JP5705493B2 - Method for producing resin particles - Google Patents

Description

  The present invention relates to a method for producing resin particles and resin particles.

  As methods for forming resin particles having higher crystallinity than conventional methods, a method of depositing a crystalline resin from an organic solvent (for example, see Patent Document 1) and a method using a phase separation solvent (for example, see Patent Document 2). Are known.

Japanese Patent Laid-Open No. 2005-15589 JP-A-8-176310

However, in the above method, it is difficult to obtain particles having a narrow particle size distribution, and the obtained resin particles are insufficient in terms of both heat-resistant storage stability and melting characteristics (low-temperature melting properties). Moreover, when coloring using a coloring agent, coloring may become non-uniform | heterogenous.
An object of the present invention is to provide a production method for obtaining resin particles in which a particle size distribution is sufficiently narrow, heat-resistant storage stability and melting characteristics can be compatible with each other, and a colorant is uniformly dispersed.

As a result of intensive studies, the inventors have reached the present invention.
That is, the present invention relates to a solvent (S) solution (L) of a resin (B) and a colorant dispersion (in a liquid or supercritical carbon dioxide (X) in which organic fine particles (A) are dispersed. By dispersing C), or by dispersing the solvent (S) solution (L) of the resin (B), the colorant dispersion (C), and the wax dispersion (D), the resin (B), colorant (k), and the solvent (S) to form an organic fine particle (a) is secured to the resin particles (Z1) on the surface of the resin particles containing (Y1) was treated with (Z1) with (X) Then, the resin particles (Z) including a step of removing (X) and (S) from the dispersion (Q) in which the obtained (Z1) is dispersed in the dispersion medium containing (X) and (S) A crystalline part in which the resin (B) contains a lactone ring-opening polymer (p) as an essential component a) a resin composed of an amorphous part (b), a colorant dispersion (C) having a colorant (k), and a total of acid value and amine value (mgKOH / g) of 20 to 250 The dispersant (l), the solvent (S), and the liquid or supercritical carbon dioxide (X) having a pressure of 2 MPa or more are mixed and then expanded under reduced pressure to vaporize and remove (X). A process for producing resin particles obtained in (1), wherein (k) having a median diameter of 1 μm or less is dispersed in (S);
And it is a resin particle (Z) obtained by said manufacturing method.

  The resin particles obtained by the production method of the present invention have a sufficiently narrow particle size distribution, can achieve both heat-resistant storage stability and melting characteristics (low-temperature melting properties), and the colorant is uniformly dispersed.

It is a flowchart of the experimental apparatus used for preparation of the resin particle in this invention.

The present invention is described in detail below.
The organic fine particles (A) used in the production method of the present invention have carbon dioxide (X) in a liquid state or a supercritical state at a glass transition temperature (hereinafter sometimes referred to as Tg) or a temperature below the melting point. Hereinafter, it may be described as carbon dioxide (X). ], The organic fine particles of 16% or less are preferred, more preferably 10% or less, and particularly preferably 5% or less. When the organic fine particles (A) having a swelling degree of 16% or less are used, aggregation of the resin particles can be suppressed, and the particle size distribution of the resin particles becomes narrow.

  A method for measuring the degree of swelling can be measured using a magnetic suspension balance. The details of the method for measuring the degree of swelling are described in J. Supercritical Fluids. 19, 187-198 (2001).

The organic fine particles (A) may be a crystalline resin or an amorphous resin.
The composition of the crystalline resin constituting the organic fine particles (A) includes a vinyl resin, an aromatic ring-containing polyester resin, a polyester resin not containing an aromatic ring, and a polyurethane resin, which will be described later as the crystalline resin constituting the resin (B). And polyamide resins and polyurea resins.
Examples of the amorphous resin include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide, polyimide, silicone resin, fluororesin, phenol resin, melamine resin, polycarbonate, cellulose, and a mixture thereof. The composition of the non-crystalline resin is not limited to obtainment, and a commonly used resin may be used.
Among these, crystalline resins, non-crystalline vinyl resins having a polyester chain, non-crystalline vinyl resins containing silicone, and cross-linkable non-crystalline resins are preferred, and crystalline or non-crystalline vinyl resins ( N) is more preferred.

The melting point of the crystalline resin is preferably 40 to 110 ° C, more preferably 45 to 100 ° C, and particularly preferably 50 to 90 ° C. When the melting point of the crystalline resin is 40 ° C. or higher, the resin particles (Z) 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 meltability is favorable.
The melting point in the present invention is the temperature of an endothermic peak due to melting at the first temperature rise (° C.) measured with a differential scanning calorimeter (DSC) according to JIS K7122 (1987) “Method for measuring the transition heat of plastic”. Means.

The crystallinity of the crystalline resin is preferably 20 to 95%, more preferably 30 to 80%, from the viewpoint of suppression of swelling by carbon dioxide (X) and adsorptivity to the resin particles (Y). . The degree of crystallinity is obtained by calculating the heat of fusion (ΔHm (J / g)) from the endothermic peak area using DSC, and calculating the degree of crystallinity (%) by the following formula based on the measured ΔHm.
Crystallinity = (ΔHm / a) × 100
In the above formula, a is the heat of fusion when extrapolated so that the crystallinity is 100%.

The number average molecular weight (hereinafter abbreviated as Mn) of the crystalline resin is preferably 1000 or more, more preferably 1500 or more, and particularly preferably 2000 or more, from the viewpoint of resin elasticity. Moreover, from a viewpoint of melt viscosity, Preferably it is 1 million or less, More preferably, it is 500,000 or less, Most preferably, it is 300000 or less.
The same range is preferable for the non-crystalline resin Mn.

The crystalline or non-crystalline vinyl resin (N) and the cross-linking non-crystalline resin, which are preferable resins as the resin constituting the organic fine particles (A), will be described in detail.
Preferable specific examples of (N) include the following (N1) to (N4), and two or more kinds may be used in combination.
(N1) An alkyl (meth) acrylate (m1) having 8 to 50 carbon atoms in the alkyl group is an essential constituent unit, and if necessary, perfluoroalkyl (alkyl) (meth) acrylate (m2), and unsaturated dicarboxylic acid And / or vinyl resin having one or more selected from the anhydride (m3) as a structural unit (N2) Vinyl resin having (meth) acrylonitrile (m4) and a crystalline vinyl monomer as essential structural units.
(N3) A vinyl resin having a polyester chain and a vinyl monomer (m5) having a number average molecular weight (Mn) of 500 to 100,000 as an essential constituent unit.
(N4) A vinyl resin containing 0.1 to 50% of a silicone-containing vinyl monomer (m6) as a structural unit.
In the above and below, “%” means “% by weight” unless otherwise specified.

The alkyl (meth) acrylate (m1) having 8 to 50 carbon atoms in the alkyl group, which is an essential constituent unit of the vinyl resin (N1), has a linear or branched alkyl group. 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, and 2-decyltetra A decyl (meth) acrylate is mentioned. Among these, linear alkyl (meth) acrylates having 18 to 30 carbon atoms in the alkyl group are preferable, and behenyl (meth) acrylate is more preferable.
In addition, the said (meth) acrylate means an acrylate and / or a methacrylate, and the same description method is used hereafter.

The perfluoroalkyl (alkyl) (meth) acrylate (m2) is preferably a perfluoroalkyl group having an even number of 2 to 12 carbon atoms and a (alkyl) moiety having 0 to 3 carbon atoms. Specific examples include (2-perfluoroethyl) ethyl (meth) acrylate, (2-perfluorobutyl) ethyl (meth) acrylate, (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl). ) Ethyl (meth) acrylate, (2-perfluorodecyl) ethyl (meth) acrylate, and (2-perfluorododecyl) ethyl (meth) acrylate. 2,2,2-trifluoroethyl acrylate is also preferred. (M2) may be a single monomer or a combination of plural monomers.
Of these, more preferred are (2-perfluorohexyl) ethyl (meth) acrylate, (2-perfluorooctyl) ethyl (meth) acrylate, and (2-perfluorodecyl) ethyl (meta) from the viewpoint of chargeability. ) Acrylate, (2-perfluorododecyl) ethyl (meth) acrylate.

  The unsaturated dicarboxylic acid and / or its anhydride (m3) is preferably an unsaturated dicarboxylic acid having 3 to 30 carbon atoms and its anhydride. Specific examples thereof include maleic acid, fumaric acid, maleic anhydride, and itaconic acid. , Itaconic anhydride, citraconic acid, citraconic anhydride and the like. (M3) may use 2 or more types together. Of these, maleic anhydride is more preferable from the viewpoint of chargeability.

The content of (m1) in the vinyl resin (N1) is preferably 30% or more, more preferably 40 to 90%, and particularly preferably 50 to 80%. When the content of (m1) is 30% or more, it has crystallinity and is sharp-melted so that it has excellent storage stability and low-temperature meltability, and good charging characteristics under high temperature and high humidity, and is 90% or less. Charging characteristics under high temperature and high humidity are better.
The content (total) of (m2) and / or (m3) in the vinyl resin (N1) is preferably 30% or less, more preferably 0.001 to 25%, and more preferably 0.01 to 20 %, Particularly preferably 0.1 to 10%, most preferably 0.1 to 5%. When the content of (m2) and / or (m3) is 30% or less, the crystallinity increases and the storage stability is improved, and when it is 0.001% or more, the charging characteristics under high temperature and high humidity. Is good.
The total content of monomers other than (m1), (m2), and (m3) in (N1) is preferably 50% or less, more preferably 30% or less. When the content of the other monomer is 50% or less, the degree of crystallinity is increased and the storage stability is improved.
As the other monomer, a vinyl monomer described later can be appropriately selected.

As the vinyl resin (N2) having (meth) acrylonitrile (m4) and a crystalline vinyl monomer as essential constituent units, the content of the constituent unit of (meth) acrylonitrile (m4) is from the viewpoint of adhesion to resin particles. The content is preferably 0.01 to 40%, more preferably 0.05 to 35%, and particularly preferably 0.1 to 30%.
The crystalline vinyl monomer used in combination is not particularly limited as long as a crystalline vinyl resin can be formed. However, the alkyl (meth) acrylate (m1) having 8 to 50 carbon atoms in the above alkyl group, and Examples include ethylene.
The content of the crystalline vinyl monomer in the vinyl resin (N2) is preferably 30 to 90%, more preferably 40 to 85%, and particularly preferably 50 to 80%.
The total content of monomers other than (m4) and the crystalline vinyl monomer in (N2) is preferably 50% or less, more preferably 40% or less. When the content of the other monomer is 50% or less, the degree of crystallinity is increased and the storage stability is improved.

Examples of the polyester chain portion in the vinyl monomer (m5) having a polyester chain in the vinyl resin (N3) include a polycondensate of diol and dicarboxylic acid, and a lactone ring-opening polymer.
The vinyl monomer (m5) having a polyester chain has an Mn of 500 to 100,000. By using the vinyl monomer (m5) having a polyester chain as an essential constituent unit, the organic fine particles (A) are fixed to the surface of the resin particle (Y1). The resin particles can be stabilized. When Mn is smaller than 500, the melting point or glass transition temperature is lowered and the stability is deteriorated. When Mn is larger than 100,000, the dispersibility of the organic fine particles (A) is deteriorated and the particle size distribution is deteriorated. Mn is preferably 600 to 70000, more preferably 700 to 50000.

In the present invention, the molecular weight [Mn and weight average molecular weight (Mw)] of the resin is measured using gel permeation chromatography (GPC) under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corporation]
Or, TSKgel GMHXL) 2 + TSKgel Multipore HXL-M [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLY made by Tosoh Corporation)
STYRENE) 12 points (Molecular weight 500 1050 2800
5970 9100 18100 37900 96400
190000 355000 1090000 2890000)

As the diol and dicarboxylic acid, those described below can be used.
The method for obtaining a polyester chain by reacting a diol with a dicarboxylic acid may be a conventional method for producing a polyester resin. Examples of the lactone ring-opening polymer include the same as the lactone ring-opening polymer (p) described later.

As a method for producing a vinyl monomer (m5) having a polyester chain,
(1) Introducing an unsaturated group capable of radical polymerization into a polyester chain by esterifying the above polyester with a hydroxyl group-containing vinyl monomer described later or a carboxyl group-containing vinyl monomer (including (m3) described later). how to,
(2) A method for producing a monomer having a urethane bond by introducing an unsaturated group capable of radical polymerization into a polyester chain by urethanizing the polyester and hydroxyl group-containing vinyl monomer with a polyisocyanate component described later,
(3) A method of introducing an unsaturated group capable of radical polymerization into a polyester chain by ring-opening polymerization of a monolactone having 3 to 12 carbon atoms, which will be described later, using a hydroxyl group-containing vinyl monomer as an initiator,
Etc.
Any of these methods may be used, but a preferable method is the method (1) or (2), which can be selected from many raw materials, and more preferably a monomer having a mild reaction condition and a urethane bond. (2) is obtained. When the vinyl monomer (m5) has a urethane bond, the crystallinity becomes high and the storage stability becomes good.
As (m5), a commercially available product having a corresponding composition can also be used.

  The content of (m5) in the resin in the vinyl resin (N3) is preferably 20 to 100%, more preferably 25 to 90%, and particularly preferably 30 to 80%. When the content of (m5) is 20% or more, the stability of the resin particles becomes good.

In the vinyl resin (N4), the resin has a silicone-containing vinyl monomer (m6) as an essential constituent unit. The content of (m6) in the resin is 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 5% by weight from the viewpoint of dispersibility in carbon dioxide (X). That's it. From the viewpoint of resin strength and heat resistant storage stability, it is 50% by weight or less, preferably 45% by weight or less, and more preferably 40% by weight or less.
Specific examples of (m6) include methacryl-modified silicone having a structure represented by the following formula.
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) aSi (CH ₃ ) ₂ R
However, a is an average value of 3 to 300, and R is an organic modified group containing a methacryl group. As examples of _{R, -C 3 H 6 OCOC (CH} 3) = CH 2 and the like.

  Examples of other vinyl monomers constituting the vinyl resin (N) include the following (1) to (10).

(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; 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 cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers other than (m3) and metal salts thereof:
C3-C30 unsaturated monocarboxylic acid, monoalkyl (C1-C24) ester of unsaturated dicarboxylic acid, for example, (meth) acrylic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, crotonic acid, Carboxyl group-containing vinyl monomers such as itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid monoalkyl ester and cinnamic acid. In addition, the said (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereafter. The alkyl chain constituting the monoalkyl (C1-24) ester preferably has a branched structure from the viewpoint of improving hydrolysis resistance.

(3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid And alkyl derivatives thereof having 2 to 24 carbon atoms, such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy- 3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxy Propanesulfonic acid, 2- (me ) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene) , Butylene: single, random or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and the following general Sulfate ester or sulfonic acid group-containing monomers represented by formulas (1-1) to (1-3); and salts thereof.

O- (AO) nSO ₃ H
｜
_{CH 2 = CHCH 2 -OCH 2 CHCH} 2 O-Ar-R (1-1)

CH = CH-CH ₃
｜
R-Ar-O- (AO) nSO 3 H (1-2)

CH ₂ COOR '
｜
HO ₃ SCHCOOCH ₂ CH (OH) CH ₂ OCH ₂ CH═CH ₂ (1-3)

(In the formula, R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different, and when they are different, they may be random or block. Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom.

(4) Phosphoric acid group-containing vinyl monomer and salt thereof:
(Meth) acryloyloxyalkyl (C1 to 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 metal salts, ammonium salts, and amine salts (including quaternary ammonium salts). Examples of the metal forming the metal salt include Al, Ti, Cr, Mn, Fe, Zn, Ba, Zr, Ca, Mg, Na, and K. Alkali metal salts and amine salts are preferred, and sodium salts, magnesium salts, aluminum salts, tertiary monoamines having 3 to 20 carbon atoms, and diamine salts are more preferred.

(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, etc.

(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, ( (Meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N- Arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, salts thereof, etc. (6-2) Amido group Vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide Nitrile group-containing vinyl monomers other than (6-3) (m4) such as N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone, etc .: cyanostyrene (6-4) quaternary ammonium cation group-containing vinyl monomers: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (Meth) acrylamide, quaternized product of tertiary amine group-containing vinyl monomers such as diallylamine (methyl chloride, dimethyl sulfate, benzyl chloride, which was quaternized with quaternizing agents such as dimethyl carbonate)
(6-5) Nitro group-containing vinyl monomer: nitrostyrene, etc.

(7) Epoxy group-containing vinyl monomer:
Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc.

(8) Halogen element-containing vinyl monomer:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, etc.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones other than (m1) and (m2):
(9-1) Vinyl esters such as vinyl butyrate, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 7 carbon atoms of alkyl group [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, etc.], dialkyl fumarate (dialkyl fumarate ester) (two alkyl groups are linear, branched or alicyclic having 2 to 8 carbon atoms. Dialkyl maleates (dialkyl maleates) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxy Alkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol [Mn300 ] Mono (meth) acrylate, polypropylene glycol (Mn500) mono (meth) acrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter abbreviated as EO) 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) Accel Relay Etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: 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.].
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, etc. (9-3) Vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone;
Vinyl sulfone, such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc.

