JP5755423B2 - Method for producing dispersion - Google Patents

Description

  The present invention relates to a method for producing a dispersion in which various fine particles such as solid particles are dispersed in a dispersion solvent, and a method for producing resin particles using the dispersion.

In various manufacturing processes such as paints, inks, cosmetics, foods, pharmaceuticals, etc., the process includes the step of creating a dispersion by refining materials such as solid particles and dispersing the particles in a dispersion solvent such as water or organic solvent. However, the conventional method and apparatus require a long time and a lot of power to disperse the fine particles such as solid particles in the solvent.
In order to improve the method as described above, after supplying a mixture of a dispersoid and a solvent to a supercritical container to be in a supercritical state, the mixture in the supercritical state is released into the atmosphere, and is put into a collision part. There has also been proposed a method in which the dispersoid is finely dispersed in a solvent by collision (for example, see Patent Document 1), but there is a problem that dispersibility of the dispersoid in the solvent is insufficient.

Japanese Patent Laid-Open No. 10-192670

  The problem to be solved by the present invention is to provide a method for producing a dispersion, in which a dispersion in which a dispersoid such as solid particles is finely dispersed in a dispersion solvent can be obtained quickly and with less power.

  According to the present invention, the dispersoid (A), the dispersant (B) having a total acid value and amine value (mgKOH / g) of 20 or more and 250 or less, the solvent (C), and the compression having a pressure of 2 MPa or more The dispersion (E) in which the dispersoid (A) having a median diameter of 1 μm or less is dispersed in the solvent (C) is obtained by mixing the reactive fluid (D) and then expanding under reduced pressure to vaporize and remove (D). ) Is provided, which solves the above problems.

  Further, according to the present invention, the dispersion (E) in which the colorant obtained by the above production method is dispersed in the solvent (C), and the liquid state or supercritical state in which the organic fine particles (F) are dispersed. Carbon dioxide (X) and a solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed, and (E) and (L) are dispersed in (X). G), resin particles (I) in which organic fine particles (F) are fixed on the surface of resin particles (H) containing a colorant and a solvent (C) are formed, and then carbon dioxide (in a liquid state or a supercritical state) A method for producing colored resin particles including a step of removing X) and the solvent (C) is provided.

  Further, according to the present invention, the dispersion (E) in which the colorant obtained by the above production method is dispersed in the solvent (C), and the organic fine particles (F) in the non-aqueous organic solvent (N). The dispersed non-aqueous dispersion and the solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed, and (E) and (L) are dispersed in the non-aqueous dispersion of (F). To form resin particles (I) in which organic fine particles (F) are fixed on the surface of resin particles (H) containing resin (G), colorant and solvent (C), and then a non-aqueous organic solvent A method for producing colored resin particles including a step of removing (N) and the solvent (C) is provided.

  Further, according to the present invention, the dispersion (E) in which the colorant obtained by the above production method is dispersed in the solvent (C), and the organic fine particles (F) are dispersed in the aqueous medium (W). The aqueous dispersion and the solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed, and (E) and (L) are dispersed in the aqueous dispersion of (F). Resin particles (I) having organic fine particles (F) fixed thereon are formed on the surface of resin particles (H) containing resin (G), colorant and solvent (C), and then aqueous medium (W) and solvent ( A method for producing colored resin particles including the step of removing C) is provided.

According to the present invention, by mixing a dispersoid, a specific dispersant and a solvent in a compressive fluid, the dispersant can penetrate into the dispersoid and promote primary particle formation. In addition, effective dispersion can be achieved by rapidly reducing the density by rapidly expanding from high pressure to the atmosphere. Dispersion with a median diameter of the dispersoid of 1 μm or less can be achieved quickly and with less power. A liquid can be obtained.
In addition, when a dispersion of a colorant obtained by the above method and using a colorant as a dispersoid is used for producing colored resin particles, resin particles in which the colorant is finely and uniformly dispersed can be obtained.

It is a flowchart of the experimental apparatus used for preparation of the dispersion liquid by the mixing method by line blend in this invention. It is a flowchart of the experimental apparatus used for preparation of the colored resin particle using the carbon dioxide of a liquid state or a supercritical state in this invention.

The present invention is described in detail below.
The dispersoid (A) used in the method for producing the dispersion of the present invention is not particularly limited, and examples thereof include colorants (dyes, pigments, etc.), waxes, fillers, antistatic agents, charge control agents, ultraviolet absorbers, Antioxidants, antiblocking agents, heat stabilizers, flame retardants and the like can be mentioned, and a colorant is preferable in terms of interaction with the dispersant (B). By using the dispersoid (A) as a colorant, the interaction with the dispersant (B) is improved, and the dispersoid (A) can be effectively dispersed in the solvent (C).
Known dyes and pigments can be widely used as the colorant. Examples of the dye include monoazo, disazo, metal complex azo, anthraquinone, indigo, phthalocyanine, pyrazolone, stilbene, thiazole, quinoline, diphenylmethane, triphenylmethane, acridine , Xanthene, azine, thiazine, oxazine, polymethine, indophenol, perylene, etc. pigments include azo lake, insoluble azo, condensed azo, phthalocyanine, perylene, dioxazine, indigo, quinacridone, isoindolinone Organic pigments such as benzene, benzimidazolone, diketopyrrolopyrrole, and metal complexes, yellow iron oxide, bengara, carbon black, titanium dioxide, metal powder pigments, colored mica, and the like, and mixtures thereof.
Specific examples include carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, rhodamine B lake, methyl violet B lake, phthalocyanine blue, pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, olazole brown B, oil pink OP and the like.

The dispersant (B) has a total acid value and amine value (unit: mg KOH / g, the same shall apply hereinafter) of 20 to 250, preferably 30 to 250, more preferably 35 to 220, particularly. 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 dispersoid (A), and the dispersibility is deteriorated.
In the present invention, the acid value of the dispersant (B) 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).
The dispersant (B) should have a peak in the molecular weight distribution 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 (B) is more easily dissolved in the solvent (C) and can be efficiently adsorbed on the surface of the dispersoid (A). Further, (B) 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 (B) is measured under the following conditions using gel permeation chromatography (GPC).
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

  The composition of the dispersant (B) is not particularly limited as long as it has the total value of the acid value and the amine value, but is 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 dispersoid (A), and the dispersion stabilization of the dispersoid (A) in the solvent (C) can be promoted.

Among the dispersants (B), 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.
In the above, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and the same description method is used hereinafter.
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 (B), a commercial 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 SOLPERSE21000, 24000, 28000, 32000, 33000, 36000, 41000 manufactured by Nippon Lubrizol. , 54000, 56000, and 71000.

  The solvent (C) is preferably one that dissolves the dispersant (B) under use conditions, such as ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, 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.), An aromatic hydrocarbon solvent (toluene, xylene, etc.), an aliphatic hydrocarbon solvent (octane, decane, etc.), etc. are mentioned. Among these, ketone solvents, ether solvents and ester solvents are preferable, and ethyl acetate and acetone are more preferable.

As the compressive fluid (D), methane, ethylene, chlorofluorocarbon alternative, or the like may be used, but liquid carbon dioxide or supercritical carbon dioxide is preferable from the viewpoint of safety and ease of handling.
The pressure of the compressive fluid (D) 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 compressible fluid (D) permeates through the dispersoid (A) and the dispersoid (A) is easily pulverized. Further, the dispersant (B) is compressed with the compressible fluid (D) and the solvent (C ) Is better dissolved in the mixed solution and easily adsorbed on the surface of the dispersoid (A).
In the present invention, carbon dioxide in a liquid state is a triple point of carbon dioxide (temperature = −57 ° C., pressure 0.5 MPa) and the criticality of carbon dioxide on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. Supercritical gas-liquid boundary line passing through a point (temperature = 31 ° C., pressure = 7.4 MPa), isotherm of critical temperature, and carbon dioxide which is the temperature / pressure condition of the part surrounded by the solid-liquid boundary line The carbon dioxide in the state represents carbon dioxide which is a temperature / pressure condition higher than the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).

  The dispersant (B) is preferably one that dissolves in the mixture of the compressive fluid (D) and the solvent (C) during the production by the method for producing a dispersion of the present invention. By dissolving, it becomes easy for the dispersant (B) to come into uniform contact with the surface of the dispersoid (A) and be easily adsorbed, thereby enhancing the dispersion stabilization effect.

