (L-5). The solvent (S-1) insoluble content of the resin (b-6) in the standard state was 0.1% or less.

Production Example 15 <Preparation of Crystalline Resin (a1-1)>
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube was charged with 500 parts of toluene, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (22 carbon atoms directly). Acrylate of alcohol having a chain alkyl group; 150 parts of Bremer VA (manufactured by NOF Corporation)) and 7.5 parts of AIBN (azobisisobutyronitrile) are charged, and the monomer is stirred and mixed at 20 ° C. A solution was prepared and charged into the dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state, and after aging at 85 ° C. for 2 hours from the end of the addition, toluene was added at 130 ° C. for 3 hours. After removing for a period of time under reduced pressure, a crystalline vinyl resin (a1-1) was obtained. The crystallinity of this resin was 42%, the melting point was 65 ° C., and Mn was 50000.

Production Example 16 <Preparation of Fine Particle (A-1) Dispersion>
After mixing 700 parts of normal hexane and 300 parts of crystalline vinyl resin (a1-1), pulverization was performed using zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). A milky white fine particle (A-1) dispersion was obtained. The volume average particle size of the fine particles (A-1) in this dispersion was 0.3 μm.

Production Example 17 <Preparation of Crystalline Resin (a1-2)>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 230 parts of dodecanedioic acid, 195 parts of 1,6-hexanediol and 0.5 part of tetrabutoxytitanate as a condensation catalyst were gradually added to 230 ° C. While raising the temperature, the reaction was carried out for 4 hours while distilling off the generated water, and the reaction was further carried out under reduced pressure of 5 to 20 mmHg, and the mixture was taken out when the melting point reached 60 ° C. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a crystalline polyester resin (a1-2). The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 8,000.

Production Example 18 <Preparation of Fine Particle (A-2) Dispersion>
In Production Example 16, a milky white fine particle (A-2) dispersion liquid was produced in the same manner as in Production Example 16 except that the crystalline polyester resin (a1-2) was used instead of the crystalline vinyl resin (a1-1). Got. The volume average particle size of the fine particles (A-2) in this dispersion was 0.4 μm.

  In the following examples, the additive (T-1) is rapeseed oil and the additive (T-2) is castor oil.

Example 1
Into a beaker, normal decane and fine particle (A-1) dispersion liquid was charged, mixed with a homomixer (manufactured by Primics) at a rotational speed of 16000 rpm for 10 seconds, and then the resin solution (L-1) and additives ( T-1) was added all at once and dispersed for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa for 2 hours, and then normal hexane was added to the obtained resin particles to extract and dissolve the additive (T-1), followed by filtration. Then, the solvent and additive (T-1) in the system are removed by drying at 40 ° C. for 6 hours, and the resin particles (B) are coated with resin particles (A) derived from the fine particles (A). C-1) was obtained. The weight ratio of the charged composition in Example 1 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-1) 60 parts Normal decane 120 parts Normal hexane 200 parts

Example 2
In Example 1, except that the resin solution (L-2) was used instead of the resin solution (L-1), the surface of the resin particle (B) was derived from the fine particles (A) in the same manner as in Example 1. Resin particles (C-2) on which a film was formed were obtained. The weight ratio of the charged composition in Example 2 is as follows.
Resin solution (L-2) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-1) 20 parts Normal decane 120 parts Normal hexane 200 parts

Example 3
In Example 1, except that the resin solution (L-3) was used instead of the resin solution (L-1), the surface of the resin particle (B) was derived from the fine particles (A) except that the resin solution (L-3) was used. Resin particles (C-3) on which a film was formed were obtained. The weight ratio of the charged composition in Example 3 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-1) 80 parts Normal decane 120 parts Normal hexane 200 parts

Example 4
In Example 1, except that the resin solution (L-4) was used instead of the resin solution (L-1), the surface of the resin particle (B) was derived from the fine particles (A) except that the resin solution (L-4) was used. Resin particles (C-4) on which a film was formed were obtained. The weight ratio of the charged composition in Example 4 is as follows.
Resin solution (L-4) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-1) 60 parts Normal decane 120 parts Normal hexane 200 parts

Example 5
In Example 1, in the same manner as in Example 1 except that the resin solution (L-5) was used instead of the resin solution (L-1), the surface of the resin particle (B) was derived from the fine particles (A). Resin particles (C-5) on which a film was formed were obtained. The weight ratio of the charged composition in Example 5 is as follows.
Resin solution (L-5) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-1) 60 parts Normal decane 120 parts Normal hexane 200 parts

Example 6
In Example 3, in place of the fine particle (A-1) dispersion, the fine particle (A-2) dispersion was used in the same manner as in Example 3, except that the fine particles (A ) -Derived resin particles (C-6) were obtained. The weight ratio of the charged composition in Example 6 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-2) dispersion 45 parts Additive (T-1) 60 parts Normal decane 120 parts Normal hexane 200 parts

Example 7
In Example 3, in place of the additive (T-1), the additive (T-2) was used in the same manner as in Example 3 except that the surface of the resin particle (B) was derived from the fine particles (A). Resin particles (C-7) on which the film was formed were obtained. The weight ratio of the charged composition in Example 7 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-1) dispersion 45 parts Additive (T-2) 60 parts Normal decane 120 parts Normal hexane 200 parts

Comparative Example 1
In Example 1, the surface of the resin particles (B) is not treated in the same manner as in Example 1 except that the additive (T-1) is not used and the operation of removing the additive (T-1) is not performed. Resin particles (C′-1) having a coating derived from the fine particles (A) were obtained. The weight ratio of the charged composition in Comparative Example 1 is as follows.
Resin solution (L-1) 270 parts Fine particle (A-1) dispersion 45 parts Normal decane 120 parts