(10) Other vinyl monomers:
Isocyanate group-containing monomer;
Isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, etc.

  Specific examples of the vinyl resin (N) include behenyl (meth) acrylate homopolymer, stearyl (meth) acrylate homopolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate copolymer. , (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) methyl acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- ( (Meth) acrylic acid-methyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-acrylonitrile copolymer, (2-perfluorododecyl) ethyl (meth) Acrylate-behenyl (meth) acrylate (Anhydrous) maleic acid copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate- (meth) acrylic acid copolymer, (2-perfluorododecyl) ethyl (meth) acrylate- Behenyl (meth) acrylate-styrene copolymer, (2-perfluorododecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-hydroxyethyl (meth) acrylate copolymer, (2-perfluorododecyl) ethyl (meta ) Acrylate-behenyl (meth) acrylate-acrylonitrile- (anhydrous) maleic acid-methyl (meth) acrylate-hydroxyethyl (meth) acrylate copolymer, behenyl (meth) acrylate- (anhydrous) maleic acid copolymer, behenyl ( (Meth) acrylate (Meth) methyl acrylate- (anhydrous) maleic acid copolymer, (2-perfluorodecyl) ethyl (meth) acrylate-behenyl (meth) acrylate-styrene-fumaric acid copolymer, vinyl monomer having a polyester chain (m5 ) Homopolymer, vinyl monomer having a polyester chain (m5)-(anhydrous) maleic acid copolymer, vinyl monomer having a polyester chain (m5)-(anhydrous) maleate- (2-perfluorobutyl) ethyl (meta ) Acrylate copolymer, vinyl monomer having polyester chain (m5)-(anhydrous) maleic acid-2,2,2-trifluoroethyl (meth) acrylate copolymer, vinyl monomer having polyester chain (m5) -behenyl (Meth) acrylate copolymer, behenyl (meth) acrylate ) Acrylic acid - (meth) acrylic-modified silicone copolymers, cyclohexyl (meth) acrylate - (meth) acrylic acid - (meth) acrylic-modified silicone copolymers.

  As a manufacturing method of vinyl resin (N), the polymerization method of well-known vinyl monomers, such as solution polymerization, block polymerization, suspension polymerization, is mentioned.

Among the crosslinkable amorphous resins, examples of the crosslinkable vinyl resin include copolymers of vinyl monomers including vinyl monomers having two or more vinyl polymerizable functional groups (such as divinylbenzene). It is done.
The crosslinkable polyester resin is a polycondensate of a polyol and a polycarboxylic acid, and at least a part of the polyol and / or the polycarboxylic acid, a trifunctional or higher functional polyol (d) and / or a trifunctional or higher functional group described later. Examples thereof include a polyester resin obtained by using the polycarboxylic acid (f).
Similarly, in the case of other resins, resins obtained using at least a part of the crosslinkable monomer are more preferable.

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

  The production method of the organic fine particles (A) containing the crystalline resin and / or the non-crystalline resin may be any production method. Specific examples thereof include a dry production method [materials constituting the organic fine particles (A). (T) is a dry pulverization method using a known dry pulverizer such as a jet mill], a wet manufacturing method [(t) powder is dispersed in an organic solvent, and a known wet disperser such as a bead mill or a roll mill is used. Wet pulverization, spray drying the solvent solution (t) with a spray dryer, etc., (t) supersaturation by adding a poor solvent or cooling to precipitate, and (t) solvent solution water or organic A method of dispersing in a solvent, a method of polymerizing the precursor of (t) in water by an emulsion polymerization method, a soap-free emulsion polymerization method, a seed polymerization method, a suspension polymerization method, or the like; In like method of polymerizing by dispersion polymerization or the like] is. Further, after the fine particles (A ′) of the amorphous resin are synthesized by the above method, the crystalline resin may be formed on the surface (A ′) by a known coating method, seed polymerization method, mechanochemical method or the like. Among these, from the viewpoint of ease of production of the organic 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 organic fine particles (A) may be used as they are, and in order to give adsorptivity to the resin particles (Y) or to modify the powder characteristics and electrical characteristics of the resin particles (Z) of the present invention, for example, The surface may be modified by 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 organic fine particles (A) and the resin particles (Y) has at least an acidic functional group on the surface and the other has at least a basic functional group on the surface.

  The organic fine particles (A) and the resin particles (Y) 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 organic fine particles (A) and the resin particles (Y) are at least a crystalline resin or a non-crystalline resin or a resin (B) constituting (A) in order to impart an acidic functional group or basic functional group to the surface thereof. A resin having an acidic functional group or a basic functional group may be used, or surface treatment may be performed to impart these functional groups to the organic fine particles (A) and the resin particles (Y).

  Examples of the crystalline resin or non-crystalline resin 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). And vinyl resins copolymerized.

  Examples of the crystalline resin or non-crystalline resin 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).

  The particle size of the organic fine particles (A) is smaller than the particle size of the resin particles (Y). The value of the particle size ratio [volume average particle diameter of organic fine particles (A) / [volume average particle diameter of resin particles (Z) obtained by the production method of the present invention]] is preferably 0.001 to 0.3. Preferably it is 0.002-0.2, More preferably, it is 0.003-0.1, Most preferably, it is 0.01-0.08. Within the above range, (A) is efficiently adsorbed on the surface of (Y), so the particle size distribution of the resulting resin particles (Z) becomes narrow.

  The volume average particle diameter of the organic fine particles (A) is not particularly limited as long as the resin particles (Z) can be dispersed, but is preferably 30 to 1000 nm, and more preferably 50 to 500 nm. If it is this range, the dispersibility of the resin particle (Z) in (X) will improve.

  In the present invention, the volume average particle size and the number average particle size are determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba, Ltd.), a laser particle size distribution measuring device (for example, LA-920: It can be measured by Horiba Seisakusho, Multisizer III (Coulter), ELS-800 (made by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system.

As the carbon dioxide (X) used in the production method of the present invention, a liquid state and a supercritical state can be used, but a supercritical state is preferable.
Here, carbon dioxide in a liquid state is a triple point of carbon dioxide (temperature = −57 ° C., pressure = 0.5 MPa) and carbon dioxide on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. This represents carbon dioxide, which is a temperature / pressure condition of a portion surrounded by a gas-liquid boundary line passing through a critical point (temperature = 31 ° C., pressure = 7.4 MPa), an isotherm of critical temperature, and a solid-liquid boundary line. On the other hand, carbon dioxide in a supercritical state represents carbon dioxide that is at a temperature / pressure condition higher than the critical temperature. The pressure in the present invention indicates the total pressure in the case of a mixed gas of two or more components.

Carbon dioxide (X) may contain other substances (u) as appropriate in order to adjust physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. Examples thereof include inert gases such as nitrogen, helium, argon and air.
The weight fraction of (X) in the total of (X) and the other substance (u) is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

The resin (B) used in the production method of the present invention is a resin composed of a crystalline part (a) having a lactone ring-opening polymer (p) as essential components and an amorphous part (b), Specifically, it is obtained by bonding a resin constituting the crystalline part (a) and a resin constituting the non-crystalline part (b).
Below, resin which comprises a crystalline part (a) is demonstrated.
The resin constituting the crystalline part (a) is not particularly limited as long as the lactone ring-opening polymer (p) is an essential constituent and has crystallinity. From the viewpoint of heat-resistant storage stability, the melting point (m) is preferably in the range of 30 to 120 ° C, more preferably 40 to 100 ° C.

As the lactone ring-opening polymer (p), a monolactone having 3 to 12 carbon atoms (one ester group in the ring) monomer in the presence of a catalyst, if necessary, using a polyol containing diol as an initiator. Examples thereof include those obtained by ring-opening polymerization and having a hydroxyl group at the terminal. In addition, (p) may be modified at its terminal so as to become, for example, a carboxyl group.
Examples of the polyol include diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. If necessary, a trifunctional or higher functional polyol is used in combination. May be.
Examples of the monolactone monomer include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Of these, ε-caprolactone is preferable from the viewpoint of crystallinity.
As the catalyst, for example, commonly used catalysts such as acids such as inorganic acids and organic acids, metal chlorides, oxides and hydroxides, fatty acid metal salts, and organometallic compounds can be used.
Of these, organic tin compounds (dibutyltin oxide, methylphenyltin oxide, etc.), organic titanium compounds (tetra-n-propyl titanate, tetraisopropyl titanate, etc.) and organic halogenated tin compounds (monobutyltin trichloride, etc.) are preferred.
The addition amount of the catalyst is preferably 0.1 to 5000 ppm with respect to the entire reaction system. The lactone ring-opening polymer (p) can be obtained by polymerization at a reaction temperature of 100 to 230 ° C., preferably in an inert atmosphere.
The ring-opening polymerization reaction may be performed without a solvent, or a reaction solvent may be used. As the reaction solvent, one or more known organic solvents such as toluene, benzene, ethylbenzene, hexane and pentane can be used.

The molecular weight of the lactone ring-opening polymer (p) is preferably such that the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 1000 to 80000. The glass transition temperature (Tg) is preferably -100 to 40 ° C, more preferably -80 to 0 ° C. The melting point (m) is preferably 40 to 100 ° C.
(P) may be a commercially available product. For example, H1P, H5, H7 of the Placel series manufactured by Daicel Chemical Industries, Ltd. (both m = about 60 ° C., Tg = about −60 ° C.) Crystalline polycaprolactone), 240 (m = 58-61 ° C., Mw 10000), 230 (m = 55-58 ° C., Mw 6300), 220 (m = 45-55 ° C., Mw 4000), 210 (m = 46-48 ° C. , Mw1900).

The resin constituting the crystalline part (a) has the lactone ring-opening polymer (p) as an essential component and is not particularly limited as long as it has crystallinity, and the lactone ring-opening polymer (p) is a single resin. Alternatively, it may be a composite resin with another resin having crystallinity. Moreover, a mixed resin with other resin which has crystallinity may be sufficient.
As other resins having crystallinity used in the composite resin, polyester resin (excluding lactone ring-opening polymer), polyurethane resin, polyurea resin can be introduced because it is easy to introduce a block of lactone ring-opening polymer (p). And one or more resins selected from polyamide resins are preferred, and polyester resins are more preferred.
Examples of the other resin having crystallinity used for the mixed resin include the same resins as the other resins used for the composite resin, preferably a polyester resin (excluding a lactone ring-opening polymer).

The crystalline polyester resin is preferably a polyester resin synthesized from a polyol component containing a diol and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polycarboxylic acid may be used in combination.
The crystalline polyurethane resin is preferably a polyurethane resin synthesized from a polyol component containing a diol and a polyisocyanate component containing a diisocyanate. However, if necessary, trifunctional or higher functional polyols or trifunctional or higher functional polyisocyanates may be used in combination.
The crystalline polyamide resin is preferably a polyamide resin synthesized from a polyamine containing a diamine and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polycarboxylic acid may be used in combination.
The crystalline polyurea resin is preferably a polyurea resin synthesized from a polyamine containing a diamine and a polyisocyanate component containing a diisocyanate. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polyisocyanate may be used in combination.

  Polyol component, polycarboxylic acid component, polyisocyanate component, and polyamine component (each including three or more functional groups) used for crystalline polyester resin, crystalline polyurethane resin, crystalline polyamide resin, crystalline polyurea resin are shown respectively. .

  Among the polyol components, examples of the diol include a diol that does not contain an aromatic ring, a diol that contains an aromatic ring, and a diol having a functional group other than a hydroxyl group.

  Among the diols that do not contain an aromatic ring, examples of the aliphatic diol include a linear aliphatic diol, an aliphatic diol having a secondary hydroxyl group, and a branched aliphatic diol.

The straight-chain aliphatic diol means a straight-chain aliphatic diol having a primary hydroxyl group at the molecular end, and a straight-chain aliphatic diol having 2 to 36 carbon atoms (for example, ethylene glycol, 1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol). It is done.
Among these, considering availability, a linear aliphatic diol having 2 to 10 carbon atoms (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol) are preferred.

Examples of the aliphatic diol having a secondary hydroxyl group include aliphatic diols having a secondary hydroxyl group having 2 to 36 carbon atoms (for example, 1,2-propylene glycol).
Examples of the branched aliphatic diol include branched aliphatic diols having 2 to 36 carbon atoms (for example, neopentyl glycol and 2,2-diethyl-1,3-propanediol).

  Examples of diols containing no aromatic ring other than aliphatic diols include alkylene ether glycols having 4 to 36 carbon atoms (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol), carbon A alicyclic diol of 4 to 36 (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A), alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO) ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] addition products (number of added moles 1 to 30), polybutadiene diol, and the like.

  Examples of the diol containing an aromatic ring include AO (EO, PO, BO, etc.) addition products (addition mole number 2-30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.).

Examples of the diol having another functional group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkylol alkanoic acids having 6 to 24 carbon atoms [for example, 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid. 2,2-dimethyloloctanoic acid].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, sulfamic acid diol [N, N-bis ( 2-hydroxyalkyl) sulfamic acid (alkyl group having 1 to 6 carbon atoms) or an AO adduct thereof (AO includes EO or PO, such as 1 to 6 added moles of AO): for example, N, N-bis (2- Hydroxyethyl) sulfamic acid, and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct], bis (2-hydroxyethyl) phosphate, and the like.
Examples of neutralizing bases for these diols include tertiary amines having 3 to 30 carbon atoms (such as triethylamine) and / or alkali metals (such as sodium salts).

Examples of the trifunctional or higher (3 to 8 or higher) polyols include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof, for example, Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerol; sugars and derivatives thereof such as sucrose and methylglucoside; AO adducts (additions) of trisphenols (such as trisphenol PA) Mole number 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymer of hydroxyethyl (meth) acrylate and other vinyl monomers, etc. ]; Etc.
Of these, preferred are AO adducts of 3 to 8 or higher polyhydric aliphatic alcohols and novolak resins.

  As a polyol component, it is preferable that content of a linear aliphatic diol is 80 mol% or more of a polyol component, More preferably, it is 90 mol% or more. If it is 80 mol% or more, the crystallinity of the resin is improved and the melting point is increased, so that the heat resistant storage stability is good.

  Among the polycarboxylic acid components, dicarboxylic acids include aliphatic dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); 6-40 alicyclic dicarboxylic acids [dimer acid (dimerized linoleic acid), etc.], C4-C36 alkene dicarboxylic acid (dodecenyl succinic acid, pentadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.) ); Aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.) .

Examples of the tri- or higher functional (3- to 6-valent or higher) polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as dicarboxylic acid and polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a C1-C4 lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The polycarboxylic acid component is preferably an aliphatic dicarboxylic acid (particularly linear carboxylic acid), an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid, and more preferably from the viewpoint of crystallinity and availability. Adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, and isophthalic acid.

  Among the polyisocyanate components, the diisocyanate includes an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, and an oil having 4 to 15 carbon atoms. Cyclic diisocyanates, araliphatic diisocyanates having 8 to 15 carbon atoms, modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone groups And the like, and mixtures of two or more thereof. Moreover, you may use trifunctional or more (3-8 valence or more) polyisocyanate together as needed.

  Specific examples of aromatic diisocyanates and trivalent or higher aromatic polyisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), Examples include crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like. .

  Specific examples of the aliphatic diisocyanate and the trivalent or higher aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, lysine diisocyanate, 2 , 6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, and the like.

  Specific examples of the alicyclic diisocyanate and the trivalent or higher alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate ( Hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic diisocyanate and the tri- or higher valent araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate ( TMXDI).

  Among these polyisocyanate components, 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, hydrogenated MDI, and IPDI.

As an example of a polyamine component, as aliphatic diamines (C2-C18),
[1] Aliphatic diamine {C2-C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) diamine [diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]};
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substitutes [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2, 5-hexamethylenediamine, methyliminobispropylamine, etc.];
[3] Alicyclic or heterocyclic-containing aliphatic diamine {alicyclic diamine (C4 to C15) [1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene Dianiline), etc.], heterocyclic diamines (C4-C15) [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane etc.];
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.);

As aromatic diamines (C6-C20),
[1] Unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine) , Diaminodiphenylsulfone, benzidine, thiodianiline, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, and the like;
[2] Aromatic diamines having a nucleus-substituted alkyl group [C1-C4 alkyl group such as methyl, ethyl, n- and i-propyl, butyl], such as 2,4- and 2,6-tolylenediamine, crude tri Rangeamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2, 4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 4,4′-diamino-3,3′-dimethyldiphenylmethane, etc.), and mixtures of these isomers in various proportions;
[3] Aromatic diamine [methylene bis-o-chloroaniline, 4-chloro-o] having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy and ethoxy; nitro group, etc.) -Phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5- Nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline, etc.];
[4] Aromatic diamine having a secondary amino group [partial or partial -NH ₂ of the aromatic diamine of the above [1] to [3] is —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl Etc.] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].