  In the method for producing a dispersion of the present invention, a dispersoid (A), a dispersant (B), a solvent (C) and a compressive fluid (D) having a pressure of 2 MPa or more are mixed, and then expanded under reduced pressure. (D) is vaporized and removed to obtain a dispersion (E) in which the dispersoid (A) having a median diameter of 1 μm or less is dispersed in the solvent (C).

The order and method of mixing the dispersoid (A), the dispersant (B), the solvent (C), and the compressive fluid (D) having a pressure of 2 MPa or more are not particularly limited, but first, the dispersion is dispersed in the solvent (C). It is preferred to dissolve the agent (B) and then mix with the dispersoid (A) and then introduce the compressible fluid (D) into the mixture.
The dispersant (B) is preferably used in an amount of 1 to 80% by weight, more preferably 5 to 70% by weight, particularly preferably 10 to 50% by weight, based on the dispersoid (A). In this range, the dispersant (B) is effectively adsorbed on the entire surface of the dispersoid (A).
The amount of the solvent (C) 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 dispersoid (A). Within this range, the dispersion (E) can be obtained with a viscosity that is easy to handle.

  When mixing a mixture of dispersoid (A), dispersant (B), and solvent (C) (hereinafter referred to as slurry) and compressible fluid (D) in a pressure-resistant container, the slurry is charged into the pressure-resistant container. The compressive fluid (D) is preferably introduced into the container and mixed with the slurry until a desired pressure is reached by a pressurizing means such as a pump provided in the pressure vessel. Since the slurry volume expands by introducing the compressive fluid (D), 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 in the method for producing a dispersion of the present invention can withstand a maximum pressure of 2 MPa or more, and is equipped with equipment capable of stirring and mixing the slurry and the compressible fluid (D) in the vessel. What has the nozzle for slurry taking out in the lower part is preferable.
The diameter of the nozzle is about 0.5 to 5.0 mm, and it is preferable that the slurry after mixing the compressive fluid (D) 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 introducing the compressive fluid (D), the dispersant (A) is adsorbed on the dispersoid (A) by stirring for a while. The stirring time may be the minimum time that the dispersant (B) can adsorb to the dispersoid (A), and is preferably stirred for about 10 to 30 minutes.
Moreover, the temperature at the time of stirring and mixing of the slurry and the compressive fluid (D) is preferably 15 to 120 ° C., more preferably from the viewpoint of preventing dispersoid aggregation due to excessive temperature rise and adjusting the temperature of the slurry at the time of discharge. Is 30-100 ° C.

  After stirring, the valve is opened from the nozzle at the bottom of the container (preferably in a fully open state), and the slurry is expanded under reduced pressure to atmospheric pressure at once. A dispersion (E) in which (A) is dispersed in the solvent (C) is obtained. Since the slurry temperature of the dispersion liquid (E) is lowered by this decompression / expansion operation, the slurry before decompression / 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 liquid temperature of the dispersion liquid (E) at the time of taking out.

The mixing of the slurry and the compressible fluid (D) can be continuously performed by a line blend (in-line mixing) method in addition to the method performed in the above-described pressure vessel, improving productivity, making quality constant, 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 the compressive fluid (D), first, the compressive fluid (D) is introduced into an apparatus for performing line blending and adjusted so that the pressure becomes 2 MPa or more, and then the slurry is changed to (D). It is preferable to introduce. The pressure (D) 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.
Dispersion liquid in which dispersoid (A) having a median diameter of 1 μm or less is dispersed in solvent (C) by expanding the mixture after line blending to atmospheric pressure and evaporating compressive fluid (D). (E) is obtained.

  The dispersoid (A) in the dispersion (E) 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 0.5 μm or less. In other words, there are no particles of 1 μm or more. 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.). Etc.).

Using the dispersion liquid (E) obtained by the production method of the present invention, resin particles in which the dispersoid (A) is finely dispersed in the particles can be produced. In particular, when the dispersoid (A) is a colorant, colored resin particles in which the colorant is finely and uniformly dispersed in the particles using the dispersion liquid (E) in which the colorant is dispersed in the solvent (C) are used. Can be obtained. As a manufacturing method of colored resin particles, the following (1) to (3) may be mentioned.
When the colored resin particles are produced in carbon dioxide (X) in a liquid state or in a supercritical state (hereinafter sometimes referred to as carbon dioxide (X)), the following production method (1) is preferred. .
Manufacturing method (1)
A dispersion (E) in which the colorant obtained by the above production method is dispersed in a solvent (C), a liquid state in which organic fine particles (F) are dispersed, or carbon dioxide (X) in a supercritical state, A solution (L) in which the resin (G) is dissolved in the solvent (C) is mixed, and (E) and (L) are dispersed in (X), whereby the resin (G), the colorant, and the solvent ( Colored resin particles by forming resin particles (I) having organic fine particles (F) fixed thereon on the surface of resin particles (H) containing C), and then removing carbon dioxide (X) and solvent (C) Manufacturing method.

Moreover, when manufacturing a colored resin particle in a non-aqueous organic solvent (N), it is preferable that it is the following manufacturing methods (2).
Manufacturing method (2)
A dispersion (E) in which the colorant obtained by the above production method is dispersed in the solvent (C), a non-aqueous dispersion in which the organic fine particles (F) are dispersed in the non-aqueous organic solvent (N), and The resin (G) is mixed with the solution (L) in which the resin (G) is dissolved in the solvent (C), and (E) and (L) are dispersed in the non-aqueous dispersion of (F). The resin particles (I) having the organic fine particles (F) fixed thereon are formed on the surfaces of the resin particles (H) containing the colorant and the solvent (C), and then the non-aqueous organic solvent (N) and the solvent (C) The manufacturing method which obtains colored resin particle | grains by removing.

Moreover, when manufacturing a colored resin particle in an aqueous medium (W), it is preferable that it is the following manufacturing methods (3).
Manufacturing method (3)
A dispersion (E) in which the colorant obtained by the above production method is dispersed in a solvent (C), an aqueous dispersion in which organic fine particles (F) are dispersed in an aqueous medium (W), a resin ( A solution (L) in which G) is dissolved in the solvent (C) is mixed, and (E) and (L) are dispersed in the aqueous dispersion of (F), whereby the resin (G) and the colorant are mixed. Coloring is performed by forming resin particles (I) with organic fine particles (F) fixed on the surface of resin particles (H) containing solvent (C), and then removing aqueous medium (W) and solvent (C). A production method for obtaining resin particles.

The production method (1) will be described in detail.
As the resin (G) used in the production methods (1) to (3), a thermoplastic resin (G1), a resin (G2) obtained by microcrosslinking the thermoplastic resin, a thermoplastic resin as a sea component, and a cured resin. A polymer blend (G3) as an island component may be mentioned, and two or more kinds may be used in combination.
Examples of the thermoplastic resin include a vinyl resin, a polyester resin, a polyurethane resin, and an epoxy resin. Among these, a vinyl resin, a polyester resin, a polyurethane resin, and a combination thereof are preferable from the viewpoint that a dispersion of fine spherical resin particles is easily obtained.

The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbon:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, α-olefins other than those described above; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7 -Octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as (di) cyclopentadiene; terpenes such as pinene.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, such as α-methylstyrene, 2,4-dimethylstyrene and the like; and vinylnaphthalene.
(2) Carboxyl group-containing vinyl monomers and salts thereof: unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and their anhydrides and monoalkyl (1 to 24 carbon atoms) esters such as (meth) acrylic Acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, Carboxyl group-containing vinyl monomers such as cinnamic acid.
(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts: alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene Sulfonic acid and the like; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, for example, sulfopropyl (meth) acrylate, and sulfuric acid ester or sulfonic acid group-containing vinyl monomer; and salts thereof.
(4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, ( (Meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2-acryloyloxyethylphosphonic acid. Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.
(5) Hydroxyl group-containing vinyl monomer: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl Alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.
(6) Nitrogen-containing vinyl monomer:
(6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, etc.
(6-2) Amide group-containing vinyl monomer: (meth) acrylamide, N-methyl (meth) acrylamide, etc.
(6-3) Nitrile group-containing vinyl monomer: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc.
(6-4) Quaternary ammonium cation group-containing vinyl monomers: tertiary amines such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized products of group-containing vinyl monomers (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate), etc.
(6-5) Nitro group-containing vinyl monomer: nitrostyrene and the like.
(7) Epoxy group-containing vinyl monomer: Glucidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.
(8) Halogen element-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.
(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
(9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl ( (Meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadec (Meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or Alicyclic groups), dialkyl maleates (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes Vinyl monomers having a polyalkylene glycol chain such as [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] [polyethylene glycol (molecular weight 300 ) Mono (meth) acrylate, polypropylene glycol (molecular weight 500) monoacrylic Rate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate 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.], etc.
(9-2) Vinyl (thio) ether, such as vinyl methyl ether,
(9-3) Vinyl ketones such as vinyl methyl ketone.
(10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