Comparative Example 2
In Example 3, the surface of the resin particle (B) is not treated in the same manner as in Example 3 except that the additive (T-1) is not used and the operation of removing the additive (T-1) is not performed. Resin particles (C′-2) having a coating derived from the fine particles (A) were obtained. The weight ratio of the charged composition in Comparative Example 2 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-1) dispersion 45 parts Normal decane 120 parts

Comparative Example 3
In Example 6, the surface of the resin particle (B) was not treated in the same manner as in Example 6 except that the additive (T-1) was not used and the operation for removing the additive (T-1) was not performed. Resin particles (C′-3) having a coating derived from the fine particles (A) were obtained. The weight ratio of the charged composition in Comparative Example 3 is as follows.
Resin solution (L-3) 270 parts Fine particle (A-2) dispersion 45 parts Normal decane 120 parts

Evaluation Results For the resin particles obtained in Examples 1 to 7 and Comparative Examples 1 to 3, the shape was observed by the above method, and the volume average particle size, particle size distribution, charging characteristics ( The charge amount) and the heat-resistant storage stability were evaluated, and the results are shown in Table 1.
<Evaluation of volume average particle size and particle size distribution>
Resin particles are dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle diameter and volume average particle diameter / number average particle diameter of the resin particles (denoted as (C) in the table) are measured by a Coulter counter. [Multisizer III (manufactured by Beckman Coulter)] was measured. The smaller the volume average particle size / number average particle size, the sharper the particle size distribution.

<Evaluation of charging characteristics>
In a 50 cc glass bottle with a stopper, 0.5 g of resin particles and 10 g of iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.) are precisely weighed, stoppered and placed in an atmosphere of 23 ° C. and 50% RH. It was set in a turbula shaker mixer (manufactured by Willy a Baschofen) and stirred for 2 minutes at a rotation speed of 90 rpm. 0.2 g of the mixed powder after stirring was loaded into a blow-off powder charge measuring device (TB-203 manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm mesh stainless steel mesh was set, and conditions of blow pressure 10 KPa and suction pressure 5 KPa Then, the charge amount of the residual iron powder was measured, and the charge amount of the resin particles was calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics.

<Evaluation of heat-resistant storage stability>
The heat resistant storage stability of the resin particles was evaluated by the following method. That is, the resin particles were allowed to stand for 15 hours in a dryer adjusted to 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs, but disperses easily when force is applied with a finger or the like.
X: Blocking occurs and does not disperse even when force is easily applied with a finger or the like.

  The resin particles obtained in Examples 1 to 7 had a small volume average particle size / number average particle size, a sharp particle size distribution, excellent heat storage stability, and excellent charging characteristics. The resin particles obtained in Examples 1 to 3 had a large particle size, a volume average particle size / number average particle size significantly deteriorated, and inferior charging characteristics.

  According to the production method of the present invention, resin particles having a sharp particle size distribution can be obtained using a non-aqueous organic solvent, and the resulting resin particles have a sharp particle size distribution and are excellent in heat-resistant storage stability and charging characteristics. Therefore, electrophotographic toner base particles, paint additives, cosmetic additives, paper coating additives, slush molding resins, powder coatings, electronic component manufacturing spacers, electronic measuring instrument standard particles, electronic paper It is useful as a particle for medical use, a carrier for medical diagnosis, a particle for electroviscosity, and other resin particles for molding.

Claims (7)

A solvent (S) solution (L) of resin (b), fine particles (A), an additive (T) containing a compound represented by the following general formula [1], and a non-aqueous organic solvent (N) are mixed. A non-aqueous dispersion (X) of resin particles (C1) in which fine particles (A) are adhered to the surface of resin particles (B1) containing resin (b), additive (T) and solvent (S) A process for producing resin particles (C), comprising a step of forming and further removing the solvent (S), the non-aqueous organic solvent (N), and, if necessary, the additive (T) from the non-aqueous dispersion (X).
CH ₂ OR ¹
｜
CHOR ² [1]
｜
CH ₂ OR ³
[Wherein R ¹ , R ² and R ³ are each independently a residue obtained by removing OH of a —COOH group from a saturated fatty acid having 8 to 24 carbon atoms, an unsaturated fatty acid having 8 to 24 carbon atoms, or a derivative thereof. Represents a group. ]   The additive (T) is selected from the group consisting of castor oil, rapeseed oil, soybean oil, corn oil, rice bran oil, safflower oil, sesame oil, cottonseed oil, palm oil, coconut oil, linseed oil, tung oil, and derivatives thereof. The production method according to claim 1, wherein the production method is at least one kind.   The production method according to claim 1 or 2, wherein the amount of the additive (T) is 0.1 to 50% by weight relative to the weight of the solvent (S) solution (L) of the resin (b).   The solvent (S) is a good solvent (S1) of (b) in which the solvent (S1) insoluble content of the resin (b) is 20% by weight or less in the standard state (23 ° C., 0.1 MPa), and the resin in the standard state The manufacturing method of any one of Claims 1-3 containing the poor solvent (S2) of resin (b) whose solvent (S2) insoluble content of (b) is 80 weight% or more.   The manufacturing method according to any one of claims 1 to 4, wherein the resin (b) is at least one resin selected from the group consisting of a polyurethane resin, an epoxy resin, a vinyl resin, and a polyester resin.   The fine particles (A) are fine particles comprising at least one material (a) selected from the group consisting of a crystalline resin (a1), an amorphous resin (a2), and an inorganic compound (a3). 6. The production method according to any one of 5 above.   In the manufacturing method of any one of Claims 1-6, the solvent (S) solution (L) of resin (b) contains a coloring agent (E), and colored resin particle (C). A process for producing resin particles for electrophotographic toner, characterized in that it is obtained.