  In addition to these, the polyamine component is obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (eg alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

The proportion of the lactone ring-opening polymer (p) in the composite resin constituting the crystalline part (a) is preferably 10% or more, more preferably 15 to 95%, particularly preferably 20 to 90%.
When a mixed resin of (p) and another resin is used as the crystalline part (a), the proportion of (p) in the mixed resin is preferably 10% or more, more preferably 15 to 95%, particularly Preferably it is 20 to 90%.

  The method of combining the lactone ring-opening polymer (p) with the crystalline polyester resin, the crystalline polyurethane resin, the crystalline polyurea resin, and the crystalline polyamide resin is combined in consideration of the reactivity of the functional group contained in each. Whether or not an agent (coupling agent) is used is selected, and when it is used, a binder suitable for the functional group contained can be selected and bonded to form a composite resin.

When a binder is not used when preparing a composite resin, for example, ring-opening polymerization of a lactone monomer in the presence of a crystalline polyester resin, a crystalline polyurethane resin, a crystalline polyurea resin, a crystalline polyamide resin, or a mixture thereof. The method of doing is mentioned.
Other examples include a method in which a lactone ring-opening polymer (p) is first prepared, and the reaction between the functional group contained in (p) and the functional group contained in the other resin is advanced while heating and reducing pressure as necessary. . 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.
By using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, acid anhydride, polyfunctional epoxy or the like as a binder, and performing a dehydration reaction or an addition reaction, the crystalline part (a) which is a composite resin is obtained. can get.
Examples of the polyvalent carboxylic acid and acid anhydride include those similar to the polycarboxylic acid component. Examples of the polyhydric alcohol include those similar to the polyol component. Examples of the polyvalent isocyanate include the same polyisocyanate components.
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 of AO adduct of hydrogenated bisphenol A, diol (ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexanediol, cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, etc.) diglycidyl ether, trimethylolpropane 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 producing the composite resin, as examples of the dehydration reaction, when the lactone ring-opening polymer (p) and other crystalline resins forming the composite resin both have a hydroxyl group, these hydroxyl groups are bound as a binder. (For example, reaction which couple | bonds with polyvalent 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 crystalline part (a) which is a composite resin.

  An example of the addition reaction is a case where the lactone ring-opening polymer (p) and the other resin forming the composite resin both have a hydroxyl group at the terminal, and these are bonded with a binder (for example, a polyvalent isocyanate) In addition, when one of the lactone ring-opening polymer (p) and the other resin forming the composite resin has a hydroxyl group at the terminal and the other is a resin having an isocyanate group at the terminal, these are used without using a binder. The reaction which couple | bonds is mentioned. In this case, for example, the lactone ring-opening polymer (p) and other resins forming the composite resin are dissolved in a solvent that can be dissolved, and if necessary, a binder is added, and the reaction temperature is 80 ° C. to 150 ° C. The crystalline part (a) which is a composite resin is obtained.

Examples of the resin constituting the amorphous part (b) include polyester resins (including lactone ring-opening polymers), polyurethane resins, polyurea resins, polyamide resins, and vinyl resins.
Of these, polyester resins (including lactone ring-opening polymers), polyurethane resins, polyurea resins, polyamide resins, and composite resins thereof are preferred, and polyurethane resins and polyester resins are more preferred.

Similar to the crystalline part (a), the polyester resin is preferably a polyester resin synthesized from a polyol component containing a diol and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polycarboxylic acid can be used in combination.
The polyurethane resin is preferably a polyurethane resin synthesized from a polyol component containing a diol and a polyisocyanate component containing a diisocyanate. However, if necessary, a trifunctional or higher functional polyol or a trifunctional or higher functional polyisocyanate can be used in combination.
The polyurea resin is preferably a polyurea resin synthesized from a polyamine containing a diamine and a polyisocyanate component containing a diisocyanate. However, if necessary, trifunctional or higher functional polyamine or trifunctional or higher functional polyisocyanate can be used together.
The polyamide resin is preferably a polyamide resin synthesized from a polyamine containing a diamine and a polycarboxylic acid component containing a dicarboxylic acid. However, if necessary, a trifunctional or higher functional polyamine or a trifunctional or higher functional polycarboxylic acid can be used in combination.
Monomers constituting the non-crystalline polyester resin, non-crystalline polyurethane resin, non-crystalline polyamide resin, and non-crystalline polyurea resin include the polyol component, the polycarboxylic acid component, the polyisocyanate component, and the polyamine component. The thing similar to what was shown as a specific example is mentioned, What kind of combination may be sufficient if it becomes non-crystalline resin.

The glass transition temperature (Tg) of the resin constituting the non-crystalline part (b) is preferably 40 to 250 ° C., more preferably 50 to 240 ° C., and particularly preferably 60 to 230 ° C. from the viewpoint of heat-resistant storage stability. .
Here, the glass transition temperature is a differential scanning calorimeter (DSC20 manufactured by Seiko Denshi Kogyo Co., Ltd., RDC220 manufactured by SII Nano Technology Co., Ltd.) in accordance with JIS K7122 (1987) “Method for measuring the transition heat of plastic”. Etc.).

The bond between the resin constituting the crystalline part (a) and the resin constituting the non-crystalline part (b) takes into account the reactivity of the respective terminal functional groups of the resin constituting (a) and (b). Whether to use a binder (coupling agent) or not, and if so, select a binder suitable for the terminal functional group, bond (a) and (b), and block polymer It can be set as resin (B) which is.
In addition, when a mixture of resin (B) and unreacted (a) and / or (b) [preferably a mixture of (B) and (a)] is obtained by the above method, the mixture is used as it is as the resin of the present invention. You may use for the manufacturing method of particle | grains.

When the binder is not used, the reaction between the terminal functional group of the resin forming (a) and the terminal functional group of the resin forming (b) is advanced while heating and reducing pressure as necessary. 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.
By using polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, acid anhydride, polyfunctional epoxy or the like as a binder, dehydration reaction or addition reaction is performed, so that crystalline part (a) and non-crystalline part By combining (b), the resin (B) is obtained.
Specific examples of these binders and bonding methods include those described above.

  The resin (B) composed of the crystalline part (a) and the amorphous part (b) is preferably a crystalline resin, and the melting point (m) is preferably 40 ° C. from the viewpoint of heat-resistant storage stability. Above, more preferably 50 ° C. or higher, particularly preferably 55 ° C. or higher. Moreover, from a viewpoint of a melt characteristic, 110 degrees C or less is preferable, More preferably, it is 100 degrees C or less, Most preferably, it is 90 degrees C or less.

The ratio (s / m) between the softening point (s) [° C.] and the melting point (m) [° C.] of the resin (B) is preferably 0.8 to 1.55, more preferably 0.85. 1.2, particularly preferably 0.85 to 1.15. Within this range, image degradation is less likely to occur when used as toner particles. The softening point (s) is a value measured as follows.
<Softening point>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

In the viscoelastic properties of the resin (B), the following [Condition 1] is preferably satisfied, and the following [Condition 1-2] is more preferably satisfied. [Condition 1] G ′ (m + 20) = 50 to 1 × 10 ⁶ [Pa]
[Condition 1-2] G ′ (m + 20) = 100 to ⁵ × 10 ⁵ [Pa]
[G ′: storage elastic modulus [Pa]]
When G ′ at (m + 20) ° C. is 50 Pa or more, when used for toner particles, hot offset hardly occurs even at low temperature fixing, and the fixing temperature range is widened. Further, if it is 1 × 10 ⁶ [Pa] or less, the viscosity is liable to be fixed on the low temperature side, and the fixing property at low temperature is improved.
The measured dynamic viscoelasticity (storage elastic modulus G ′, loss elastic modulus G ″) is measured using a dynamic viscoelasticity measuring device RDS-2 manufactured by Rheometric Scientific, under a frequency of 1 Hz. The measurement temperature range is 30. By measuring the melt viscoelasticity between these temperatures at a temperature between 200 ° C. and 200 ° C., it can be obtained as a curve of temperature-G ′ and temperature-G ″.
The resin (B) satisfying [Condition 1] can be obtained by adjusting the ratio of the crystalline component in the composition constituting (B), adjusting the resin molecular weight, or the like. For example, when the ratio of the crystalline part (a) or the ratio of the crystalline component is increased, the value of G ′ (m + 20) decreases. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like. Also, the value of G ′ (m + 20) is decreased by decreasing the resin molecular weight.

The melting start temperature (x) of the resin (B) is preferably within the temperature range of (m ± 20) ° C. (m is the melting point), more preferably within the temperature range of (m ± 15) ° C., particularly preferably It is within the temperature range of (m ± 10) ° C. Specifically, (x) is preferably 30 to 100 ° C, more preferably 40 to 80 ° C. The melting start temperature (x) is a value measured as follows.
<Melting start temperature>
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. After extruding from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and after a slight increase of the piston due to thermal expansion of the sample, the piston again Is read from the graph, and this value is taken as the melting start temperature.

The resin (B) preferably satisfies the following [Condition 2], more preferably satisfies [Condition 2-2] with respect to the loss modulus G ″ and the melting start temperature (x), and [Condition 2]. −3] is particularly preferable, and [Condition 2-4] is most preferably satisfied.
[Condition 2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.0
[G ": Loss elastic modulus [Pa]]
[Condition 2-2] | LogG ″ (x + 20) −LogG ″ (x) |> 2.5
[Condition 2-3] | LogG ″ (x + 15) −LogG ″ (x) |> 2.5
[Condition 2-4] | LogG ″ (x + 10) −LogG ″ (x) |> 2.5
When the melting start temperature (x) of the resin (B) is within the above range and [Condition 2] is satisfied, the resin has a low viscosity reduction speed. The same image quality can be obtained on the side. Moreover, the process from the start of melting to the fixable viscosity is fast, which is advantageous for obtaining excellent low-temperature fixability. [Condition 2] is an index of the sharp melt property of the resin, which indicates how fast it can be fixed with less heat, and is obtained experimentally.
The resin (B) satisfying the preferable range of the melting start temperature (x) and [Condition 2] can be obtained by adjusting the ratio of the crystalline component in the constituent components of (B). For example, when the ratio of the crystalline component is increased, the temperature difference between (m) and (x) is decreased.

Further, in the viscoelastic properties of the resin (B), the ratio of the loss elastic modulus G ″ at (m + 30) ° C. to the loss elastic modulus G ″ at (m + 70) ° C. [G ″ (m + 30) / G ″ (m + 70)] is 0. It is preferably 0.05 to 50, and more preferably 0.1 to 10 [m: melting point of (B)].
By maintaining the ratio of the loss elastic modulus within the above range, when the toner particles are used, a more stable image quality can be obtained in the fixing temperature region.
The resin (B) satisfying the above G ″ ratio can be obtained by adjusting the ratio of the crystalline component in the composition constituting (B), the molecular weight of the crystalline part (a), and the like. For example, when the ratio of the crystalline part (a) or the ratio of the crystalline component is increased, the value of [G ″ (m + 30) / G ″ (m + 70)] decreases. The molecular weight of the crystalline part (a) is decreased. Increasing the value decreases the value of [G ″ (m + 30) / G ″ (m + 70)]. Examples of the crystalline component include polyols having a linear structure, polyisocyanates, and the like.

The weight average molecular weight (Mw) of the resin (B) is preferably 5000 to 100,000, more preferably 6000 to 80000, and particularly preferably 8000 to 50000 from the viewpoint of melting characteristics.
As for Mw of the crystalline part (a) which comprises (B), 2000-80000 are preferable, More preferably, it is 3000-60000, Most preferably, it is 4000-50000.
Moreover, 500-50000 are preferable, as for Mw of the non-crystalline part (b) which comprises (B), More preferably, it is 750-20000, Most preferably, it is 1000-10000.
The Mw of the crystalline part (a) and the non-crystalline part (b) is determined by measuring the weight average molecular weight (Mw) of the resin constituting (a) and the resin constituting (b) before bonding. can get. In addition, (Mw) is measured on the said conditions using a gel permeation chromatography (GPC).

  The proportion of the crystalline part (a) in the resin (B) is preferably 30 to 95%, more preferably 40 to 90%, and particularly preferably 50 to 85%. Within this range, the crystallinity of the resin (B) is not impaired, and the heat resistant storage stability is good.

Resin (B) is a block resin composed of a crystalline part (a) and an amorphous part (b), and (a) and (b) are linearly bonded in the following format. It is preferable that both ends are resins of (a), and the average value n of the number of repeating units of {-(b)-(a)} is 0.5 to 3.5, more preferably n = 0. 0.7 to 2.0, particularly preferably n = 0.9 to 1.5.
(A) {-(b)-(a)} n
Specifically, the above formula shows that the crystalline part (a) and the non-crystalline part (b)
(A) [n = 0],
(A)-(b)-(a) [n = 1],
(A)-(b)-(a)-(b)-(a) [n = 2],
(A)-(b)-(a)-(b)-(a)-(b)-(a) [n = 3]
And the like, and mixtures thereof (except for those consisting only of n = 0). In addition, containing that whose n is 0 means containing resin which comprises a crystalline part (a) with resin (B).
When n is 3.5 or less, the crystallinity of the resin (B) is not impaired. Further, when n is 0.5 or more, the elasticity after melting of (B) is good, and when used for toner, hot offset hardly occurs during fixing, and the fixing temperature region becomes wider. Note that n is a calculated value obtained from the amount of raw material used [molar ratio of (a) and (b)]. Moreover, it is preferable that both ends of (B) are crystalline parts (a) from a viewpoint of the crystallinity degree of resin (B).
In addition, when both ends are non-crystalline parts (b), the crystallinity is lowered, so that the ratio of the crystalline parts (a) in (B) in order to give the resin (B) crystallinity. Is preferably 75% or more.

Examples of the solvent (S) used for the solution (L) in which the resin (B) is dissolved include ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl). Ethers, cyclic ethers, etc.), ester solvents (acetic acid esters, pyruvate esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohol solvents (methanol, ethanol, isopropanol, fluorine-containing alcohols, etc.) ), Aromatic hydrocarbon solvents (toluene, xylene, etc.), and aliphatic hydrocarbon solvents (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.
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-hydroxyisobutyric acid ester, lactate ester, and fluorine-containing alcohol, 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.

The solubility parameter (SP value) of the resin (B) is preferably 8 to 16, and more preferably 9 to 14. Moreover, 9-16 are preferable and, as for SP value of a solvent (S), More preferably, it is 10-15.
The SP value is expressed 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.
It is expressed by the square root of the ratio of the child volume.

The solution (L) of the resin (B) is produced by dissolving the resin (B) in the solvent (S).
The viscosity of the solution (L) at 40 ° C. is preferably 10 to 1,000,000 mPa · s, more preferably 500 to 500,000 mPa · s, and particularly preferably 100 to 200,000 mPa · s. . If it is this range, the dispersibility of the resin particle (Z) will improve.
The weight ratio of the resin (B) in the solution (L) is preferably 5 to 95%, more preferably 10 to 90%, and particularly preferably 15 to 85%. Within this range, the resin particles (Y) can be efficiently formed.

  Further, since the solution (L) of the resin (B) is dispersed in the carbon dioxide (X), it is preferable that the resin (B) has an appropriate viscosity at the temperature when mixed with the (X), and from the viewpoint of the particle size distribution, Is 100,000 mPa · s or less, more preferably 50,000 mPa · s or less. The solubility of the resin (B) in (X) is preferably 3% or less, more preferably 1% or less.

  The colorant dispersion (C) used in the production method of the present invention comprises a colorant (k), a dispersant (l) having a total acid value and amine value (mgKOH / g) of 20 or more and 250 or less, a solvent (S ), And carbon dioxide (X) in a liquid state or a supercritical state having a pressure of 2 MPa or more, and then expanded under reduced pressure to vaporize and remove (X), and a coloring having a median diameter of 1 μm or less It is a dispersion liquid in which the agent (k) is dispersed in the solvent (S).

As the colorant (k), known dyes and pigments can be widely used. Examples of the dye include monoazo, disazo, metal complex azo, anthraquinone, indigo, phthalocyanine, pyrazolone, stilbene, thiazole, quinoline, diphenylmethane, triphenyl Phenylmethane, acridine, xanthene, azine, thiazine, oxazine, polymethine, indophenol, perylene, etc., pigments include azo lake, insoluble azo, condensed azo, phthalocyanine, perylene, dioxazine, indigo, quinacridone , Isoindolinone, benzimidazolone, diketopyrrolopyrrole, organic pigments such as metal complexes, yellow iron oxide, bengara, carbon black, titanium dioxide, metal powder pigments, colored mica, etc., and mixtures thereof Raised It is.
Specific examples include carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Pigment Red, Carmine FB, Pigment Orange R, Lake Red 2G, rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, olasol brown B, and oil pink OP.