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

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

  Diol (11) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, Tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol) An alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; an alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenol; Examples include polylactone diol (such as poly ε-caprolactone diol) and polybutadiene diol. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

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

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

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

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

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

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

The following are mentioned as an example of a polyamine (16).
Aliphatic polyamines (C2 to C18):
[1] Aliphatic polyamine {C2-C6 alkylenediamine (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, etc.}}
[2] These alkyl (C1-C4) or hydroxyalkyl (C2-C4) substituted products [dialkyl (C1-C3) aminopropylamine, etc.]
[3] Alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]
[4] Aromatic ring-containing aliphatic amines (C8 to C15) (such as xylylenediamine, tetrachloro-p-xylylenediamine),
-Alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.
Aromatic polyamines (C6-C20):
[1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine and the like; nucleus-substituted alkyl group [C1-C4 alkyl such as methyl, ethyl, n- and i-propyl, butyl, etc.] Aromatic polyamines such as 2,4- and 2,6-tolylenediamine etc.), and mixtures of various proportions of these isomers [2] nuclear substituted electron withdrawing groups (Cl, Br, I, Aromatic polyamines having halogens such as F; alkoxy groups such as methoxy and ethoxy; nitro groups, etc. [methylene bis-o-chloroaniline, etc.]
[3] Aromatic polyamine having a secondary amino group [Any or all of —NH ₂ of the aromatic polyamines (4) to (6) above is —NH—R ′ (R ′ is a lower group such as methyl, ethyl, etc.) Substituted with an alkyl group] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.],
Heterocyclic polyamines (C4 to C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc.
Polyamide polyamine: low molecular weight polyamide polyamine obtained by condensation of dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid) polyamine (such as alkylene diamine, polyalkylene polyamine, etc.)
-Polyether polyamine: hydride of cyanoethylated polyether polyol (polyalkylene glycol and the like).

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

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

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

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

  The resin (G2) obtained by finely crosslinking a thermoplastic resin is a resin in which a crosslinked structure is introduced and the Tg of the resin (G) is 20 to 200 ° C. Such a cross-linked structure may be any cross-linked form such as covalent bond, coordinate bond, ionic bond, hydrogen bond, and the like. As a specific example, for example, when a polyester is selected as the resin (G2), a cross-linked structure is introduced by using a polyol or polycarboxylic acid at the time of polymerization, or a compound having a functional group number of three or more in both. be able to. When a vinyl resin is selected as the resin (G2), a crosslinked structure can be introduced by adding a monomer having two or more double bonds during polymerization.

  As a polymer blend (G3) having a thermoplastic resin as a sea component and a cured resin as an island component, those having a Tg of 20 to 200 ° C. and a softening start temperature of 40 to 220 ° C., specifically vinyl resins and polyesters Resins, polyurethane resins, epoxy resins and mixtures thereof.

  The number average molecular weight (measured by GPC, hereinafter abbreviated as Mn) of the resin (G) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000, and the solubility parameter (SP value, details are ) Is preferably 7 to 18, more preferably 8 to 16, and particularly preferably 9 to 14. Moreover, when it is desired to modify the thermal characteristics of the resin particles (I), the resin (G2) or the resin (G3) may be used.

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

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

  In the production method (1), the insoluble content of the resin (G) with respect to the solvent (C) in the equal weight mixture of the solvent (C) and the resin (G) in the standard state of 23 ° C. and 0.1 MPa is the resin ( Preferably it is 20 weight% or less with respect to the weight of G), More preferably, it is 15 weight% or less. If the insoluble matter weight is 20% by weight or less, the particle size distribution of the obtained resin particles becomes narrow.

Moreover, 9-16 are preferable and, as for the solubility parameter (SP value) of a solvent (C), 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 = (ΔE / V) 1} /2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is determined by Robert, EF. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science Vol. 14, pages 147-154.

Examples of the solvent (C) for dissolving the resin (G) in the production method (1) include the same solvents (C) used for the production of the dispersion (E), and two or more of these solvents can be used. A mixed solvent or a mixed solvent of these organic solvents and water can also be used.
Preferably, from the viewpoint of ease of particle formation, a mixed solvent (particularly, a mixed solvent of acetone, methanol and water, a mixed solvent of acetone and methanol, a mixed solvent of acetone and ethanol, a mixed solvent of acetone and water, and methyl ethyl ketone) And water mixed solvent).

  The solution (L) of the resin (G) is produced by dissolving the resin (G) in the solvent (C). The concentration of the resin (G) with respect to the weight of the solution (L) is preferably 10 to 90% by weight, and more preferably 20 to 80% by weight.

  Since the solution (L) of the resin (G) is dispersed in (X), it preferably has an appropriate viscosity. From the viewpoint of particle size distribution, it is preferably 100 Pa · s or less, more preferably 10 Pa at 25 ° C. -S or less. The solubility of the resin (G) in (X) is preferably 3% or less, more preferably 1% or less.

The organic fine particles (F) used in the method for producing colored resin particles of the present invention may be any material that can be dispersed in the solvent (C) and fixed to the surface of the resin particles (H).
The organic fine particles (F) used in the production method (1) have a degree of swelling by carbon dioxide (X) (hereinafter, degree of swelling) at a glass transition temperature (hereinafter sometimes referred to as Tg) or a temperature below the melting point. Is preferably 16% or less, more preferably 10% or less, and particularly preferably 5% or less. When the organic fine particles (F) having a swelling degree of 16% or less are used, aggregation of the resin particles is easily suppressed, and the particle size distribution of the resin particles becomes good.

  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).

  As the resin (f) constituting the organic fine particles (F), at least one selected from a crystalline resin (f1) and an amorphous resin (f2) is used. As the non-crystalline resin (f2), a cross-linkable non-crystalline resin is preferable. Of these, the crystalline resin (f1) is preferable.

  The melting point of the crystalline resin (f1) is preferably 50 to 110 ° C, more preferably 55 to 100 ° C, and particularly preferably 60 to 90 ° C. If the melting point of the crystalline resin (f1) is 50 ° C. or higher, the resin particles (I) are difficult to block even during long-term storage. When it is 110 ° C. or lower, the low-temperature fixability is good when used as the base particle of the electrophotographic toner. The melting point can be measured from an endothermic peak in differential scanning calorimetry (hereinafter referred to as DSC).

The degree of crystallinity of the crystalline resin (f1) 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 (H). %. The degree of crystallinity is obtained by calculating the heat of fusion [ΔHm (J / g)] from the area of the endothermic peak 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%.

  Mn of the crystalline resin (f1) is preferably 1000 or more, more preferably 1500 or more, 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 composition of the crystalline resin (f1) is not particularly limited, but preferred specific examples include, for example, crystalline having aliphatic or aromatic polyester, aliphatic polyurethane and / or polyurea, and alkyl (meth) acrylate as an essential constituent unit. Examples thereof include a vinyl resin, a crystalline vinyl resin (f14) having (meth) acrylonitrile and a crystalline vinyl monomer as essential constituent units, and a crystalline polyolefin (f15).

As the aliphatic or aromatic polyester, the diol (11) and dicarboxylic acid (13) can be used, and in particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and 2 to 50 carbon atoms. A linear aliphatic dicarboxylic acid having an alkylene chain is an essential structural unit, and the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is 10 to 52, and if necessary, the number of carbon atoms Crystalline polyester (f11) having 6 to 30 aromatic dicarboxylic acid as a structural unit is preferred.
From the viewpoint of storage stability, the total number of carbon atoms of the alkylene chain of the diol and the alkylene chain of the dicarboxylic acid is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. . Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

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

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

As the aliphatic polyurethane and / or polyurea, the diol (11), diamine [divalent one of the polyamine (16)] and diisocyanate [divalent one of the polyisocyanate (15)] are used. In particular, a linear aliphatic diol having an alkylene chain having 2 to 50 carbon atoms and / or a linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms and an alkylene chain having 2 to 50 carbon atoms A crystalline polyurethane having a linear aliphatic diisocyanate as an essential constituent unit, and the total number of carbon atoms of the alkylene chain of the diol and / or diamine and the alkylene chain of the diisocyanate being 10 to 52, and / or Polyurea (f12) is preferred.
In addition, from the polyester diol obtained by making the linear aliphatic diol which has a C2-C50 alkylene chain and the said dicarboxylic acid (13) react, and the linear aliphatic diisocyanate which has a C2-C50 alkylene chain. The resulting polyurethane is also included in (f12).
From the viewpoint of storage stability, aliphatic polyurethane and / or polyurea has a carbon number of alkylene chain of diol and / or diamine (when a mixture of diol and diamine is used, carbon of alkylene chain averaged by the weight ratio). Number) and the total number of carbon atoms of the alkylene chain of the diisocyanate is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

The preferable carbon number of an alkylene chain and the preferable specific example of the said linear aliphatic diol which has a C2-C50 alkylene chain are the same as that in the crystalline polyester (f11).
From the viewpoint of crystallinity, the number of carbon atoms in the alkylene chain of the linear aliphatic diamine having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more. . From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diamine are tetramethylene diamine and hexamethylene diamine.
In addition, the number of carbon atoms in the alkylene chain of the linear aliphatic diisocyanate having an alkylene chain having 2 to 50 carbon atoms is preferably 2 or more, more preferably 3 or more, and particularly preferably 4 or more from the viewpoint of crystallinity. It is. From the viewpoint of fixability, it is preferably 50 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less. Preferred as the linear aliphatic diisocyanate are tetramethylene diisocyanate and hexamethylene diisocyanate.

As the crystalline vinyl resin having an alkyl (meth) acrylate as an essential constituent unit, a crystalline vinyl resin (f13) having an alkyl (meth) acrylate having an alkyl group having 12 to 50 carbon atoms as an essential constituent unit is preferable. From the viewpoint of storage stability, the alkyl group preferably has 12 or more carbon atoms, more preferably 14 or more, and particularly preferably 18 or more. Further, from the viewpoint of fixability, it is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. From the viewpoint of storage stability, the alkyl group is preferably a straight chain. Preferred as the alkyl (meth) acrylate having an alkyl group with 12 to 50 carbon atoms are octadecyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl acrylate.
The crystalline vinyl resin containing alkyl (meth) acrylate as an essential constituent unit may be a homopolymer of alkyl (meth) acrylate or a copolymer with other monomers. As the other monomer, a monomer having an acidic functional group (for example, the vinyl monomer such as a carboxyl group-containing vinyl monomer and a sulfone group-containing vinyl monomer can be appropriately selected.
The content of the constituent unit of alkyl (meth) acrylate having an alkyl group of 12 to 50 carbon atoms in the crystalline vinyl resin (f13) is preferably 40% by weight or more, more preferably 45% by weight or more, particularly preferably. Is 60% by weight or more.

As the crystalline vinyl resin (f14) having (meth) acrylonitrile and a crystalline vinyl monomer as essential structural units, the content of the structural unit of (meth) acrylonitrile is 0.01 to from the viewpoint of adhesion to resin particles. It is preferably 40% by weight, more preferably 0.05 to 35% by weight, and particularly preferably 0.1 to 30% by weight.
The crystalline vinyl monomer used in combination is not particularly limited as long as a crystalline vinyl resin can be formed, but alkyl (meth) acrylate having 12 to 50 carbon atoms in the above alkyl group, ethylene, and the like Can be mentioned.

  Examples of the crystalline polyolefin (f15) include polyethylene and polypropylene.

  Examples of the method for producing an aliphatic or aromatic polyester include a method of reacting a low molecular polyol and / or a polyalkylene ether diol having an Mn of 1000 or less and a polycarboxylic acid, a method by ring-opening polymerization of a lactone, a low molecular diol and a lower molecular diol. Well-known manufacturing methods, such as the method of making it react with carbonic acid diester of alcohol (methanol etc.), are mentioned.

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

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

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

  Of the crystalline resin (f1), particularly preferred are (f11), (f12), (f13), and (f14), and most preferred is (f13).

Examples of the amorphous resin (f2) include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide, polyimide, silicone resin, fluorine resin, phenol resin, melamine resin, polycarbonate, cellulose, and a mixture thereof. . Specific examples of the amorphous resin (f2) include those similar to the resin (G). As the non-crystalline resin (f2), a cross-linkable non-crystalline resin is preferable.
The composition of (f2) is not particularly limited, and a commonly used resin may be used.
For example, as the crosslinkable vinyl resin, a copolymer of vinyl monomers including a vinyl monomer (divinylbenzene or the like) having two or more vinyl polymerizable functional groups can be used.
The crosslinkable polyester resin is a polycondensate of a polyol and a polycarboxylic acid, and at least part of the polyol and / or polycarboxylic acid, the trivalent or higher polyol (12) and / or the trivalent or higher polyvalent polyresin. Examples thereof include polyester resins obtained using carboxylic acid (14).
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 (F), a crystalline resin (f1) and an amorphous resin (f2) may be used in combination. The melting point of the mixture of (f1) and (f2) is preferably 50 to 150 ° C. The content of (f2) is preferably 0 to 50% by weight with respect to the total weight of (f1) and (f2). Moreover, the microparticles | fine-particles which coat | covered the amorphous resin (f2) with the crystalline resin (f1) may be sufficient.

The production method of the organic fine particles (F) containing the crystalline resin (f1) and / or the amorphous resin (f2) may be any production method. Specific examples thereof include a dry production method [organic fine particles ( F) The resin constituting (f) is dry pulverized by a known dry pulverizer such as a jet mill], the wet manufacturing method [(f) powder is dispersed in an organic solvent, such as a bead mill or a roll mill. A method of wet pulverizing with a known wet disperser, a method of spray drying the solvent solution of (f) with a spray dryer or the like, a method of supersaturating the solvent solution of (f) by adding a poor solvent or cooling and precipitating, A method of dispersing a solvent solution in water or an organic solvent, a method of polymerizing the precursor of (f) in water by an emulsion polymerization method, a soap-free emulsion polymerization method, a seed polymerization method, a suspension polymerization method, or the like; Precursor method of polymerizing by dispersion polymerization or the like in an organic solvent] is cited.
Further, after synthesizing the organic fine particles (F ′) of the amorphous resin (f2) by the above method, the crystalline resin (f1) is converted to the (F ′) surface by a known coating method, seed polymerization method, mechanochemical method or the like. You may form in. Among these, from the viewpoint of ease of production of the organic fine particles (F), 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 (F) may be used as they are, and in order to have the adsorptivity to the resin particles (H) or to modify the powder characteristics and electrical characteristics of the resin particles (I), for example, silane-based, The surface may be modified by surface treatment with a coupling agent such as 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 (F) and the resin particles (H) 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 (F) and the resin particles (H) 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 (F) and the resin particles (H) have at least an acidic functional group or basic functional group as the crystalline resin (f1) or resin (G) in order to impart an acidic functional group or basic functional group to the surface thereof. In order to impart these functional groups to the organic fine particles (F) and the resin particles (H), a surface treatment may be performed.

  As the crystalline resin (f1) having an acidic functional group, an aliphatic polyester having an acid value and a monomer having an acidic functional group (for example, the carboxyl group-containing vinyl monomer and the sulfone group-containing vinyl monomer) are copolymerized. Vinyl resin and the like.

  Examples of the crystalline resin (f1) having a basic functional group include a vinyl resin obtained by copolymerizing a monomer having a basic functional group (for example, the amino group-containing vinyl monomer).

  The volume average particle size of the organic fine particles (F) is preferably 0.01 to 0.5 μm, particularly preferably 0.015 to 0.4 μm. In the present invention, the volume average particle size is determined using 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.), multi It can be measured with sizer III (manufactured by Beckman Coulter). The preferable volume average particle diameter of (F) is the same in the production methods (2) and (3) of the colored resin particles.

  In the method (1) for producing colored resin particles of the present invention, any method may be used for dispersing the organic fine particles (F) in carbon dioxide (X). For example, (F) and (X) are charged in a container. , A method in which (F) is directly dispersed in (X) by stirring, ultrasonic irradiation, or the like, or a method in which a dispersion liquid in which organic fine particles (F) are dispersed in a solvent (C) is introduced into (X). Etc.