The dispersant (l) has a total acid value and amine value (unit: mg KOH / g, the same shall apply hereinafter) of 20 or more and 250 or less, preferably 30 or more and 250 or less, more preferably 35 or more and 220 or less. Preferably they are 40 or more and 210 or less. When it is less than 20 or exceeds 250, it becomes difficult to interact with the colorant (k), and the dispersibility is deteriorated.
In the present invention, the acid value of the dispersant (l) is measured by the method defined in JIS K0070 (1992 edition). The amine value is measured by the method defined in JIS K7237 (1996 edition).
Further, the dispersant (l) should have a peak in the molecular weight distribution in the range of at least 1,000 or more and 1,000,000 or less, and the peak molecular weight is preferably 1,050 or more and 100,000 or less, Preferably they are 1,100 or more and 30,000 or less, Especially preferably, they are 1,200 or more and 10,000 or less. By having a peak in this range, the dispersant (l) is more easily dissolved in the solvent (S) and can be efficiently adsorbed on the surface of the colorant (k). Moreover, (l) may have a peak in the range of less than 1,000 (preferably 200 to 990) in addition to the above peak.
In the present invention, the molecular weight distribution of the dispersant (l) is measured under the above conditions using gel permeation chromatography (GPC).

  The composition of the dispersant (l) is not particularly limited as long as it has the total value of the above acid value and amine value, but a polymerized polymer having an acidic or basic functional group, or a salt of a polymer compound Is preferred. Examples thereof include vinyl copolymers having acidic groups and / or basic groups, polyesters, and polyolefins, and alkylammonium salts of polymer compounds having acidic groups. By having a functional group, it becomes easier to adsorb on the surface of the colorant (k), and the dispersion stabilization of the colorant (k) in the solvent (S) can be promoted.

Among the dispersants (l), for example, vinyl copolymers having acidic groups and / or basic groups include vinyl monomers having acidic groups and / or vinyl monomers having basic groups, and other vinyls if necessary. A monomer copolymer may be mentioned.
Examples of vinyl monomers having an acidic group include monocarboxylic acids [having 3 to 15 carbon atoms, such as (meth) acrylic acid, crotonic acid, cinnamic acid], dicarboxylic acids [having 4 to 15 carbon atoms, such as (anhydrous) maleic acid, fumaric acid. Acid, itaconic acid, citraconic acid], dicarboxylic acid monoester [monoalkyl (carbon number 1 to 18) ester of the above dicarboxylic acid, such as maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, citraconic acid Carboxyl group-containing vinyl monomers such as monoalkyl esters], and sulfone group-containing vinyl monomers.
Examples of the vinyl monomer having a basic group include alkylamino group-containing (meth) acrylates having 1 to 18 carbon atoms, such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
Examples of other vinyl monomers include alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group such as methyl (meth) acrylate and butyl (meth) acrylate, and styrene.
For other resins, for example, a resin obtained from a monomer containing an acid group-containing monomer and / or a basic group-containing monomer is used.

  As the dispersant (l), a commercially available product having the total value of the acid value and the amine value may be used. Specific examples include DISPERBYK 106, 108, 145, BYK9076, 9077, and ANTI-TERRA-U100 manufactured by Big Chemie Japan, and SOLPERSE 21000, 24000, 28000, 32000, 33000, 36000, 41000, manufactured by Nippon Lubrizol. 54000, 56000, 71000 and the like.

  The solvent (S) is preferably one that dissolves the dispersant (1) under the use conditions, and examples thereof include those described above. Among these, ketone solvents, ether solvents and ester solvents are preferable, and ethyl acetate and acetone are more preferable.

  The pressure of carbon dioxide (X) is 2 MPa or more, preferably 3 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 15 MPa or less. In this pressure range, the carbon dioxide (X) penetrates by the colorant (k) and the colorant (k) is easily pulverized, and the dispersant (l) is carbon dioxide (X) and the solvent (S). It dissolves better in the mixed solution and is easily adsorbed on the surface of the colorant (k).

  The dispersant (l) is preferably one that dissolves in a mixture of carbon dioxide (X) and solvent (S) during the production of the dispersion. By dissolving, it becomes easy for the dispersant (l) to come into uniform contact with the surface of the colorant (k) and be adsorbed, thereby enhancing the dispersion stabilization effect.

  By mixing the colorant (k), the dispersant (l), the solvent (S) and carbon dioxide (X) having a pressure of 2 MPa or more, and then expanding under reduced pressure to vaporize and remove (X). A colorant dispersion (C) in which a colorant (k) having a median diameter of 1 μm or less is dispersed in a solvent (S) is obtained.

The order and method of mixing the colorant (k), the dispersant (l), the solvent (S), and the carbon dioxide (X) having a pressure of 2 MPa or more are not particularly limited. It is preferred to dissolve (l) and then mix with the colorant (k) and then introduce carbon dioxide (X) into the mixture.
The dispersant (l) is preferably used in an amount of 1 to 80%, more preferably 5 to 70%, and particularly preferably 10 to 50% based on the colorant (k). In this range, the dispersant (l) is effectively adsorbed on the entire surface of the colorant (k).
The amount of the solvent (S) is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight, and particularly preferably 3 to 50 parts by weight with respect to 1 part by weight of the colorant (k). Within this range, the colorant dispersion (C) can be obtained with a viscosity that is easy to handle.

  A mixture of the colorant (k), the dispersant (l), and the solvent (S) (hereinafter referred to as slurry) is charged into a pressure resistant container, and a desired pressure is applied by a pressurizing means such as a pump provided in the pressure resistant container. It is preferable that carbon dioxide (X) is introduced into the container until it reaches the point of mixing and mixed with the slurry. Since the slurry volume expands by introducing carbon dioxide (X), the initial charge amount of the slurry is preferably 10 to 60% by volume with respect to the volume of the container.

  The pressure vessel used for the production of the colorant dispersion (C) can withstand a maximum pressure of 2 MPa or more, and is equipped with equipment capable of stirring and mixing the slurry and carbon dioxide (X) in the vessel. What has the nozzle for slurry taking out in the lower part is preferable. The diameter of the nozzle is preferably about 0.5 to 5.0 mm, and it is preferable that the slurry after carbon dioxide (X) mixing can be ejected from the high pressure state into the atmosphere at once by opening and closing the needle valve or the ball valve.

After the introduction of carbon dioxide (X), the dispersant (l) is adsorbed to the colorant (k) by stirring for a while. The stirring time may be a minimum time during which the dispersant (l) can be adsorbed to the colorant (k), and is preferably stirred for about 10 to 30 minutes.
Moreover, the temperature at the time of stirring and mixing of the slurry and carbon dioxide (X) is preferably 15 to 120 ° C., more preferably, from the viewpoint of preventing aggregation of the colorant due to excessive temperature rise and adjusting the temperature of the slurry at the time of discharge. 30-100 ° C.

  After stirring, the valve is opened from the nozzle at the bottom of the container (preferably in a fully opened state), and the slurry is expanded under reduced pressure to atmospheric pressure at once, and carbon dioxide (X) is vaporized and removed, whereby a colorant having a median diameter of 1 μm or less ( A colorant dispersion (C) in which k) is dispersed in the solvent (S) is obtained. Since the slurry temperature is lowered by this decompression and expansion operation, the slurry before decompression and expansion may be heated to some extent (preferably 50 to 100 ° C.). By adjusting the temperature, it is possible to prevent moisture from being mixed due to a decrease in the temperature of the colorant dispersion (C) at the time of removal.

The mixing of the slurry and carbon dioxide (X) can be continuously performed by a line blend (in-line mixing) method, in addition to the method performed in the pressure vessel, improving productivity, stabilizing quality, and manufacturing. This is preferable from the viewpoint of space reduction.
Specific examples of the apparatus used for the line blending method include static inline mixers such as static mixers, inline mixers, lamond super mixers, and sulzer mixers, and stirring inline mixers such as vibrator mixers and turbo mixers. It is done. There is no limitation on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand a maximum pressure of 2 MPa or more.
The outlet of the apparatus used for the line blending method is preferably provided with a nozzle for removing the slurry, similar to the pressure vessel.

As a mixing method of the slurry and carbon dioxide (X), first, carbon dioxide (X) is introduced into an apparatus for performing line blending to adjust the pressure to 2 MPa or more, and then the slurry is introduced to (X). Is preferred. The pressure (X) is preferably the same pressure as that used in the pressure vessel.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.
The mixture after line blending is expanded under reduced pressure to atmospheric pressure, and carbon dioxide (X) is vaporized and removed to disperse the colorant (k) having a median diameter of 1 μm or less in the solvent (S). A liquid (C) is obtained.

  The colorant (k) in the colorant dispersion (C) preferably has a median diameter of 0.8 μm or less, more preferably 0.6 μm or less, and particularly preferably 0.01 μm or more and 0.00. That is, there are no particles of 5 μm or less and 1 μm or more. In the present invention, the median diameter is determined by a dynamic light scattering particle size distribution measuring device (for example, LB-550: manufactured by Horiba, Ltd.), a laser particle size distribution measuring device (for example, LA-920: manufactured by Horiba, Ltd.), and Multisizer III ( Beckman Coulter, Inc.).

  The wax dispersion (D) used as necessary in the production method of the present invention comprises a mixture having a temperature equal to or higher than the melting point of (w) containing the wax (w) and the solvent (S), and carbon dioxide in a liquid state or a supercritical state. The wax (w) obtained by mixing (X) and then expanding under reduced pressure to precipitate (w) below the melting point of (w) and vaporize (X) to remove (w) having a median diameter of 1 μm or less. ) Is a dispersion liquid dispersed in the solvent (S).

Examples of the wax (w) include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, fatty acid ester having 30 to 50 carbon atoms, and mixtures thereof.
Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.
Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax.
Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid. Examples of the fatty acid ester having 30 to 50 carbon atoms include stearyl stearate.
The melting point of the wax (w) is preferably 40 to 120 ° C, more preferably 50 to 110 ° C.

The solvent (S) is not particularly limited as long as it is difficult for the wax (w) to dissolve at room temperature, and examples thereof include those described above. Among these, ketone solvents, ether solvents and ester solvents are preferable, and ethyl acetate and acetone are more preferable.
The solubility of the wax (w) in the solvent (S) is preferably 5% or less at 25 ° C., more preferably 2% or less.

You may use additives, such as a dispersing agent, as needed with a wax (w).
The dispersant is not particularly limited, and known ones can be used. A unit having high compatibility with the wax (w) and a unit having high compatibility with the resin (B) exist as a block body. And polymers and oligomers to be used. A polymer or oligomer in which one of the unit having high compatibility with the wax (w) and the unit having high compatibility with the resin (B) is grafted on the other [for example, a vinyl monomer in the presence of the wax (w) Obtained by polymerization), unsaturated hydrocarbons (such as ethylene, propylene, butene, styrene, and α-methylstyrene), and α, β-unsaturated carboxylic acids or esters thereof or anhydrides thereof (acrylic acid, methacrylic acid). Acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like), vinyl resin and polyester resin block or graft copolymers, and the like.

  The pressure of carbon dioxide (X) is 2 MPa or more, preferably 3 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 15 MPa or less. Within this pressure range, carbon dioxide (X) permeates with the wax (w) and the wax (w) is easily crushed.

  Carbon dioxide (X) having a pressure of 2 MPa or more is mixed with a mixture having a temperature equal to or higher than the melting point of (w) containing the wax (w) and the solvent (S), and then expanded under reduced pressure to obtain a melting point of (w). The wax dispersion (D) in which the wax (w) having a median diameter of 1 μm or less is dispersed in the solvent (S) is obtained by precipitating (w) and evaporating (X) as follows. It is done.

When producing the wax dispersion (D), first, the wax (w) and the solvent (S) are mixed. The amount of the solvent (S) is preferably 1 to 100% based on the wax (w), more preferably 5 to 80%, and particularly preferably 10 to 60%. Within this range, the wax dispersion (D) can be obtained with a viscosity that is easy to handle.
There is no particular limitation on the procedure for mixing (w) and (S) to obtain a mixture having a temperature equal to or higher than the melting point of (w) [preferably a solvent (S) solution of wax (w)]. And (S) may be heated after mixing, or the other may be introduced into heated (w) or (S).
In addition, when using additives, such as said dispersing agent, adding to this mixture is preferable.

The method of mixing the mixture of the wax (w) and the solvent (S) (hereinafter referred to as the (w) -containing mixture) and carbon dioxide (X) having a pressure of 2 MPa or more is not particularly limited, but carbon dioxide (X ) Is preferably introduced.
As a preferred specific method, the (w) containing mixture is charged into a pressure-resistant container, and when the temperature of the (w) containing mixture is lower than the melting point of the wax (w), the mixture is heated to a temperature equal to or higher than the melting point (w ). After (w) is completely melted, carbon dioxide (X) is introduced into the container by a pressurizing means such as a pump provided in the pressure resistant container until the desired pressure is reached, and mixed with the mixture containing (w). Since the volume of the mixture expands by introducing carbon dioxide (X), the initial charge amount of the (w) -containing mixture is preferably 10 to 60% by volume with respect to the volume of the container.

  The pressure vessel used for the production of the wax dispersion (D) can withstand a maximum pressure of 2 MPa or more, and is equipped with equipment capable of stirring and mixing the (w) -containing mixture and carbon dioxide (X) in the vessel. Further, it is preferable that the container is provided with a nozzle for taking out at the lower part of the container. The diameter of the nozzle is about 0.5 to 5.0 mm, and the mixture containing carbon dioxide (X) after mixing with carbon dioxide (X) can be ejected from the high pressure state into the atmosphere at once by opening and closing the needle valve or the ball valve. Those are preferred.

After introducing carbon dioxide (X), (X) is sufficiently permeated into the mixture containing (w) by stirring for a while. The stirring time may be a minimum time during which carbon dioxide (X) is sufficiently mixed with the whole, and is preferably stirred for about 10 to 30 minutes. By sufficiently mixing (X), the viscosity of the (w) -containing mixture can be lowered, and the wax (w) can be effectively made fine by expansion under reduced pressure in the next step.
Moreover, the temperature at the time of stirring and mixing the (w) -containing mixture and carbon dioxide (X) is preferable from the viewpoint of preventing aggregation of (w) due to excessive temperature rise and adjusting the temperature of the (w) -containing mixture at the time of discharge. Is 15 to 120 ° C, more preferably 30 to 100 ° C.

  After stirring, the valve is opened from the nozzle at the bottom of the container (w) and the containing mixture is expanded to atmospheric pressure under reduced pressure. As a result, the temperature of the (w) -containing mixture is drastically lowered and becomes a temperature below the melting point of the wax (w), so that the dissolved wax (w) is deposited. Further, the carbon dioxide (X) is vaporized and removed to obtain a wax dispersion (D) in which the wax (w) having a median diameter of 1 μm or less is dispersed in the solvent (S). In this crystallization process by expansion under reduced pressure, the temperature of the mixture containing (w) is sufficiently lowered to sufficiently precipitate the wax (w), so the temperature of the mixture containing (w) before expansion under reduced pressure is the melting point of the wax (w). Alternatively, it is preferable to keep the temperature slightly higher than the melting point [preferably (melting point) to (melting point + 5) ° C.]. Moreover, as a method of expanding the mixture (w) under reduced pressure at a stretch, it is preferable to discharge from a high pressure by opening and closing a needle valve or a ball valve attached to the nozzle. The nozzle diameter is preferably 0.1 to 5 mm, more preferably 0.5 to 4 mm, and particularly preferably 1 to 3 mm.

(W) In addition to the method in which the contained mixture and carbon dioxide (X) are mixed in the above-described pressure vessel, continuous mixing by a line blend (in-line mixing) method may improve productivity and stabilize quality. From the standpoint of reducing the manufacturing space, etc.
Specific examples of the apparatus used for the line blending method include static inline mixers such as static mixers, inline mixers, lamond super mixers, and sulzer mixers, and stirring inline mixers such as vibrator mixers and turbo mixers. It is done. There is no limitation on the length and pipe diameter of the mixer portion of the apparatus and the number of mixing apparatuses (elements), but it must be able to withstand a maximum pressure of 2 MPa or more.
The outlet of the apparatus used for the line blending method is preferably provided with a nozzle for taking out the mixture, similar to the pressure vessel.

(W) As a method of mixing the containing mixture and carbon dioxide (X), first, carbon dioxide (X) is introduced into an apparatus for performing line blending, and the pressure is adjusted to 2 MPa or more, and then (w) containing It is preferred to introduce the mixture into (X). The pressure (X) is preferably the same pressure as that used in the pressure vessel.
The temperature at which line blending is performed is the same as in the case of mixing using the above-described pressure vessel. The residence time in the apparatus is not particularly limited as long as mixing is sufficiently performed, but is preferably 0.1 to 1800 seconds.
A wax dispersion liquid in which a wax (w) having a median diameter of 1 μm or less is dispersed in a solvent (S) by expanding the mixture after line blending under reduced pressure to atmospheric pressure and vaporizing and removing carbon dioxide (X) ( D) is obtained.

  The wax (w) in the wax dispersion (D) is preferably refined with a median diameter of 0.8 μm or less, more preferably 0.6 μm or less, particularly preferably 0.01 μm or more and 0.5 μm or less. In other words, there are no particles of 1 μm or more.

  In the method for producing resin particles of the present invention, in the dispersion step of dispersing the solution (L) of the resin (B) in carbon dioxide (X) in which the organic fine particles (A) are dispersed, the following dispersion stabilizer (v ) Can be used. The dispersion stabilizer (v) is a compound having at least one of a dimethylsiloxane group and a functional group containing fluorine. Further, it preferably has a chemical structure having an affinity for the resin (B) together with a dimethylsiloxane group and a fluorine-containing group having an affinity for carbon dioxide.

For example, when the resin (B) is a vinyl resin, the dispersion stabilizer (v) is preferably a vinyl resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
Examples of the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group include the methacryl-modified silicone.

  Specific examples of the fluorine-containing monomer (M1-2) include perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE); perfluoro (alkyl vinyl ether) ) (PFAVE), perfluoro (1,3-dioxole), perfluoro (2,2-dimethyl-1,3-dioxole) (PFDD), perfluoro- (2-methylene-4-methyl-1,3- Peroxo vinyl ethers such as dioxolane) (MMD), perfluorobutenyl vinyl ether (PFBVE); vinylidene fluoride (VdF), trifluoroethylene, 1,2-difluoroethylene, vinyl fluoride, trifluoropropylene, 3, 3, 3-trifluoro-2-to Hydrogen-containing fluoroolefins such as fluoromethylpropene, 3,3,3-trifluoropropene, perfluoro (butyl) ethylene (PFBE); 1,1-dihydroperfluorooctyl acrylate (DPFOA), 1,1-dihydroper Fluorooctyl methacrylate (DPFOMA), 2- (perfluorooctyl) ethyl acrylate (PFOEA), 2- (perfluorooctyl) ethyl methacrylate (PFOEMA), 2- (perfluorohexyl) ethyl methacrylate (PFHEMA), 2- (Per Polyfluoroalkyl (meth) acrylates such as fluorobutyl) ethyl methacrylate (PFBEMA); α-fluorostyrene, β-fluorostyrene, α, β-difluorostyrene, β, β-difluorostyrene α, β, β-trifluorostyrene, α-trifluoromethylstyrene, 2,4,6-trifluoro (trifluoromethyl) styrene, 2,3,4,5,6-pentafluorostyrene, 2,3,4 , 5,6-pentafluoro-α-methylstyrene, 2,3,4,5,6-pentafluoro-β-methylstyrene and the like.

When the resin (B) is a urethane resin, the dispersion stabilizer (v) is preferably a urethane resin having as a structural unit a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine. .
(M1-1) is preferably a polysiloxane having a functional group containing active hydrogen, such as amino-modified silicone, carboxyl-modified silicone, carbinol-modified silicone, or mercapto-modified silicone. (M1-2) includes 2,2-bis (4-hydroxyphenyl) hexafluoropropane, fluorine-containing polyols such as 3,3,4,4-tetrafluoro-1,6-hexanediol, fluorine-containing groups ( Fluorine compound having a functional group containing active hydrogen such as poly) amine, fluorine-containing group (poly) thiol, bis (isocyanatomethyl) perfluoropropane, bis (isocyanatomethyl) perfluorobutane, bis (isocyanatomethyl) Fluorine-containing (poly) isocyanates such as perfluoropentane and bis (isocyanatomethyl) perfluorohexane are preferred.

  When the resin (B) has an acid value, the dispersion stabilizer (v) preferably has an amino group from the viewpoint of dispersibility. The acid value of the resin (B) is preferably 1 to 50, more preferably 3 to 40, and most preferably 5 to 30. The amino group may be primary, secondary, or tertiary, and is introduced at any position on the side chain, one end, both ends, or both ends of the side chain of a compound containing a fluorine-containing group or a dimethylsiloxane group. May be used.

  As the dispersion stabilizer (v), for example, a monomer having a dimethylsiloxane group (or reactive oligomer) (M1-1) and / or a monomer (M1-2) containing fluorine, and the resin (B) described above are used. A copolymer with a constituting monomer (for example, a copolymer of methacryl-modified silicone and methyl methacrylate, a copolymer of heptafluorobutyl methacrylate and methyl methacrylate, or the like) is preferable. The form of copolymerization may be random, block or graft, but block or graft is preferred.

  When the resin (B) has an acid value, the organic fine particles (A) preferably have an amino group on the particle surface from the viewpoint of dispersion stability. The amino group may be any of primary, secondary, and tertiary, and the form in which the amino group is incorporated is not particularly limited. For example, the amino group-containing compound is dispersed or impregnated in the organic fine particles (A). A method of containing, a method of using a compound having an amino group as a component constituting the organic fine particles (A), a method of reacting an amino group-containing coupling agent on the surface of the organic fine particles (A), a surface of the organic fine particles (A) Examples thereof include a method for adsorbing an amino group-containing compound.

  From the viewpoint of dispersion stability, the addition amount of the dispersion stabilizer (v) is preferably 0.01 to 50%, more preferably 0.02 to 40%, particularly preferably 0. 0% with respect to the weight of the resin (B). 03 to 30%. The range of the preferable weight average molecular weight of the dispersion stabilizer (v) is 100 to 100,000, more preferably 200 to 50,000, and particularly preferably 500 to 30,000. Within this range, the dispersion stabilizing effect of (v) is improved.

  Other additives (filler, antistatic agent, charge control agent, ultraviolet absorber, oxidation agent) in the resin particles (Y) and resin particles (Z) containing the resin (B) obtained in the production method of the present invention An inhibitor, an antiblocking agent, a heat stabilizer, a flame retardant, etc.). The resin particles (Y) and (Z) may contain other additives by mixing the resin (B) or (B) solution (L) with the additives in advance and then adding the additives in (X). It is preferable to add and disperse the mixture.

  In the method for producing resin particles of the present invention, a solution in which resin (B) is dissolved in solvent (S) in carbon dioxide (X) in a liquid state or a supercritical state in which organic fine particles (A) are dispersed ( L), the colorant dispersion (C), and optionally the wax dispersion (D), to disperse the resin (B), the colorant (k), the solvent (S), and optionally the wax (w). Resin particles (Z1) in which organic fine particles (A) are fixed are formed on the surface of the resin particles (Y1) contained, (Z1) is treated with (X), and then carbon dioxide in a liquid state or a supercritical state ( X) and the solvent (S) are removed to produce resin particles (Z).

  In the production method of the present invention, any method may be used for dispersing the organic fine particles (A) containing the crystalline resin and / or the amorphous resin in carbon dioxide (X), for example, in a container ( A method in which A) and (X) are charged and (A) is directly dispersed in (X) by stirring, ultrasonic irradiation or the like, or a dispersion in which organic fine particles (A) are dispersed in a solvent (S). Examples include a method of introducing into (X).

  The weight ratio of the organic fine particles (A) to the weight of carbon dioxide (X) is preferably 50% or less, more preferably 30% or less, and particularly preferably 0.1 to 20%. If it is this range, a resin particle (Z1) can be manufactured efficiently.

  Examples of the solvent (S) for dispersing the organic fine particles (A) include those described above. From the viewpoint of dispersibility of the organic fine particles (A), an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.) and an ester solvent (ethyl acetate, butyl acetate, etc.) are preferable.

  The weight ratio (%) between the organic fine particles (A) and the solvent (S) is not particularly limited, but the organic fine particles (A) are preferably 50% or less, more preferably 30% or less with respect to the solvent (S). And particularly preferably 20% or less. Within this range, the organic fine particles (A) can be efficiently introduced into (X).

  There is no particular limitation on the method for dispersing the organic fine particles (A) in the solvent (S). However, the organic fine particles (A) can be dispersed in the solvent (S) and directly dispersed by stirring, ultrasonic irradiation or the like. Examples thereof include a method of crystallization by dissolving in a solvent (S) at a high temperature.

  In this manner, a dispersion (X0) in which (A) is dispersed in carbon dioxide (X) is obtained. As the organic fine particles (A), those having a swelling degree in the above-mentioned range and not stably dissolved in (X) but stably dispersed in (X) are preferable.

  The solution (L) in which the resin (B) is dissolved in the solvent (S), the colorant dispersion (C), and, if necessary, the wax dispersion (D), the organic fine particles (A) in carbon dioxide (X). When dispersing in the dispersed dispersion (X0), the colorant dispersion (C), the solution (L), and, if necessary, the wax dispersion (D) are mixed in advance, and the mixture is then mixed in (X0). It may be introduced into and dispersed in (X0), or separately in (X0), but (C) and (L) may be mixed with (D) if necessary before (X0) It is preferable to be dispersed. If it does so, a coloring agent (k) and wax (w) can be disperse | distributed more uniformly in resin (B).

  The amount of the colorant dispersion (C) used is preferably such that the amount of the colorant (k) relative to the resin (B) is 0.1 to 50%, more preferably 0.5 to 30%. Especially preferably, it is 1 to 10%.

  Further, the amount used when the wax dispersion (D) is used is preferably such that the amount of the wax with respect to the resin (B) is 0.1 to 70%, more preferably 0.5 to 60%, Especially preferably, it is 1 to 50%.

  In the production method of the present invention, the solvent (S) solution (L) of the resin (B), the colorant dispersion (C), and, if necessary, the wax dispersion (D) are mixed with organic fine particles in carbon dioxide (X). Any method may be used as the method of dispersing the dispersion (X0) in which (A) is dispersed. As a specific example, a method of dispersing a mixture of a colorant dispersion (C), a solution (L), and, if necessary, a wax dispersion (D) in a dispersion (X0) with a stirrer or a disperser (C ), (L) and, if necessary, a mixture of (D) is sprayed through a spray nozzle into a dispersion (X0) in which (A) is dispersed in (X) to form droplets. (C) from a method in which the resin in the droplet is supersaturated and the resin particles are precipitated (known as ASES: Aerosol Solvent Extraction System), coaxial multiple tubes (double tubes, triple tubes, etc.) And (L) and, if necessary, a mixture of (D) and dispersion (X0) are simultaneously ejected from a separate tube together with a high-pressure gas, an entrainer, etc. Method for obtaining particles (SEDS: So ution Enhanced Dispersion known as by Supercritical Fluids), and a method of irradiating an ultrasonic wave and the like.

In this manner, in the dispersion (X0) in which the organic fine particles (A) are dispersed in carbon dioxide (X), a solution (L) of the colorant dispersion (C) and the resin (B), and a wax if necessary. By dispersing the dispersion (D) and allowing the organic resin (A) to be adsorbed on the surface and growing the dispersed resin (B), the resin (B), the colorant (k), and the solvent (S ), And if necessary, resin particles (Z1) in which the organic fine particles (A) are fixed on the surface of the resin particles (Y1) containing the wax (w). A dispersion (Q) is obtained by dispersing (Z1) in a dispersion medium containing (X) and (S).
The dispersion (Q) is preferably a single phase. That is, it is not preferable that the solvent (S) phase is separated in addition to the phase containing carbon dioxide (X) in which (Z1) is dispersed. Therefore, it is preferable to set the amount of the solution (L) of (B) with respect to the dispersion (X0) so that the solvent phase does not separate. For example, 90% or less is preferable with respect to (X0), more preferably 5 to 80%, and particularly preferably 10 to 70%.
In addition, the amount of the solvent (S) contained in the resin particles (Y1) is preferably 10 to 90%, more preferably 20 to 70%.
The weight ratio of the resin (B) to carbon dioxide (X) is preferably (B) :( X) is 1: (0.1-100), more preferably 1: (0.5-50). Especially preferably, it is 1: (1-20).

The weight ratio of the crystalline resin and / or amorphous resin constituting the organic fine particles (A) and the resin (B) constituting the resin particles (Y) 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 is within this range because both low-temperature meltability and long-term storage stability are compatible.
The weight ratio between the organic fine particles (A) and the resin particles (Y) is not particularly limited, but is preferably 0.1 to 20%, more preferably, (A) with respect to the resin particles (Y). 0.5 to 15%. If it is this range, the dispersibility of the resin particle (Z) will improve.

In the production method of the present invention, the resin particles (Z1) to be formed are treated in carbon dioxide (X) during dispersion, and then the carbon dioxide (X) is removed to obtain the target resin particles (Z ) Can be obtained. Here, the treatment means that the resin particles (Z1) are dispersed in (X), brought into contact with (X) for a certain time, and (Z1) is swollen.
The predetermined time [including the time required for forming the resin particles (Z1). ] Is usually 10 seconds to 180 minutes, preferably 30 seconds to 60 minutes.
Swelling occurs when carbon dioxide (X) permeates into resin particles (Z1) by bringing resin particles (Z1) into contact with carbon dioxide (X) for a certain period of time. Therefore, the degree of swelling can be adjusted by the contact time with (X), the pressure and temperature of (X).

  In the production method of the present invention, the treatment with carbon dioxide (X) is preferably performed at the temperature described below. That is, in order to prevent carbon dioxide from undergoing a solid phase transition in the pipe during decompression and block the flow path, the temperature is preferably 30 ° C. or higher, and the organic fine particles (A), resin particles (Y1), resin particles ( In order to prevent thermal degradation of Z1), 200 ° C. or lower is preferable. Furthermore, 30-150 degreeC is preferable, More preferably, it is 34-130 degreeC, Especially preferably, it is 35-100 degreeC, Most preferably, it is 40-80 degreeC. The same applies to the temperatures of the dispersion (X0) and the dispersion (Q). The treatment with carbon dioxide (X) can be carried out at a temperature above or below the Tg or melting point of the organic fine particles (A), but is preferably carried out at a temperature below the Tg or melting point.

  When processing with carbon dioxide (X), it is preferable to carry out at the pressure described below. That is, in order to disperse resin particles (Z1) well in (X), it is preferably 3 MPa or more, and preferably 40 MPa or less from the viewpoints of equipment cost and operation cost. More preferably, it is 3.5-35 MPa, More preferably, it is 4-30 MPa, Most preferably, it is 4.5-25 MPa, Most preferably, it is 5-20 MPa. The same applies to the pressure in the vessel forming the dispersion (X0) and the dispersion (Q).

  The temperature and pressure when treating in carbon dioxide (X) are set within a range in which the resin particles (Z1) do not dissolve in (X) and carbon dioxide (X) can penetrate into (Z1). It is preferable. Usually, (Z1) tends to not dissolve in (X) at lower temperatures and lower pressures, and (X) tends to penetrate into (Z1) at higher temperatures and pressures.

In the production method of the present invention, a resin in which organic fine particles (A) are fixed on the surface of resin particles (Y1) containing resin (B), colorant (k), solvent (S), and, if necessary, wax (w) After forming and treating the dispersion (Q) in which the particles (Z1) are dispersed in a dispersion medium containing (X) and (S), it is necessary to remove or reduce the solvent (S).
As a method of removing or reducing the solvent (S), there is a method of reducing the pressure of the container as it is, but the solvent dissolved in (Y1) is condensed and the resin particles (Y1) are redissolved, or the resin particles When collecting (Z), there may be a problem that the resin particles (Z) are united with each other.
As a preferred method, for example, carbon dioxide (X) is further mixed with the dispersion (Q) in which the resin particles (Z1) are dispersed in the dispersion medium containing (X) and (S), and the resin particles (Z1 ) From the solvent (S) into the carbon dioxide (X) phase, and then the carbon dioxide (X) containing the solvent (S) is replaced with carbon dioxide (X) containing no solvent (S); And a method of reducing the pressure.

  In the mixing method of carbon dioxide (X), carbon dioxide (X) having a pressure higher than that of the dispersion (Q) may be added, and the dispersion (Q) is added to carbon dioxide (X) having a pressure lower than that of the dispersion. Although it may be added, the latter is more preferable from the viewpoint of ease of continuous operation. The amount of carbon dioxide (X) mixed with the dispersion (Q) is preferably 1 to 50 times the volume of the dispersion (Q) from the viewpoint of preventing coalescence of the resin particles (Z1), more preferably 1 to 40 times, most preferably 1 to 30 times. By removing or reducing the solvent contained in the resin particles (Z1) as described above, and then removing the carbon dioxide (X), it is possible to prevent the resin particles (Z1) from uniting with each other. .

  As a method of replacing carbon dioxide (X) containing the solvent (S) with carbon dioxide (X) not containing the solvent (S), the resin particles (Z1) are once supplemented with a filter or cyclone, and then the pressure is maintained. And a method of circulating carbon dioxide (X) until the solvent (S) is completely removed. The amount of carbon dioxide (X) to be circulated is preferably from 1 to 100 times, more preferably from 1 to 70 times, most preferably from the volume of the dispersion (Q) from the viewpoint of solvent removal from the dispersion (Q). Preferably it is 1 to 50 times.