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

  Examples of the solvent (C) used in the dispersion liquid (F) include the same solvents as those used in the method for producing the dispersion liquid. The solvent (C) is preferably an aliphatic hydrocarbon solvent (decane, hexane, heptane, etc.) and an ester solvent (ethyl acetate, butyl acetate, etc.) because of the dispersibility of the organic fine particles (F).

  The weight ratio of the organic fine particles (F) to the solvent (C) is not particularly limited, but the organic fine particles (F) are preferably 50% by weight or less, more preferably 30% by weight or less with respect to the solvent (C). It is particularly preferably 20% by weight or less. Within this range, the organic fine particles (F) can be efficiently introduced into (X).

  The method for dispersing the organic fine particles (F) in the solvent (C) is not particularly limited, but the organic fine particles (F) are charged in the solvent (C) and directly dispersed by stirring, ultrasonic irradiation, or the like. Examples thereof include a method of crystallizing fine particles by dissolving them in a solvent (C) at a high temperature.

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

  In the production method (1), in the dispersion step of dispersing the resin (G) solution (L) in carbon dioxide (X), the following dispersion stabilizer (J) can be used. The dispersion stabilizer (J) is a compound having at least one group of a dimethylsiloxane group and a functional group containing fluorine. Furthermore, it is preferable to have a chemical structure having affinity for the resin (G) together with a dimethylsiloxane group and a fluorine-containing group having affinity for carbon dioxide.

For example, when the resin (G) is a vinyl resin, the dispersion stabilizer (J) 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. .
As the monomer (or reactive oligomer) (M1-1) having a dimethylsiloxane group, methacryl-modified silicone is preferable and has 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 15-45, and R is an organic modification group containing a methacryl group. An example of R includes —C ₃ H ₆ OCOC (CH ₃ ) ═CH ₂ .

  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 (G) is a urethane resin, the dispersion stabilizer (J) is preferably a urethane resin having a monomer having at least one of a dimethylsiloxane group and a functional group containing fluorine as a structural unit. .
(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 (G) has an acid value, the dispersion stabilizer (J) preferably has an amino group from the viewpoint of dispersibility. 1-50 are preferable, as for the acid value of resin (G), More preferably, it is 3-40, Most preferably, it is 5-30. 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 (J), for example, a monomer (or reactive oligomer) having a dimethylsiloxane group (M1-1) and / or a monomer (M1-2) containing fluorine, and the resin (G) 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 (G) has an acid value, the organic fine particles (F) 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 (F). A method of containing, a method of using a compound having an amino group as a component constituting the organic fine particles (F), a method of reacting an amino group-containing coupling agent on the surface of the organic fine particles (F), a surface of the organic fine particles (F) Examples thereof include a method for adsorbing an amino group-containing compound.

  The addition amount of the dispersion stabilizer (J) is preferably from 0.01 to 50% by weight, more preferably from 0.02 to 40% by weight, particularly preferably from the viewpoint of dispersion stability, based on the weight of the resin (G). 0.03 to 30% by weight. The range of the weight average molecular weight of the dispersion stabilizer (J) is preferably 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 (J) is improved.

  In the method (1) for producing colored resin particles of the present invention, in the resin particles (H) containing the resin (G), the colorant and the solvent (C), a colorant, a dispersant (B), a dispersion stabilizer (J ) Other additives (fillers, antistatic agents, release agents, charge control agents, ultraviolet absorbers, antioxidants, antiblocking agents, heat stabilizers, flame retardants, etc.) may be included. . As a method for adding other additives to the resin particles (H), the resin (G) or the solvent (C) solution (L) of (G) and the additive are mixed in advance, and then (X) It is preferable to add and disperse the mixture. For example, when the resin particles are used as base particles of an electrophotographic toner, a release agent and / or a charge control agent is added to the resin particles as necessary.

  The dispersion liquid (E) in which the colorant is dispersed in the solvent (C), the solution (L) in which the resin (G) is dissolved in the solvent (C), and the organic fine particles (F) in carbon dioxide (X). When the dispersion (X0) is dispersed in the dispersion (X0), the dispersion (E) and the solution (L) may be mixed in advance, and then the mixture may be introduced into (X0) and dispersed. Although it may be introduced into (X0) and dispersed, it is preferable that (E) and (L) are mixed in advance and then dispersed in (X0). If it does so, a coloring agent can be more uniformly disperse | distributed in resin (G).

  The amount of the colorant dispersion (E) used is preferably such that the amount of the colorant relative to the resin (G) is 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, Particularly preferably, it is 1 to 10% by weight.

  In the production method (1), the dispersion (E) in which the colorant is dispersed in the solvent (C) and the solution (L) of the resin (G) are dispersed in the organic fine particles (F) in carbon dioxide (X). Any method may be used for dispersing in the dispersion (X0). As a specific example, a method of dispersing a mixed liquid of the dispersion (E) and the solution (L) in the dispersion (X0) with a stirrer or a dispersing machine, a mixed liquid of the dispersion (E) and the solution (L) , (F) is dispersed in the dispersion (X0) in which (F) is dispersed through a spray nozzle to form droplets, the resin in the droplets is supersaturated, and resin particles are deposited. A method (known as ASES: Aerosol Solvent Extraction System), a mixture of dispersion (E) and solution (L), dispersion (X0) from a coaxial multiple tube (double tube, triple tube, etc.) A method in which particles are obtained by simultaneously ejecting from a separate tube together with a high-pressure gas, an entrainer, etc., and applying an external stress to the droplets to promote breakup to obtain particles (SEDS: Solution Enhanced Dispersion by Su ercritical known as Fluids), and a method of irradiating an ultrasonic wave and the like.

In this way, the dispersion (E) of the colorant and the solution (L) of the resin (G) are dispersed in the dispersion (X0) in which the organic fine particles (F) are dispersed in carbon dioxide (X). The surface of the resin particles (H) containing the resin (G), the colorant and the solvent (C) is grown by growing the dispersed resin (G) while adsorbing the organic fine particles (F) on the surface. Resin particles (I) to which the organic fine particles (F) are fixed are formed. A dispersion in which (I) is dispersed in (X) is referred to as dispersion (X1).
The dispersion (X1) is preferably a single phase. That is, it is not preferable that the solvent (C) phase is separated in addition to the phase containing carbon dioxide (X) in which (I) is dispersed. Therefore, it is preferable to set the amount of the solution (L) of (G) with respect to the dispersion (X0) so that the solvent phase is not separated. For example, it is preferably 90% by weight or less with respect to (X0), more preferably 5 to 80% by weight, and particularly preferably 10 to 70% by weight.
The amount of (C) contained in the resin particles (H) containing the resin (G), the colorant and the solvent (C) is preferably 10 to 90% by weight, more preferably 20 to 70% by weight. is there.
The weight ratio of the resin (G) to carbon dioxide (X) is preferably (G) :( X) is 1: (0.1-100), more preferably 1: (0.5-50). Especially preferably, it is 1: (1-20).

  In the method (1) for producing colored resin particles of the present invention, the operation performed in carbon dioxide (X) is preferably performed at the temperature described below. That is, in order to prevent carbon dioxide from undergoing a phase transition in the pipe during decompression to block the flow path, the temperature is preferably 30 ° C. or higher, and organic fine particles (F), resin particles (H), resin particles ( In order to prevent thermal degradation of I), 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 temperature of the dispersion (X0) and the dispersion (X1). In the method (1) for producing colored resin particles of the present invention, the operation performed in carbon dioxide (X) can be performed at a temperature above or below the Tg or melting point of the organic fine particles (F). It is preferable to carry out at a temperature below the melting point.

  In the method (1) for producing colored resin particles of the present invention, the operation performed in carbon dioxide (X) is preferably performed at the pressure described below. That is, in order to disperse resin particle (I) well in (X), it is preferably 7 MPa or more, and preferably 40 MPa or less from the viewpoint of equipment cost and operation cost. More preferably, it is 7.5-35 MPa, More preferably, it is 8-30 MPa, Most preferably, it is 8.5-25 MPa, Most preferably, it is 9-20 MPa. The same applies to the pressure in the container forming the dispersion (X0) and the dispersion (X1).

  In the method (1) for producing colored resin particles of the present invention, the temperature and pressure of the operation performed in carbon dioxide (X) are such that the resin (G) is not dissolved in (X) and (G) is aggregated. It is preferable to set it within a range that can be united. Normally, the target dispersion tends to not dissolve in (X) at lower temperatures and lower pressures, and (G) tends to aggregate and coalesce at higher temperatures and pressures. The same applies to the dispersion (X0) and the dispersion (X1).