From the dispersion (Q) in which the resin particles (Z1) are dispersed, the carbon dioxide (X) and the solvent (S) are usually removed under reduced pressure to obtain the resin particles (Z) of the present invention. At that time, the pressure may be reduced stepwise by providing independent pressure-controlled containers in multiple stages, or may be reduced to normal temperature and normal pressure at a stretch.
The method of collecting the resin particles (Z) is not particularly limited, and examples thereof include a method of filtering with a filter and a method of centrifuging with a cyclone or the like.
The resin particles (Z) may be collected after depressurization, or may be collected under high pressure before depressurization and then depressurized. As a method of taking out the resin particles (Z) from under high pressure when collecting under high pressure and then depressurizing, the collection container may be depressurized by batch operation, or continuously with a rotary valve. An operation may be performed.

As a method for removing the solvent (S) in the dispersion (Q) in which the resin particles (Z1) are dispersed in a dispersion medium containing carbon dioxide (X) and the solvent (S), from the viewpoint of solvent removal efficiency. It is more preferable to include a step of cooling the dispersion (Q) in which the resin particles (Z1) are dispersed.
By cooling the dispersion (Q), the solubility of the resin (B) in the solvent (S) is lowered, and the solvent (S) in the resin particles (Z1) is changed from the inside of the particles to carbon dioxide (X) and the solvent (S ), The solvent (S) content in the resin particles (Z1) can be efficiently reduced to 10% by weight or less at which the particles do not coalesce with each other. Any other solvent removal method may be used as long as the method includes this cooling step.

  The cooling temperature is determined by the exothermic peak temperature Ta [° C.] when the DSC measurement temperature of the solvent (S) solution (L) of (B) has the same composition as that used, and is cooled below Ta [° C.]. There is a need. When the cooling temperature is higher than Ta [° C.], the precipitation of the resin (B) does not occur, and the content of the solvent (S) in the resin particles (Z1) does not decrease to 10% by weight or less.

The cooling method may be any method as long as it can be set to Ta [° C.] or less, but is already (Ta-10) [° C.] or less [preferably (Ta-20) to (Ta-60) [ The method of adding liquid carbon dioxide (X1) cooled to [° C.] to the dispersion (Q) is preferred. By adding liquid carbon dioxide (X1) cooled to (Ta-10) [° C.] or less, the process time can be greatly shortened.
The amount of liquid carbon dioxide (X1) added for cooling is preferably 0.5 times or more, more preferably 1 to 10 times the weight of the dispersion (Q). When the weight of (X1) is 0.5 times or more, the temperature of (Q) easily becomes Ta [° C.] or less.

A dispersion medium containing liquid carbon dioxide (X1) and a solvent (S) after cooling the temperature of the dispersion (Q) to Ta [° C.] or less to remove the solvent (S) from the resin particles (Z1); The resin particles (Z) are preferably collected by solid-liquid separation to collect the resin particles (Z).
The method for collecting the resin particles (Z) in this case is not particularly limited, and examples thereof include a method of filtering the dispersion (Q) after cooling to Ta [° C.] or less, and a method of centrifuging with a cyclone or the like. As mentioned. The resin particles (Z) may be collected after depressurization, or may be collected under high pressure before depressurization and then depressurized. As a method of taking out the resin particles (Z) from under high pressure when collecting under high pressure and then depressurizing, the collection container may be depressurized by batch operation, or continuously with a rotary valve. An operation may be performed.
Among the above methods, a preferred collection method is a method in which the dispersion (Q) cooled to Ta [° C.] or less is filtered off and then collected under reduced pressure. After depressurization, liquid carbon dioxide (X1) is preferably added in an amount of 2.5 to 5 times the solid weight of the resin particles (Z) [weight excluding (S) and (X)]. Then, by performing an operation of further extracting the solvent (S) from the resin particles (Z), the coalescence of the resin particles (Z) can be further suppressed.

  When the organic fine particles (A) contain a crystalline resin, after forming the resin particles (Z), if necessary, as a further step, the crystalline resin, preferably the melting point minus 50 ° C. or more, more preferably Is heated to a melting point minus 10 ° C. or higher, more preferably higher than the melting point to melt the organic fine particles (A) adhering to the surface of the resin particles (Y), and the organic fine particles (A) are converted into resin particles (Y). It is also possible to perform a step of forming resin particles (Z ′) by forming a film adhered to the surface of the resin or forming a film derived from the organic fine particles (A). From the viewpoint of suppressing the aggregation of (Z ′), the heating time is preferably 0.01 to 1 hour, and more preferably 0.05 to 0.7 hour.

In the resin particles (Z) obtained by the resin particle production method of the present invention, the organic fine particles (A) are once fixed to the surface of the resin particles (Y1). For example, when (A) contains a crystalline resin Depending on the composition of the crystalline resin and the resin (B) and the type of the solvent (S), the organic fine particles (A) are formed into a film during the manufacturing process, and (A) is formed into a film on the surface of (Y). A film may be formed.
The resin particles (Z) finally obtained by the production method of the present invention are those in which the organic fine particles (A) are fixed on the surfaces of the resin particles (Y), those in which a film derived from (A) is formed, Any of (A) partly formed into a film may be used. The organic fine particles (A) are fixed to the surface of the resin particles (Y) does not include the case where (A) simply adheres to the surface of (Y) and easily desorbs.
The surface state and shape of the resin particles (Z) 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 resin particles (Z) of the present invention obtained by the above production method are improved in crystallinity by treatment with carbon dioxide (X) in a liquid or supercritical state, and the melting heat of melting increases.

  The volume average particle diameter of the resin particles (Z) obtained by the production method of the present invention is preferably 1 to 12 μm, more preferably 2 to 10 μm, and further preferably 3 to 8 μm. When it is 1 μm or more, the handling property as a powder is improved. When it is 12 μm or less, the melting characteristics are improved.

  The ratio of the volume average particle diameter Dv of the resin particles (Z) to the number average particle diameter Dn of (Z): Dv / Dn is preferably 1.0 to 1.5, more preferably 1.0 to 1.4. More preferably, it is 1.0 to 1.3. When it is 1.5 or less, the handling property and melting characteristics as powder are remarkably improved.

The volume average particle diameter of the resin particles (Z) and the ratio (Dv / Dn) of the volume average particle diameter Dv to the number average particle diameter Dn are the resin (B) and organic fine particles (A) dissolved in the solvent (S). Can be adjusted by the stirring speed and the ratio of the organic fine particles (A) with respect to the resin (B). When the stirring speed is increased, the volume average particle diameter is decreased, and when the ratio of the organic fine particles (A) to the resin (B) is increased, the volume average particle diameter is decreased.
The same applies to Dv / Dn of the resin particles (Z). When the stirring speed is increased, Dv / Dn decreases, and when the ratio of the organic fine particles (A) to the resin (B) is increased, Dv / Dn decreases. .
The resin particles (Z) thus obtained are classified using an air classifier or a sieve, if necessary, and the volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter are further adjusted. can do.

The resin particles (Z) are derived from the organic fine particles (A) or (A) from the viewpoint of particle size uniformity, powder fluidity, storage stability, etc., at least 5% of the surface of the resin particles (Y). It is preferable that it is covered with a film of, 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 (Y) of the portion covered with the film derived from (A) or (A)] / [covered with the film derived from (A) or (A) (Y) surface area of the portion + area of the portion where the surface of (Y) is exposed]

Moreover, it is preferable that the heat of fusion of the resin particles (Z) obtained by differential scanning calorimetry (DSC) measurement satisfies the following relational expression.
0 ≦ H2 / H1 ≦ 0.9 (1)
H1 represents the heat of fusion (J / g) at the first temperature rise by DSC measurement, and H2 represents the measurement value of the heat of fusion (J / g) at the second temperature rise by DSC measurement.

Here, the heat of fusion is measured in accordance with JIS K7122 (1987) “Method of measuring the transition heat of plastic”.
Specifically, a sample (5 mg) is collected and placed in an aluminum pan, and a differential scanning calorimeter (DSC) (for example, “RDC220 manufactured by SII Nano Technology Co., Ltd.”, “DSC20 manufactured by Seiko Electronics Industry Co., Ltd.) The temperature of the endothermic peak due to melting [melting point (m)] (° C.) can be determined at a heating rate of 10 ° C. per minute. Further, the heat of fusion can be determined from the area of the endothermic peak. In addition, after the first temperature increase, the cooling before the second temperature increase is performed at a cooling rate of 90 ° C./min to 0 ° C.

As shown in the relational expression (1), H2 / H1 is preferably 0 or more, more preferably 0.01 or more, and particularly preferably 0.1 or more.
Further, H2 / H1 is preferably 0.9 or less, more preferably 0.85 or less, and particularly preferably 0.8 or less. When it is 0.9 or less, the heat resistant storage stability is good.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, parts are parts by weight.

The following swelling degree, crystallinity, number average molecular weight (Mn), melting point, glass transition temperature, and volume average particle diameter were measured by the following methods.
<Measurement method of swelling degree>
A sample (5 mg) was collected, and the weight at which carbon dioxide in a supercritical state at 40 ° C. and 10 MPa permeated into the sample was measured using a magnetic suspension balance (MSB-SCC / SCW Nippon Bell Co., Ltd.). The degree of swelling (%) was determined.
<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 Measure the crystallinity 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 number average molecular weight (Mn)>
Each sample was dissolved in tetrahydrofuran at a concentration of 2.5 g / L and measured by GPC using polystyrene as a standard substance.
GPC model: HLC-8120GPC, manufactured by Tosoh Corp. Column: 2 TSKgel GMHXL) + TSKgel Multipore HXL-M (produced by Tosoh Corp.)
<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 temperature rising rate of 10 ° C. 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.).
<Measurement method of volume average particle diameter>
The resin particles were dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle size was measured with a Coulter counter [Multisizer III (manufactured by Beckman Coulter)].

[Production of Resin (B) and Solution (L)]
Production Example 1
In a reaction vessel, 2 parts of 1,4-butanediol, 650 parts of ε-caprolactone, and 2 parts of dibutyltin oxide were added, and the reaction was carried out at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere. The mixture was further cooled to 100 ° C. to obtain a lactone ring-opening polymer [crystalline part (a-1)]. [Crystalline part (a-1)] was Mw 4500, melting point (m) 60 ° C., and hydroxyl value 54.

Production Example 2
A reaction vessel was charged with 42 parts of terephthalic acid, 18 parts of isophthalic acid, 40 parts of 1,5-pentanediol, and 2 parts of dibutyltin oxide, and after dehydration reaction at normal pressure and 230 ° C. for 5 hours, 0.5 kPa The dehydration reaction was performed for 5 hours under reduced pressure.
Furthermore, 500 parts of ε-caprolactone was added and reacted at 150 ° C. for 10 hours under normal pressure and nitrogen atmosphere to obtain a composite resin [crystalline part (a-2)] of a lactone ring-opening polymer and a polyester resin. It was. [Crystalline part (a-2)] was Mw 4000, melting point (m) 65 ° C., and hydroxyl value 52.

Production Example 3
A reaction vessel was charged with 1000 parts of methyl ethyl ketone, 19 parts of 1,4-butanediol, and 54 parts of hexamethylene diisocyanate and reacted at 80 ° C. for 7 hours, and then polycaprolactone diol having a hydroxyl value of 56 (Daicel Chemical Industries, Ltd.) ), Product name “Placcel 220”) 427 parts are charged, reacted at 80 ° C. for 7 hours, desolvated at 80 ° C. and 20 kPa, and composite resin of lactone ring-opening polymer and polyurethane resin [crystalline part (A-3)] was obtained. [Crystalline part (a-3)] was Mw 9500, melting point (m) 54 ° C., and hydroxyl value 28.

Production Example 4
In a mixing container, 150 parts of polycaprolactone diol having a hydroxyl value of 28 (product name “Placcel 240” manufactured by Daicel Chemical Industries, Ltd.) and a crystalline polyester diol composed of 1,6-hexanediol having a hydroxyl value of 22 and sebacic acid ( 350 parts of Toyokuni Oil Co., Ltd., trade name “HS2H-500S”) was added and mixed for 1 hour at 100 ° C., and mixed resin of lactone ring-opening polymer and polyester resin [crystalline part (a-4 )]. [Crystalline part (a-4)] was Mw 12000, melting point (m) 64 ° C., and hydroxyl value 24.

Production Example 5
Into a reaction vessel, 500 parts of tetrahydrofuran, 360 parts of 1,2-propylene glycol and 640 parts of toluene diisocyanate are charged, reacted at 80 ° C. for 5 hours, desolvated at 80 ° C. and 20 kPa, and polyurethane resin [non-crystalline part (B-1)] was obtained. [Amorphous part (b-1)] was Mw 3000 and the NCO content was 1.2%.

Production Example 6
A reaction vessel was charged with 270 parts of terephthalic acid, 730 parts of a PO2 molar adduct of bisphenol A, and 5 parts of dibutyltin oxide. After dehydration reaction at normal pressure and 230 ° C. for 5 hours, under a reduced pressure of 0.5 kPa. A dehydration reaction was performed for 5 hours to obtain a polyester resin [amorphous part (b-2)]. [Amorphous part (b-2)] was Mw5000 and hydroxyl value 55.

Production Example 7
Except for using 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-1)] and 1000 parts of the above [crystalline part (a-1)], the same procedure as in Production Example 5 was carried out to obtain a resin ( B-1) was obtained. (B-1) was Mw11500, softening point (s) 65 ° C., melting point (m) 60 ° C., softening point (s) to melting point (m) ratio (s / m) 1.08.
G ′ (m + 20) was 9 × 10 ² Pa, the melting start temperature (x) was 57 ° C., and the value of | LogG ″ (x + 20) −LogG ″ (x) | was 3.6.
The ratio [G ″ (m + 30) / G ″ (m + 70)] of the loss elastic modulus G ″ (m + 30) at (m + 30) ° C. to the loss elastic modulus G ″ (m + 70) at (m + 70) ° C. was 1.3.
It was n = 1.20 in the formula of the combined form of (b) and (a). The physical property values are listed in Table 1.
To the reaction vessel, 300 parts of this resin (B-1), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-1).

Production Example 8
Except for using 500 parts of tetrahydrofuran, 200 parts of the above [noncrystalline part (b-1)], and 1000 parts of the above [crystalline part (a-2)], the same procedure as in Production Example 5 was carried out to obtain a resin ( B-2) was obtained. The physical property values of the resin (B-2) are shown in Table 1.
To the reaction vessel, 300 parts of this resin (B-2), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-2).

Production Example 9
Into a reaction vessel, 500 parts of tetrahydrofuran, 200 parts of the above-mentioned [non-crystalline part (b-2)] and 38 parts of m-xylylene diisocyanate were added and reacted at 80 ° C. for 5 hours. Sex part (a-1)] 270 parts was added, the reaction was carried out at 80 ° C. for 5 hours, and the solvent was removed at 80 ° C. and 20 kPa to obtain a resin (B-3). The physical property values of the resin (B-3) are shown in Table 1.
To the reaction vessel, 300 parts of this resin (B-3), 630 parts of acetone, and 70 parts of ion exchange water were added and dissolved to obtain a resin solution (L-3).

Production Example 10
Resin (B-4) was prepared in the same manner as in Production Example 9 except that 280 parts of [Crystalline part (a-2)] was used instead of 270 parts of [Crystalline part (a-1)]. Got. The physical property values of the resin (B-4) are shown in Table 1.
To the reaction vessel, 300 parts of this resin (B-4), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-4).

Production Example 11
Production Example, except that 850 parts of methyl ethyl ketone was used instead of 500 parts of tetrahydrofuran, and 665 parts of the above [crystalline part (a-3)] were used instead of 270 parts of [crystalline part (a-1)]. In the same manner as in No. 9, a resin (B-5) was obtained. The physical property values of the resin (B-5) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (B-5), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-5).

Production Example 12
Production Example, except that 1000 parts of methyl ethyl ketone was used instead of 500 parts of tetrahydrofuran, and 960 parts of [crystalline part (a-4)] were used instead of 270 parts of [crystalline part (a-1)]. In the same manner as in No. 9, resin (B-6) was obtained. The physical property values of the resin (B-6) are shown in Table 1.
In a reaction vessel, 300 parts of this resin (B-6), 630 parts of acetone, and 70 parts of ion-exchanged water were added and dissolved to obtain a resin solution (L-6).

[Production of vinyl resin (N) and organic fine particles (A)]
Production Example 13
Into a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube (the same applies to the reaction vessel used for the production of the crystalline vinyl resin described below), 500 parts of toluene was added to another glass product. In a beaker, 350 parts of toluene, 150 parts of behenyl acrylate (an acrylate of an alcohol having a linear alkyl group having 22 carbon atoms; Bremer VA [manufactured by NOF Corporation], the same shall apply hereinafter) 150 parts, AIBN (azobisisobutyro Nitrile) 7.5 parts was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N1-1). The crystallinity of this resin was 42%, the melting point was 65 ° C., and Mn was 50000.