  In the carbon dioxide (X) in the production method (1) of the colored resin particles of the present invention, other properties are adjusted to adjust the physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium. The substance (Y) may be appropriately contained, and examples thereof include inert gases such as nitrogen, helium, argon, and air.

  The weight fraction of carbon dioxide (X) in the total of carbon dioxide (X) and the other substance (Y) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. is there.

  When the organic fine particles (F) contain the crystalline resin (f1), after forming the resin particles (I), the crystalline resin (f1) preferably has a melting point minus, as a further step, if necessary. By heating to 50 ° C. or more, more preferably melting point minus 10 ° C. or more, more preferably melting point or more, the organic fine particles (F) adhering to the surface of the resin particles (G) are melted, and the organic fine particles (F) Can be fixed to the surface of the resin particles (G), or a film derived from the organic fine particles (F) can be formed to form the resin particles (I ′). From the viewpoint of suppressing the aggregation of (I ′), the heating time is preferably 0.01 to 1 hour, and more preferably 0.05 to 0.7 hour.

In the resin particles (I) obtained by the method (1) for producing colored resin particles of the present invention, the organic fine particles (F) are once fixed on the surface of the resin particles (H), but (F) is a crystalline resin ( In the case of containing f1), depending on the composition of the crystalline resin (f1) and the resin (G) and the type of the solvent (C), the organic fine particles (F) are formed into a film during the production process. A film in which (F) is formed into a film may be formed on the surface.
The resin particles (I) finally obtained by the production method (1) are those in which the organic fine particles (F) are fixed on the surfaces of the resin particles (H), those in which a film derived from (F) is formed, Any of those obtained by forming a part of (F) into a film may be used. The same applies to the manufacturing methods (2) and (3) described later.
The surface state and shape of the resin particles (I) 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).

  From the dispersion (X1) in which the resin particles (I) are dispersed, the carbon dioxide (X) and the solvent (C) are usually removed under reduced pressure to obtain colored resin particles. 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 obtained resin particles 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 may be collected after depressurization, or once collected under high pressure before depressurization, and then depressurized. When collecting the resin particles under high pressure after collecting under high pressure, the collection container may be depressurized by batch operation, or the continuous extraction operation is performed using a rotary valve. May be.

  After forming the resin particles (I) [including the case of the resin particles (I ′)], it is preferable to perform a step of removing or reducing the solvent (C) before the above-described removal step by reduced pressure. That is, since the dispersion (X1) in which (I) is dispersed in (X) contains the solvent (C), if the container is decompressed as it is, the solvent dissolved in (X1) is condensed and resin particles There may be a problem that the resin particles (I) are re-dissolved or the resin particles (I) are united when collecting the resin particles (I). As a method for removing or reducing the solvent, for example, resin particles (X) obtained by dispersing a dispersion liquid (E) of a colorant and a solvent (C) solution (L) of a resin (G) ( The dispersion (X1) containing I) is further mixed with carbon dioxide (X) to extract the solvent (C) from the resin particles (I) into the carbon dioxide (X) phase, and then the solvent (C ) Containing (X) is preferably replaced with (X) containing no solvent (C), and then the pressure is reduced.

  In the mixing method of the dispersion (X1) in which the resin particles (I) are dispersed in carbon dioxide (X) and (X), (X) having a pressure higher than (X1) may be applied, and (X1) May be added to (X) at a lower pressure than (X1), but the latter is more preferable from the viewpoint of ease of continuous operation. From the viewpoint of preventing coalescence of the resin particles (I), the amount of (X) mixed with (X1) is preferably 1 to 50 times the volume of (X1), more preferably 1 to 40 times, most preferably 1 to 30 times. By removing or reducing the solvent contained in the resin particles (I) as described above and then removing (X), it is possible to prevent the resin particles (I) from being united.

  As a method of replacing carbon dioxide (X) containing solvent (C) with (X) not containing solvent (C), the resin particles (I) are once supplemented with a filter or cyclone, and then the solvent is maintained while maintaining the pressure. A method of circulating carbon dioxide (X) until (C) is completely removed can be mentioned. The amount of (X) to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, most preferably 1 to 1 times the volume of (X1) from the viewpoint of solvent removal from the dispersion (X1). 30 times

The manufacturing method (2) of the colored resin particles of the present invention will be described in detail.
Examples of the resin (f) and the resin (G) constituting the organic fine particles (F) used in the production method (2) include the same as those used in the production method (1). The resin (f) is preferably a crystalline resin (f), more preferably a crystalline vinyl resin (f13) having an alkyl (meth) acrylate having an alkyl group with 12 to 50 carbon atoms as an essential constituent unit. is there.

The non-aqueous organic solvent (N) used in the production method (2) is preferably an organic solvent in which the solubility of the resin (G) is 1% or less in the solvent (C). If the solubility of the resin (G) is 1% or less, it is preferable that the resin particles (I) are difficult to unite with each other. The solubility of the resin (G) in the non-aqueous organic solvent (N) is determined from the non-aqueous dispersion containing the insoluble content of (G) in which (G) is dissolved in (N) until saturation is reached. The weight of the supernatant obtained by sedimentation of the dissolved component by centrifugation, and the weight of the residue after drying at the boiling point of the non-aqueous organic solvent (N) with a vacuum dryer is taken as the value.
Specifically, it is calculated by the following procedure.
The non-aqueous dispersion (25 ° C.) is centrifuged at 3000 rpm for 10 minutes, and about 2 g (wg) of the supernatant is collected in an aluminum container. Further, the supernatant is dried with a vacuum dryer under a reduced pressure of 20 mmHg for 1 hour under the temperature condition of the boiling point of the non-aqueous organic solvent (N), and the weight of the residue is weighed. If the residue weight at this time is Wg, the solubility of the resin (G) in the non-aqueous organic solvent (N) can be calculated by W / w × 100 [%].
Specifically, the non-aqueous organic solvent (N) is preferably a hydrocarbon solvent (hexane, octane, decane, dodecane, isododecane, liquid paraffin, etc.) and silicone oil.

  In the method (2) for producing colored resin particles of the present invention, any method may be used for dispersing the organic fine particles (F) in the non-aqueous organic solvent (N), for example, (F) and (N) in a container. And a method of directly dispersing (F) in (N) by stirring, spraying, ultrasonic irradiation, etc., a method of introducing the solvent dispersion of (F) into (N), and the like. As the organic fine particles (F), those which do not dissolve in (N) and are stably dispersed in (N) are preferable.

The solubility parameter (SP value) of the solvent (C) for dissolving the resin (G) used in the method (2) for producing colored resin particles of the present invention is preferably in the range of 9.5 to 20, more preferably 10 to 10. 19. When the SP value of the solvent (C) is within this range, when the solvent (C) solution (L) of the resin (G) is dispersed in the non-aqueous organic solvent (N), (C) is in (N). This is preferable because the particle size distribution of the resin particles (I) is not widened.
When a mixed solvent is used as the solvent (C), the SP value is assumed to satisfy the addition rule, and the average value calculated from the SP value of each solvent is preferably within the above range.

  As solvent (C) used for manufacturing method (2), what is suitable for the combination with resin (G) within the said range can be selected suitably, and aromatic hydrocarbons, such as toluene, xylene, ethylbenzene, tetralin, etc. Solvents: Aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, cyclohexane, etc .; methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloro Halogen solvents such as ethylene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene Ether solvents such as recall monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol Alcohol solvents such as 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; The mixed solvent of seed | species or more is mentioned.

  For example, when a polyester resin, a polyurethane resin, or an epoxy resin is selected as the resin (G), preferable solvents (C) include acetone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and a mixed solvent of two or more of these. be able to.

  Any method may be used for preparing the solution (L) by dissolving the resin (G) in the solvent (C). For example, the resin (G) is added to the solvent (C). And a stirring method and a heating method.

Content of resin (G) in a solution (L) becomes like this. Preferably it is 10 to 90 weight%, More preferably, it is 20 to 80 weight%.
Since the solvent (C) solution (L) of the resin (G) is dispersed in (N), it preferably has an appropriate viscosity. From the viewpoint of particle size distribution, preferably at 25 ° C., preferably 100 Pa · s or less, More preferably, it is 10 Pa · s or less.

Production method (2) of colored resin particles of the present invention [the same applies to the production method (3) described later. In the organic solvent (C) solution (L) of the resin (G), additives other than the dispersant (B) and the colorant (release agent, charge control agent, antioxidant, blocking prevention) An additive, a heat stabilizer, a fluidizing agent, etc.) and other additives can be contained in the resulting resin particles (H).
When the resin particles are used as, for example, base particles of an electrophotographic toner, a release agent and / or a charge control agent is added to the solution (L) as necessary.

  In the method (2) for producing colored resin particles of the present invention, a non-aqueous dispersion in which organic fine particles (F) are dispersed in a non-aqueous organic solvent (N) and a colorant are dispersed in the solvent (C). The dispersion (E) and the solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed to disperse (E) and (L) in the non-aqueous dispersion of (F). Then, by forming resin particles (H) containing (G), a colorant and (C) in the non-aqueous dispersion of (F), organic fine particles (F) are formed on the surfaces of the resin particles (H). A non-aqueous dispersion of resin particles (I) having a structure in which is fixed is obtained.

  The dispersion liquid (E) in which the colorant is dispersed in the solvent (C) and the solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed with organic fine particles (N) in the non-aqueous organic solvent (N). As a method of dispersing in the non-aqueous dispersion in which F) is dispersed, the dispersion (E) and the solution (L) are mixed in advance, and then the mixture is introduced into the non-aqueous dispersion of (F) and dispersed. Or may be separately introduced and dispersed in the non-aqueous dispersion of (F), but (E) and (L) are mixed in advance before the non-aqueous dispersion of (F) It is preferable to be dispersed. If it does so, a coloring agent can be more uniformly disperse | distributed in resin (G).

  The amount of the colorant dispersion (E) used is preferably such that the amount of the colorant relative to the resin (G) is 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, Particularly preferably, it is 1 to 10% by weight.

  The amount of the non-aqueous dispersion of (F) used with respect to 100 parts by weight of the resin (G) is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (G) is good, and if it is 2,000 parts by weight or less, it is economical.

When the dispersion liquid (E) of the colorant and the solvent (C) solution (L) of the resin (G) are dispersed in the non-aqueous dispersion liquid (F), a dispersion device can be used.
The dispersion apparatus used in the method (2) for producing colored resin particles of the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. Specific examples thereof include JP-A-2002-284881. The thing as described in the gazette is mentioned.

As a method for removing the solvent (C) and the non-aqueous organic solvent (N) from the non-aqueous dispersion of the resin particles (I) to obtain the resin particles (I),
[1] Method of drying solvent (C) and non-aqueous organic solvent (N) under reduced pressure or normal pressure [2] Solid-liquid separation with a centrifuge, spacula filter, filter press, etc., and drying the resulting powder Method [3] Method in which solvent (C) and non-aqueous organic solvent (N) are frozen and dried (so-called lyophilization)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.
During the manufacturing process such as the solvent removal process, the organic fine particles (F) may be formed into a film, and a film in which the (F) is formed into a film may be formed on the surface of the resin particles (H).

The manufacturing method (3) of the colored resin particles of the present invention will be described in detail.
The resin (f), resin (G), solvent (C), and solution (L) constituting the organic fine particles (F) used in the production method (3) are the same as those used in the production method (1). Can be mentioned.

  The aqueous medium (W) constituting the aqueous dispersion in which the organic fine particles (F) are dispersed contains, in addition to water, an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) in the solvent (C). May be. At this time, the organic solvent to be contained does not cause aggregation of the organic fine particles (F) and the resin particles (H), does not dissolve (F) and (H), and granulates the resin particles (I). Any kind and any content can be used as long as they do not impede, but 40% by weight or less of the total amount of water and organic solvent is used to dry the resin particles ( Those which do not remain in I) are preferred.

Although it does not specifically limit as a method of producing the aqueous dispersion liquid of organic fine particles (F), The following [1]-[8] are mentioned.
[1] In the case of a vinyl resin, an aqueous dispersion of organic fine particles (F) is directly produced by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material. how to.
[2] In the case of a polyaddition or condensation resin such as a polyester resin, a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof is dispersed in an aqueous medium (W) in the presence of an appropriate dispersant if necessary. And then heating or adding a curing agent to cure the precursor to produce an aqueous dispersion of organic fine particles (F).
[3] In the case of a polyaddition or condensation resin such as a polyester resin, a precursor (monomer, oligomer, etc.) or an organic solvent solution thereof (preferably a liquid, which may be liquefied by heating) is necessary. A method of producing an aqueous dispersion of organic fine particles (F) by dissolving an appropriate emulsifier, then adding water to effect phase inversion emulsification, and adding a curing agent to cure the precursor.
[4] A resin previously prepared by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc. The same applies to the polymerization reaction in the following section). A method in which resin particles are obtained by pulverization using a fine pulverizer such as a mechanical rotary type or a jet type and then classified, and then dispersed in an aqueous medium (W) in the presence of an appropriate dispersant.
[5] After obtaining resin particles by spraying a resin solution in which a resin prepared in advance by a polymerization reaction is dissolved in an organic solvent in the form of a mist, the resin particles are placed in an aqueous medium (W) in the presence of a suitable dispersant. How to disperse into.
[6] The resin particles are precipitated by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent, or by cooling a resin solution previously heated and dissolved in an organic solvent. A method of removing the solvent to obtain resin particles, and then dispersing the resin particles in the aqueous medium (W) in the presence of an appropriate dispersant.
[7] A method in which a resin solution prepared by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent is dispersed in an aqueous medium (W) in the presence of an appropriate dispersant, and the organic solvent is removed by heating or decompression. .
[8] A method in which a suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent, and then water is added to perform phase inversion emulsification.

  In the above methods [1] to [8], as the emulsifier or dispersant used in combination, a known surfactant, water-soluble polymer, or the like can be used. Moreover, a solvent (C), a plasticizer, etc. can be used together as an auxiliary agent for emulsification or dispersion. Specific examples thereof include those described in JP-A-2002-284881.

  In the method (3) for producing colored resin particles of the present invention, an aqueous dispersion in which organic fine particles (F) are dispersed in an aqueous medium (W), and a dispersion in which a colorant is dispersed in a solvent (C). (E) and a solution (L) in which the resin (G) is dissolved in the solvent (C) are mixed, and (E) and (L) are dispersed in the aqueous dispersion of (F). A structure in which (F) is fixed to the surface of (H) by forming resin particles (H) containing resin (G), colorant and solvent (C) in the aqueous dispersion of (F). An aqueous dispersion of resin particles (I) can be obtained.

  A dispersion (E) in which a colorant is dispersed in a solvent (C) and a solution (L) in which a resin (G) is dissolved in the solvent (C) are dispersed in an aqueous dispersion of organic fine particles (F). As a method for the above, the dispersion (E) and the solution (L) may be mixed in advance, and then the mixture may be introduced and dispersed in the aqueous dispersion of (F), or the aqueous dispersion of (F) separately. It may be introduced and dispersed in the liquid, but it is preferable to mix (E) and (L) in advance and then disperse in the aqueous dispersion of (F). If it does so, a coloring agent can be more uniformly disperse | distributed in resin (G).

  The amount of the colorant dispersion (E) used is preferably such that the amount of the colorant relative to the resin (G) is 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, Particularly preferably, it is 1 to 10% by weight.

  The amount of the aqueous dispersion of (F) used with respect to 100 parts by weight of the resin (G) is preferably 50 to 2,000 parts by weight, and more preferably 100 to 1,000 parts by weight. If it is 50 parts by weight or more, the dispersed state of (G) is good, and if it is 2,000 parts by weight or less, it is economical.

  When the dispersion liquid (E) of the colorant and the solvent (C) solution (L) of the resin (G) are dispersed in the aqueous dispersion liquid (F), a dispersion device can be used. Examples of the dispersing device include those described above.

As a method of removing the aqueous medium (W) and the solvent (C) from the aqueous dispersion of the resin particles (I) to obtain the resin particles (I),
[1] A method of drying an aqueous dispersion under reduced pressure or normal pressure.
[2] A method of solid-liquid separation with a centrifuge, a spatula filter, a filter press, etc., and drying the obtained powder.
[3] Method of freezing aqueous dispersion and drying (so-called lyophilization)
Etc. are exemplified.
In the above [1] and [2], when the obtained powder is dried, it can be performed using a known facility such as a fluidized bed dryer, a vacuum dryer, or a circulating dryer.
Moreover, it can classify | classify using a wind classifier etc. as needed, and can also be set as predetermined particle size distribution.
During the manufacturing process such as the solvent removal process, the organic fine particles (F) may be formed into a film, and a film in which the (F) is formed into a film may be formed on the surface of the resin particles (H).