Production Example 14
In a reaction vessel, 500 parts of toluene is charged, and in another glass beaker, 350 parts of toluene, 120 parts of behenyl acrylate, 30 parts of 2-decyltetradecyl methacrylate, and 7.5 parts of AIBN (azobisisobutyronitrile) are charged. The monomer solution was prepared by stirring and mixing at 20 ° C. and charged into the dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N1-2). The crystallinity of this resin was 36%, the melting point was 62 ° C., and Mn was 50000.

Production Example 15
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 150 parts of behenyl acrylate, 50 parts of butyl acrylate, and 7.5 parts of AIBN (azobisisobutyronitrile) were charged at 20 ° C. A monomer solution was prepared by stirring and mixing, and charged into a dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state. Removal under reduced pressure gave a vinyl resin (N1-3). This resin had a crystallinity of 20%, a melting point of 50 ° C., and Mn of 40000.

Production Example 16
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 135 parts of behenyl acrylate, 15 parts of acrylonitrile, 7.5 parts of AIBN (azobisisobutyronitrile) were charged and stirred at 20 ° C. The monomer solution was prepared by mixing and charged into the dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state. Removal under reduced pressure gave a vinyl resin (N2-4). The crystallinity of this resin was 41%, the melting point was 62 ° C., and Mn was 50000.

Production Example 17
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, stearyl acrylate (an acrylate of an alcohol having a straight-chain alkyl group having 18 carbon atoms; Bremmer SA [manufactured by NOF Corp.], The same applies hereinafter.) 150 parts and 7.5 parts of AIBN (azobisisobutyronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state. Removal under reduced pressure gave a vinyl resin (N1-5). This resin had a crystallinity of 32%, a melting point of 54 ° C., and Mn of 50000.

Production Example 18
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 120 parts of behenyl acrylate, 22.5 parts of methyl methacrylate, (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries) 7 .5 parts and 10 parts of AIBN (azobisisobutyronitrile) were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N1-6). The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 8,000.

Production Example 19
In a reaction vessel, 500 parts of toluene is charged, and in another glass beaker, 350 parts of toluene, 75 parts of stearyl acrylate, 15 parts of 2-hydroxyethyl methacrylate, 29.85 parts of methyl methacrylate, 15 parts of acrylonitrile, 15 parts of methacrylic acid. , 0.12-part of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries) and 2.5 parts of AIBN (azobisisobutyronitrile) are stirred and mixed at 20 ° C. to obtain a monomer solution. Prepared and charged into dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N2-7). The crystallinity of this resin was 50%, the melting point was 50 ° C., and Mn was 300,000.

Production Example 20
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 112.5 parts of behenyl acrylate, 37.5 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN 7.5 parts of (azobisisobutyronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N1-8). The crystallinity of this resin was 20%, the melting point was 55 ° C., and Mn was 50000.

Production Example 21
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 120 parts of behenyl acrylate, 28.5 parts of methyl methacrylate, (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries) 1 .5 parts and AIBN (azobisisobutyronitrile) 2.5 parts were stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave vinyl resin (N1-9). The crystallinity of this resin was 70%, the melting point was 70 ° C., and Mn was 300,000.

Production Example 22
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 120 parts of behenyl acrylate, 27 parts of methyl methacrylate, 3 parts of maleic anhydride, 8 parts of AIBN (azobisisobutyronitrile). Charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. for 2 hours in a sealed state. Removal under reduced pressure gave a vinyl resin (N1-10). The crystallinity of this resin was 65%, the melting point was 65 ° C., and Mn was 30000.

Production Example 23
In a reaction vessel, 500 parts of toluene was charged, and in another glass beaker, 350 parts of toluene, 125 parts of behenyl acrylate, 18 parts of styrene, 2 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), fumaric acid 5 parts and 6 parts of AIBN (azobisisobutyronitrile) were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase portion of the reaction vessel with nitrogen, the monomer solution was added dropwise at 80 ° C. over 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. Removal under reduced pressure gave a vinyl resin (N1-11). The crystallinity of this resin was 60%, the melting point was 60 ° C., and Mn was 70000.

Production Example 24 <Preparation of Vinyl Monomer Intermediate (m′5)>
428 parts of 2-hydroxyethyl methacrylate was dropped into 572 parts of TDI and reacted at 55 ° C. for 4 hours to obtain a vinyl monomer intermediate (m′5).

Production Example 25 <Preparation of vinyl monomer (m5-1) solution>
480 parts of HS2H-500S (1,6-hexanediol / sebacic acid-based crystalline polyester resin, manufactured by Toyokuni Oil Co., Ltd.) is dissolved in 500 parts of THF at 70 ° C., and 20 parts of vinyl monomer intermediate (m′5) is added dropwise. The mixture was reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (m5-1) solution.

Production Example 26 <Preparation of vinyl monomer (m5-2) solution>
450 parts of NIPPOLAN 4073 (1,6-hexanediol / adipic acid-based crystalline polyester resin, manufactured by Nippon Polyurethane) was dissolved in 500 parts of THF at 70 ° C., and 50 parts of vinyl monomer intermediate (m′5) was dropped. The mixture was reacted at 70 ° C. for 4 hours to obtain a vinyl monomer (m5-2) solution.

Production Example 27 <Preparation of vinyl monomer (m5-3) solution>
500 parts of PLACCEL FM5 (vinyl monomer having a polycaprolactone chain, manufactured by Daicel) was dissolved in 500 parts of THF at 70 ° C. to obtain a vinyl monomer (m5-3) solution.

Production Example 28
A reaction vessel was charged with 400 parts of a vinyl monomer (m5-1) solution, and another glass beaker was charged with 196 parts of THF and 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) at 20 ° C. A monomer solution was prepared by stirring and mixing, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state. Removal under reduced pressure gave a vinyl resin (N3-12). This resin had a crystallinity of 90%, a melting point of 70 ° C., and Mn of 7500.

Production Example 29
A reaction vessel was charged with 560 parts of a vinyl monomer (m5-1) solution, and another glass beaker was charged with 316 parts of THF, 120 parts of maleic acid, and 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile). Charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-13). The crystallinity of this resin was 70%, the melting point was 65 ° C., and Mn was 7500.

Production Example 30
In a reaction vessel, 560 parts of a vinyl monomer (m5-1) solution, 316 parts of THF, 60 parts of maleic acid, 60 parts of 2,2,2-trifluoroethyl acrylate (manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2 , 4-dimethylvaleronitrile) was charged, and the mixture was stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-14). This resin had a crystallinity of 70%, a melting point of 65 ° C., and Mn of 7500.

Production Example 31
In a reaction vessel, 560 parts of a vinyl monomer (m5-2) solution was charged, and in another glass beaker, 316 parts of THF, 60 parts of maleic acid, 60 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-15). This resin had a crystallinity of 50%, a melting point of 54 ° C., and Mn of 3000.

Production Example 32
A reaction vessel was charged with 560 parts of a vinyl monomer (m5-3) solution, and in another glass beaker, 316 parts of THF, 60 parts of maleic anhydride, 60 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-16). The crystallinity of this resin was 20%, the melting point was unknown, and Mn was 1000.

Production Example 33
Into a reaction vessel, 560 parts of a vinyl monomer (m5-1) solution was charged, and in another glass beaker, 316 parts of THF, 120 parts of (2-perfluorobutyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), 2,2′- 4 parts of azobis (2,4-dimethylvaleronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-17). The crystallinity of this resin was 70%, the melting point was 65 ° C., and Mn was 7500.

Production Example 34
Into a reaction vessel, 560 parts of a vinyl monomer (m5-1) solution was charged, and in another glass beaker, 316 parts of THF and behenyl acrylate (an acrylate of an alcohol having a linear alkyl group with 22 carbon atoms: Blemmer VA [NOF) (Made by Co., Ltd.)] 120 parts and 4 parts of benzoyl peroxide were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 70 ° C. for 2 hours in a sealed state, and after aging at 70 ° C. for 2 hours after completion of the dropwise addition, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N3-18). The crystallinity of this resin was 90%, the melting point was 68 ° C., and Mn was 7500.

Production Example 35
In a reaction vessel, 316 parts of THF, 213 parts of behenyl acrylate (alcohol having a linear alkyl group having 22 carbon atoms: Bremer VA [manufactured by NOF Corporation)], 80 parts of methacrylic acid, methacryl-modified silicone (functional group) Equivalent amount: 12,000 g / mol, Mn 12,000: X22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.)) 106 parts, 1.5 parts of azobisisobutyronitrile were charged, stirred and mixed at 20 ° C. A monomer solution was prepared and charged into a dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was dropped over 2 hours at 70 ° C. in a sealed state, and after aging at 70 ° C. for 6 hours from the end of dropping, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N4-19). This resin had a crystallinity of 40%, a melting point of 55 ° C., and Mn of 52,000.

Production Example 36
In a reaction vessel, 321 parts of THF, 272 parts of cyclohexyl methacrylate (Blenmer CHMA [manufactured by NOF Corporation)], 50 parts of methacrylic acid, methacrylic modified silicone (functional group equivalent: 12,000 g / mol, Mn 12,000: X22- 2426 (manufactured by Shin-Etsu Chemical Co., Ltd.)) and 1.5 parts of azobisisobutyronitrile were charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. After substituting the gas phase part of the reaction vessel with nitrogen, the monomer solution was dropped over 2 hours at 70 ° C. in a sealed state, and after aging at 70 ° C. for 6 hours from the end of dropping, THF was added at 80 ° C. for 3 hours. Removal under reduced pressure gave a vinyl resin (N4-20). The crystallinity of this resin was 0%, the melting point was unknown, and Mn was 78000.

Production Example 37
After mixing 700 parts of normal hexane and 300 parts of each of vinyl resins [N (1-4)-(1-20)], the particle size is 0.3 mm with a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises). The zirconia beads were pulverized to obtain milky white organic fine particles (A-1) to organic fine particles (A-20) hexane dispersion. The volume average particle diameter of the dispersion was 0.05 to 0.4 μm as described in Tables 2 to 4. Moreover, the swelling degree of the organic fine particles (A-1) to (A-20) was as shown in Tables 2 to 4.

Production Example 38
After mixing 700 parts of ion-exchanged water and 300 parts of vinyl resin (N1-1), the above-mentioned bead mill is pulverized using zirconia beads having a particle diameter of 0.3 mm, and organic fine particles (A′-1) for a comparative example An aqueous dispersion was obtained. The volume average particle diameter of this dispersion was 0.3 μm.

[Production of Colorant Dispersion (C)]
Production Example 39
Dispersant (DISPERBYK106: salt of a polymer compound having an acid value of 132 and an amine value of 74, having peaks at molecular weights of 1,200 and 460, manufactured by Big Chemie Japan) in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. 1.2 parts of acetone solution 40 parts, phthalocyanine pigment [cyanine blue (CI Pigment Blue 15: 3)] 8.85 parts are charged to 40% of the reaction vessel volume, sealed and stirred. The temperature was raised to 85 ° C. in the system. After heating, carbon dioxide is supplied to 5 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere to vaporize and remove carbon dioxide, and the colorant dispersion (C -1) was obtained. The median diameter of the dispersoid LA-920 (same for the following dispersoids) was 0.36 μm, and the ratio of 1 μm or more was 0% by volume.

Production Example 40
Dispersant (SOLSPERSE 71000: comb polymer having an acid value of 0 and an amine value of 78, having a peak at a molecular weight of 3,800, manufactured by Nippon Lubrizol Co., Ltd.) 1.0 part in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer 45 parts of an acetone solution and 4.0 parts of azo lake pigment [Pigment Red (CI Pigment Red 57: 1)] were charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, The temperature was raised to an internal temperature of 85 ° C. After heating, carbon dioxide is supplied to 5 MPa and stirred for 10 minutes, and then the nozzle attached to the lower part of the container is fully opened and opened to the atmosphere to vaporize and remove carbon dioxide, and the colorant dispersion (C -2) was obtained. The median diameter of the dispersoid was 0.23 μm, and the ratio of 1 μm or more was 0% by volume.

Production Example 41
1. Dispersant (BYK9076: salt of polymer copolymer having an acid value of 38 and an amine value of 44, having a peak at a molecular weight of 3,000, manufactured by Big Chemie Japan) in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. 55 parts of a methyl ethyl ketone solution and 4.0 parts of carbon black pigment were charged to 30% of the volume of the reaction vessel, sealed and heated with stirring, and the system temperature was raised to 90 ° C. After raising the temperature, carbon dioxide was supplied to 3 MPa, and the mixture was stirred for 10 minutes. Then, the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere to vaporize and remove the carbon dioxide. C-3) was obtained. The median diameter of the dispersoid was 0.43 μm, and the ratio of 1 μm or more was 0.9% by volume.

Production Example 42
1.0 part of a dispersant (SOLSPERSE 54000: a chain polymer having an acid value of 35 and an amine value of 0, having a peak at a molecular weight of 2,900, manufactured by Nippon Lubrizol) in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer 45 parts of tetrahydrofuran solution and 7.0 parts of benzimidazolone pigment [Pigment Yellow (CI Pigment Yellow 180)] were charged to 60% of the volume of the reaction vessel, sealed and heated with stirring. The temperature was raised to 50 ° C. After raising the temperature, carbon dioxide was supplied to 7 MPa, and the mixture was stirred for 15 minutes. Then, the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere to vaporize and remove the carbon dioxide, and the colorant dispersion ( C-4) was obtained. The median diameter of the dispersoid was 0.31 μm, and the ratio of 1 μm or more was 0% by volume.

Production Example 43
Dispersant (DISPERBYK145: salt of a polymer compound having an acid value of 76 and an amine value of 71, having a peak at a molecular weight of 1,700, manufactured by Big Chemie Japan) 1.0 part in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer 45 parts of ethyl acetate solution and 4.0 parts of quinacridone pigment [CI Pigment Red 122] were charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, The temperature was raised to 80 ° C. After the temperature rise, carbon dioxide was supplied to 9 MPa and stirred for 20 minutes, and then the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere to vaporize and remove the carbon dioxide, and the colorant dispersion ( C-5) was obtained. The median diameter of the dispersoid was 0.46 μm, and the ratio of 1 μm or more was 2.3% by volume.

Comparative production example 1
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 1.2 parts of the dispersant (DISPERBYK106) 40 parts of acetone solution, phthalocyanine pigment [Cyanine Blue (C.I. Pigment Blue 15: 3)] 8.85 The portion was charged, sealed, heated with stirring, and the temperature was raised to 85 ° C. in the system. After stirring for 10 minutes after raising the temperature, the nozzle attached to the lower part of the container was fully opened and opened to the atmosphere to obtain a comparative colorant dispersion (C′-1). The median diameter of the dispersoid was 0.50 μm, and the ratio of 1 μm or more was 34.2% by volume.

[Production of wax dispersant]
Production Example 44
454 parts of xylene and 150 parts of low molecular weight polyethylene [Sanwax LEL-400: softening point 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 parts are placed in a pressure-resistant reaction vessel equipped with a stirrer and a thermometer. The resulting mixture was sufficiently dissolved, and a mixed solution of 716 parts of styrene, 46 parts of butyl acrylate, 88 parts of acrylonitrile, 34 parts of di-t-butylperoxyhexahydroterephthalate, and 119 parts of xylene at 170 ° C. in 3 hours. The solution was dropped to polymerize, and further maintained at this temperature for 30 minutes. Next, the solvent was removed to obtain [Wax Dispersant 1]. The Mw of [Wax Dispersant 1] was 5200.

[Production of Wax Dispersion (D)]
Production Example 45
In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 240 parts of an acetone solution of 12.0 parts of [Wax Dispersant 1] obtained in Production Example 44, paraffin wax (HNP-9, melting point: 76 ° C., Nippon Seiki) Wax Co., Ltd. (24.0 parts) was charged to 40% of the volume of the pressure-resistant reaction vessel, sealed and heated with stirring, and the system temperature was raised to 80 ° C. After raising the temperature and supplying carbon dioxide to 5 MPa and stirring for 10 minutes, by fully opening the nozzle attached to the lower part of the container and opening it to the atmosphere, paraffin wax is precipitated, and carbon dioxide is vaporized and removed. A wax dispersion (D-1) was obtained. The median diameter of the dispersoid was 0.33 μm, and the ratio of 1 μm or more was 0% by volume.

Production Example 46
In a pressure-resistant reaction vessel in which a stir bar and a thermometer were set, 240 parts of an acetone solution of 12.0 parts of [Wax Dispersant 1] obtained in Production Example 44 and 24.0 parts of carnauba wax (melting point: 83 ° C.) were obtained. It charged to 40% of the capacity | capacitance of a pressure-resistant reaction container, and it heated, sealing and stirring, and heated up to 85 degreeC in system temperature. After raising the temperature and supplying carbon dioxide to 5 MPa and stirring for 10 minutes, by fully opening the nozzle attached to the bottom of the container and opening it to the atmosphere, carnauba wax is precipitated, and carbon dioxide is vaporized and removed. A wax dispersion (D-2) was obtained. The median diameter of the dispersoid was 0.44 μm, and the ratio of 1 μm or more was 0% by volume.

Example 1
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 are closed, and carbon dioxide (0 ° C., purity 99.99%) is introduced into the particle recovery tank T4 from the cylinder B2 using the pump P4. It was adjusted. Further, a mixture of the resin solution (L-1), the colorant dispersion (C-1), and the wax dispersion (D-1) is mixed in the resin solution tank T1, and the organic fine particles (A- 1) A hexane dispersion was charged.
Next, liquid carbon dioxide is charged into the dispersion tank T3 from the liquid carbon dioxide cylinder B1 using the pump P3, adjusted to a supercritical state (9 MPa, 40 ° C.), and further from the tank T2 using the pump P2. Then, an organic fine particle (A-1) hexane dispersion was introduced.
Next, while stirring the inside of the dispersion tank T3 at 2000 rpm, the liquid mixture of (L-1), (C-1), and (D-1) is transferred from the tank T1 to the dispersion tank T3 using the pump P1. Introduced. After the introduction, the pressure inside T3 was 14 MPa.

In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (C-1) 60 parts Wax dispersion (D-1) 160 parts Organic fine particles (A-1) Hexane dispersion 45 parts Carbon dioxide 550 parts

The weight of the introduced carbon dioxide is calculated by calculating the density of carbon dioxide from the temperature of carbon dioxide (40 ° C.) and the pressure (15 MPa) according to the state equation described in the following document, and the volume of the dispersion tank T3. (The same applies hereinafter).
Literature: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

A dispersion in which resin particles (Z-1) are dispersed in carbon dioxide in a supercritical state after introducing a mixed solution of (L-1), (C-1), and (D-1) and stirring for 1 minute ( Q-1) was obtained.
Next, the valve V1 was opened, and the dispersion (Q-1) was transferred from T3 to T4 by introducing supercritical carbon dioxide into T3 and T4 using B1 to P3. While the dispersion (Q-1) was transferred from T3 to T4, the opening degree of V2 was adjusted so that the pressure was kept constant. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin dispersion (Q) transferred into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the organic fine particles (A-1) were fixed to the surface of the resin particles (Y-1) formed from the resin solution (L-1), and resin particles (Z-1) were generated.
Next, the pressure was maintained at 14 MPa by adjusting the opening of the pressure adjusting valve V2 while introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4. .
By this operation, carbon dioxide containing the solvent was discharged into the solvent trap tank T5, and the resin particles (Z-1) were captured by the filter F1. The operation of introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 was stopped when 5 times the amount of carbon dioxide introduced into the dispersion tank T3 was introduced into the particle recovery tank T4. . At the time of this stop, the operation of replacing carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (Z-1) in the filter F1 was completed. Further, the pressure regulating valve V2 is opened little by little, and the inside of the particle recovery tank is depressurized to the atmospheric pressure, whereby the surface of the resin particles (Y-1) supplemented by the filter F1 is derived from the organic fine particles (A-1). The resin particles (Z-1) of the present invention in which the colorant and the wax were finely and uniformly dispersed in (Y-1) were obtained.

Examples 2-6
Each surface of resin particles (Y-2) to (Y-6) is the same as in Example 1 except that the resin solution (L-1) is changed to resin solutions (L-2) to (L-6). In addition, a resin particle (Z-2) of the present invention in which a film derived from organic fine particles (A-1) is formed, and a colorant and a wax are finely and uniformly dispersed in (Y-2) to (Y-6) To (Z-6) were obtained.

Examples 7-25
The organic fine particle (A-1) hexane dispersion is changed to the organic fine particles (A-2) to (A-20) hexane dispersion, the colorant dispersion (C-1) is changed to the colorant dispersion (C-2), Organic fine particles were formed on the surfaces of the resin particles (Y-7) to (Y-25) in the same manner as in Example 1 except that the wax dispersion (D-1) was changed to the wax dispersion (D-2). Resin particles of the present invention (Z-) in which films derived from (A-2) to (A-20) are formed and colorants and waxes are finely and uniformly dispersed in (Y-7) to (Y-25). 7) to (Z-25) were obtained.

Examples 26-28
Resin particles (Y-26) to (Y-28) in the same manner as in Example 1 except that the colorant dispersion (C-1) is changed to the colorant dispersions (C-3) to (C-5). ) A resin particle of the present invention in which a coating derived from organic fine particles (A-1) is formed on each surface, and a colorant and wax are finely and uniformly dispersed in (Y-26) to (Y-28). Z-26) to (Z-28) were obtained.

Example 29
In the same manner as in Example 1, after introducing the liquid mixture of (L-1), (C-1), and (D-1), the mixture was stirred for 1 minute, and the resin particles (Z-29 ) Was dispersed (Q-29). The valve V1 was opened, the dispersion (Q-29) was introduced into T4, and the opening degree of V2 was adjusted so that the pressure was kept constant during this time. This operation was performed for 60 seconds, and V1 was closed. The temperature of (Q-29) after introduction into T4 was 30 ° C. Next, carbon dioxide (−40 ° C., purity 99.99%) of the weight of (Q-29) is introduced into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4, and the dispersion (Q-29) After cooling the temperature to −15 ° C., the pressure adjustment valve V2 was opened to reduce the pressure to 4 MPa. Thereafter, V4 was opened again, and carbon dioxide (0 ° C., purity 99.99%) three times the solid weight of the resin particles (Z-29) was introduced from the pressure cylinder B1 and pump P3 to bring the pressure to 14 MPa. Thereafter, the pressure adjustment valve V2 was immediately opened to reduce the pressure to atmospheric pressure. During this time, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5, and the resin particles are captured by the filter F1, and a film derived from the fine particles (A-1) is formed on the surfaces of the resin particles (Y-29). As a result, the resin particles (Z-29) of the present invention in which the colorant and the wax were finely and uniformly dispersed in (Y-29) were obtained.

Examples 30-34
In the same manner as in Example 29 except that the material to be used is changed to be the same as in Example 2, 5, 9, 17, or 24, on the surface of each of the resin particles (Y-30) to (Y-34), Films derived from the organic fine particles (A) are formed, and the resin particles (Z-30) to (Z-) of the present invention in which the colorant and wax are finely and uniformly dispersed in (Y-30) to (Y-34). 34) was obtained.

Comparative Example 1
In a beaker, 97 parts of ion-exchanged water, 15.4 parts of an organic fine particle (A′-1) aqueous dispersion, 1 part of sodium carboxymethylcellulose, and a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “ 10 parts of “ELEMINOL MON-7”) were uniformly dissolved. Next, while stirring the TK homomixer at 10,000 rpm at 25 ° C., 75 parts of the resin solution (L-1), 15 parts of the colorant dispersion (C-1), and 30 of the wax dispersion (D-1) Part was added and stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. until the concentration became 0.5% or less to obtain an aqueous resin dispersion of resin particles.
Subsequently, it is filtered and dried at 40 ° C. for 18 hours, the volatile matter is 0.5% or less, and a film derived from organic fine particles (A′-1) is formed on the surface of the resin particles (Y′-1). Comparative resin particles (R-1) containing a colorant and a wax in Y′-1) were obtained. Thereafter, physical properties were evaluated without performing supercritical carbon dioxide treatment.

Comparative Example 2
In a beaker, 97 parts of ion-exchanged water, 1 part of sodium carboxymethyl cellulose, and 15 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (manufactured by Sanyo Chemical Industries, “Eleminol MON-7”) were uniformly dissolved.
Next, while stirring the TK homomixer at 12,000 rpm at 25 ° C., 75 parts of the resin solution (L-1), 15 parts of the colorant dispersion (C-1), and 30 of the wax dispersion (D-1) 30 Part was added and stirred for 2 minutes. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirrer and a thermometer, and the temperature was raised and acetone was distilled off at 35 ° C. until the concentration became 0.5% or less to obtain an aqueous resin dispersion of resin particles.
Next, the mixture was filtered and dried at 40 ° C. for 18 hours to obtain a comparative resin particle (R-2) containing a colorant and a wax with a volatile content of 0.5% or less. Thereafter, physical properties were evaluated without performing supercritical carbon dioxide treatment.

Comparative Example 3
Comparative resin particles (R-3) containing a colorant and a wax were obtained in the same manner as in Example 1 except that the organic fine particle (A-1) hexane dispersion was not charged in Example 1.

Comparative Example 4
In Example 1, resin particles (Y′−) were used in the same manner as in Example 1 except that the comparative colorant dispersion (C′-1) was used instead of the colorant dispersion (C-1). A film derived from the organic fine particles (A-1) was formed on the surface of 4), and comparative resin particles (R-4) containing a colorant and a wax in (Y′-4) were obtained.
The comparative resin particle (R-4) has poor dispersibility of the colorant. When confirmed with an optical microscope, aggregation of the colorant was confirmed, and particles in which the colorant was not contained in the resin particle were also observed.

Evaluation Results For the resin particles obtained in Examples 1 to 29 and Comparative Examples 1 to 4, the melting point, heat of fusion, particle size distribution, heat resistant storage resistance, moisture heat resistant storage resistance, and low temperature meltability were evaluated by the evaluation methods described below. The results are shown in Tables 6-8. In addition, about Example 30-34, since the evaluation result was the same as the Example using the same material which respond | corresponds, description was abbreviate | omitted.

<Measurement of melting point and heat of fusion>
A sample (5 mg) is collected and placed in an aluminum pan, and the DSC (measuring device: RDC220, manufactured by SII Nano Technology Co., Ltd.) is used to determine the temperature (° C) of the endothermic peak due to melting at a heating rate of 10 ° C per minute. This was determined as the melting point.
The heat of fusion was determined from the area of the endothermic peak. Using the obtained heat of fusion, the ratio of heat of fusion was obtained from the following formula.
Ratio of heat of fusion = H2 / H1

<Evaluation of particle size distribution>
The resin particles were dispersed in an aqueous sodium dodecylbenzenesulfonate solution (concentration: 0.1%), and the volume average particle size / number average particle size of the resin particles was measured with a Coulter counter [Multisizer III (manufactured by Beckman Coulter)]. . The smaller the volume average particle size / number average particle size, the sharper the particle size distribution.

<Evaluation of heat-resistant storage stability>
The heat resistant storage stability of the resin particles was evaluated by the following method.
10 g of resin particles were collected in a 30 ml glass screw tube having a diameter of about 3 cm. The glass screw tube containing the resin particles was allowed to stand for 15 hours in a thermostat controlled at 50 ° C., and evaluated according to the following criteria depending 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 even if force is easily applied with a finger or the like, it does not disperse.
<Evaluation of moisture and heat resistant storage stability>
The moisture resistance and 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 thermostatic oven controlled at 50 ° C. and humidity 80%, and evaluated according to the following criteria depending 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.

<Evaluation of low-temperature meltability>
The melting temperature was evaluated by the following method.
Using a commercially available corona charging spray gun on a standard zinc phosphate-treated steel plate made by Nippon Test Panel, resin particles are electrostatically coated so that the film pressure is 20 to 40 μm, and the baking temperature is changed for evaluation. The minimum temperature at which the surface smoothness by visual confirmation after baking for 5 minutes was good was measured.

  The evaluation results and the physical property values of the resin particles of the present invention are shown in Tables 6-8.

  While the resin particles of Examples 1 to 34 were excellent in heat-resistant storage stability and low-temperature meltability, the resin particles of Comparative Example 1 were remarkably deteriorated in low-temperature meltability and also had heat-resistant and moisture-resistant heat-resistant storage properties. It got worse. Further, the resin particles of Comparative Example 2 had good low-temperature meltability, but the heat-resistant storage stability and the moisture-resistant heat-resistant storage stability were significantly deteriorated. In the resin particles of Comparative Example 3, the particles aggregated and the particle size distribution was significantly deteriorated. In addition, the resin particles of Comparative Example 4 had poor dispersibility of the colorant as described above.

  The resin particles obtained by the production method of the present invention are excellent in heat storage stability and low-temperature meltability, and since the colorant is uniformly dispersed, the base particles of electrophotographic toner, additives for paints, additives for cosmetics, paper Useful as coating additives, slush molding resins, powder paints, electronic component manufacturing spacers, standard particles for electronic measuring instruments, electronic paper particles, medical diagnostic carriers, electrorheological particles, and other molding resin particles It is.

T1: Resin solution tank T2: Solution tank T3: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C.)
T5: Solvent trap F1: Ceramic filter (mesh: 0.5 μm)
B1, B2: Carbon dioxide cylinder P1, P2: Solution pump P3, P4: Carbon dioxide pump V1: Valve V2: Pressure adjustment valve

Claims (8)

Disperse the solvent (S) solution (L) of the resin (B) and the colorant dispersion (C) in carbon dioxide (X) in the liquid state or supercritical state in which the organic fine particles (A) are dispersed. Or by dispersing the solvent (S) solution (L), the colorant dispersion (C), and the wax dispersion (D) of the resin (B), the resin (B) and the colorant (k). And resin particles (Z1) in which organic fine particles (A) are fixed on the surface of resin particles (Y1) containing solvent (S ) , and (Z1) is treated with (X), and then obtained. (Z1) is a process for producing resin particles (Z) comprising a step of removing (X) and (S) from dispersion (Q) dispersed in a dispersion medium containing (X) and (S). And
The resin (B) is a resin composed of a crystalline part (a) and a non-crystalline part (b) having the lactone ring-opening polymer (p) as essential constituents,
The colorant dispersion (C) is a colorant (k), a dispersant (l) having a total acid value and amine value (mgKOH / g) of 20 to 250, a solvent (S), and a pressure of 2 MPa or more. (K) having a median diameter of 1 μm or less (S) obtained by mixing carbon dioxide (X) in a liquid state or supercritical state, and then expanding under reduced pressure to vaporize and remove (X) A method for producing resin particles, which is a dispersion liquid dispersed therein.
The resin (B) is a resin in which a crystalline part (a) and an amorphous part (b) are linearly bonded in the following format, and n is 0.5 to 3.5. The manufacturing method as described.
(A) {-(b)-(a)} n The production method according to claim 1 or 2, wherein the organic fine particles (A) are at least one vinyl resin (N) selected from the following (N1) to (N4).
(N1) An alkyl (meth) acrylate (m1) having 8 to 50 carbon atoms in the alkyl group as an essential constituent unit, or an alkyl (meth) acrylate (m1) having 8 to 50 carbon atoms in the alkyl group Is an essential structural unit, and further contains at least one member selected from perfluoroalkyl (alkyl) (meth) acrylate (m2) and unsaturated dicarboxylic acid and / or anhydride (m3) as a structural unit.
(N2) Vinyl resin having (meth) acrylonitrile (m4) and a crystalline vinyl monomer as essential constituent units.
(N3) A vinyl resin having a polyester chain and a vinyl monomer (m5) having a number average molecular weight of 500 to 100,000 as an essential constituent unit.
(N4) A vinyl resin containing 0.1 to 50% by weight of a silicone-containing vinyl monomer (m6) as a structural unit.   The wax dispersion (D) is a mixture having a temperature equal to or higher than the melting point of (w) containing the wax (w) and the solvent (S), and carbon dioxide (X) in a liquid state or a supercritical state where the pressure is 2 MPa or higher. And then expanding under reduced pressure to precipitate (w) below the melting point of (w) and vaporize and remove (X) to remove the wax (w) having a median diameter of 1 μm or less as the solvent ( The production method according to any one of claims 1 to 3, which is a dispersion liquid dispersed in S). When removing (X) and (S) from the dispersion (Q) in which the resin particles (Z1) are dispersed in a dispersion medium containing carbon dioxide (X) and a solvent (S) in a liquid state or a supercritical state The manufacturing method of any one of Claims 1-4 including the process of cooling the temperature of a dispersion (Q) below Ta [degreeC] below.
Ta: Exothermic peak temperature [° C.] at the time of DSC measurement of the solvent (S) solution (L) of the resin (B)   Claims including a step of cooling the dispersion (Q) by adding liquid carbon dioxide (X1) of (Ta-10) [° C] or less to the dispersion (Q) when cooling the temperature of the dispersion (Q) to Ta [° C] or less. Item 6. The manufacturing method according to Item 5.   The method includes a step of solid-liquid separation of a liquid mixture of liquid carbon dioxide (X1) and a solvent (S) and resin particles (Z) after cooling the temperature of the dispersion (Q) to Ta [° C.] or less. 7. The production method according to 5 or 6.   The resin particle (Z) obtained by the manufacturing method in any one of Claims 1-7.

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