  The volume average particle diameter of the resin particles (I) obtained by the production methods (1) to (3) of the resin particles during coloring is preferably 1 to 10 μm, more preferably 2 to 8 μm.

  The colored resin particles (I) obtained by the production methods (1) to (3) of the colored resin particles of the present invention have good dispersion of the colorant and are useful as colored resin particles used in various applications.

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

Example 1
Dispersant (DISPERBYK-106: salt of a polymer compound having an acid value of 132 and an amine value of 74. Peaks at molecular weights of 1,200 and 460, manufactured by Big Chemie Japan, in a pressure-resistant reaction vessel in which a stir bar and a thermometer are set. ) 40 parts of acetone solution of 1.2 parts and 8.85 parts of phthalocyanine pigment [cyanine blue (CI pigment blue 15: 3)] are charged to 40% of the volume of the reaction vessel, sealed and stirred. The system was heated to an internal temperature of 85 ° C. After raising the temperature, carbon dioxide was supplied to 5 MPa and stirred for 10 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 ( E-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.

Example 2
1.0 part of a 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) was placed 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 an 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 85 ° C. After raising the temperature, carbon dioxide was supplied to 5 MPa and stirred for 10 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 ( E-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.

Example 3
Dispersant (BYK-9076: 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 thermometer 2.0 parts of 55 parts of 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. E-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.

Example 4
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 ( E-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.

Example 5
Dispersant (DISPERBYK-145: 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) in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. 45 parts of an ethyl acetate solution of 45 parts, 4.0 parts of quinacridone pigment [Pigment Red (CI Pigment Red 122)] were charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, The system 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 ( E-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.

Example 6
Dispersant (BYK-9077: high molecular copolymer having an acid value of 0 and an amine value of 48, having a peak at a molecular weight of 4,000, manufactured by Big Chemie Japan) in a pressure-resistant reaction vessel equipped with a stir bar and a thermometer. Charge 2 parts of acetone solution 45 parts, silica (Aerosil R972, primary particle average diameter 16 nm, made by Nippon Aerosil; filler) to 40% of the volume of the reaction vessel, seal and heat with stirring. The system temperature was raised to 80 ° C. After raising the temperature, carbon dioxide was supplied to 4 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. -6) was obtained. The median diameter of the dispersoid was 0.76 μm, and the ratio of 1 μm or more was 14.9% by volume.

Example 7
In an experimental apparatus using the line blending method shown in FIG. 1 (as a line blending apparatus (M1), a static mixer (manufactured by Noritake Company Limited; inner diameter 3.4 mm, number of elements 27) was used), first, a dispersant ( DISPERBYK-106) 411.5 parts of acetone solution of 11.5 parts and 88.5 parts of phthalocyanine pigment [Cyanine Blue (CI Pigment Blue 15: 3)] were charged, sealed and heated with stirring, The temperature was raised to an internal temperature of 85 ° C. to prepare a slurry. Carbon dioxide was introduced from the cylinder B1 and the pump P2 at a flow rate of 0.2 L / h, and the valve V1 was adjusted to 5 MPa. Next, the slurry is introduced from the tank T1 and the pump P1 at a flow rate of 0.5 L / h, and while maintaining 5 MPa, the mixed liquid line-blended with M1 is released from the nozzle into T2 (atmospheric pressure). Carbon dioxide was vaporized and removed to obtain a colorant dispersion (E-7). The median diameter of the dispersoid was 0.21 μm, and the ratio of 1 μm or more was 0% by volume.

Example 8
Instead of an acetone solution of a dispersing agent (DISPERBYK-106), 411.5 parts of an acetone solution of 20 parts of a dispersing agent (SOLSPERSE 71000) are used instead of a phthalocyanine pigment [cyanine blue (CI pigment blue 15: 3)]. In the same manner as in Example 7 except that 80 parts of an azo lake pigment [Pigment Red (CI Pigment Red 57: 1)] was charged, a colorant dispersion (E-8) was obtained. The median diameter of the dispersoid was 0.20 μm, and the ratio of 1 μm or more was 0% by volume.

Comparative Example 1
7. In a pressure-resistant reaction vessel equipped with a stir bar and a thermometer, 1.2 parts of a dispersant (DISPERBYK-106) 40 parts of an acetone solution, a phthalocyanine pigment [cyanine blue (CI pigment blue 15: 3)] 85 parts were charged, sealed and heated with stirring, and the system temperature was raised to 85 ° C. 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 (E′-1). The median diameter of the dispersoid was 1.10 μm, and the ratio of 1 μm or more was 34.2% by volume.

Comparative Example 2
Dispersant (SOLSPERSE 17000: chain polymer having an acid value of 17 and an amine value of 0, having a peak at a molecular weight of 4,000, manufactured by Nippon Lubrizol Co., Ltd.) 1.2 40 parts of acetone solution and 8.85 parts of phthalocyanine pigment [cyanine blue (CI Pigment Blue 15: 3)] were charged to 40% of the volume of the reaction vessel, sealed and heated with stirring, The temperature in the system was raised to 85 ° C. After heating, carbon dioxide is supplied to 5 MPa and stirred for 10 minutes, and then the nozzle attached to the bottom of the container is fully opened and opened to the atmosphere to vaporize and remove the carbon dioxide, thereby dispersing the comparative colorant A liquid (E′-2) was obtained. The median diameter of the dispersoid was 1.05 μm, and the ratio of 1 μm or more was 49.3 vol%.

Production Example 1 <Preparation of Resin (G-1)>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 831 parts of 1,2-propylene glycol (hereinafter referred to as propylene glycol), 703 parts of terephthalic acid, 47 parts of adipic acid, and tetrabutoxy as a condensation catalyst 0.5 parts of titanate was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the water produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and the softening point becomes 87 ° C. After cooling to 180 ° C., 24 parts of trimellitic anhydride and 0.5 part of tetrabutoxy titanate were added, reacted for 90 minutes, and then taken out. The recovered propylene glycol was 442 parts. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a polyester resin (G-1). This resin had Mn of 1900 and Tg of 45 ° C.

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

Production Example 3 <Preparation of Resin Solution (L-1)>
In a container equipped with a stirrer, 228 parts of resin (G-1) obtained in Production Example 1 was added to solvent (C-1), which is a mixed solvent consisting of 490 parts of acetone, 175 parts of methanol, and 35 parts of ion-exchanged water. Then, 57 parts of the resin (G-2) obtained in Production Example 2 was charged and stirred until the resin (G-1) and the resin (G-2) were completely dissolved to obtain a resin solution (L-1). It was.
The solvent (C-1) is 0.1% by weight of the insoluble content of the resin (G) with respect to the weight of the resin (G) in the equal weight mixture of the resin (G) and the solvent (C-1) in the standard state. Hereinafter, the SP value of the solvent (C-1) was 11.8.

Production Example 4 <Preparation of Resin (f-1)>
A reaction vessel equipped with a stirrer, heating / cooling device, thermometer, dropping funnel, and nitrogen blowing tube was charged with 500 parts of toluene, and another glass beaker was charged with 350 parts of toluene and behenyl acrylate (22 carbon atoms directly). 120 parts of an alcohol acrylate (Blenmer VA, manufactured by NOF), 22.5 parts of methyl methacrylate, 7.5 parts of (2-perfluorodecyl) ethyl acrylate (manufactured by Wako Pure Chemical Industries), AIBN (azo) 10 parts of bisisobutyronitrile) was stirred and mixed at 20 ° C. to prepare a monomer solution, which was then charged into a dropping funnel, which was purged with nitrogen in the gas phase portion of the reaction vessel, and then sealed at 80 ° C. The monomer solution was added dropwise over 2 hours, and after aging at 85 ° C. for 2 hours from the end of dropping, toluene was removed under reduced pressure at 130 ° C. for 3 hours to obtain resin (f-1). It was. The melting point of the resin 60 ° C., Mn was 8000.

Production Example 5 <Preparation of Nonaqueous Dispersion of Organic Fine Particles (F-1)>
After mixing 700 parts of normal hexane and 300 parts of resin (f-1), the mixture was pulverized with zirconia beads having a particle diameter of 0.3 mm in a bead mill (Dynomill Multilab: manufactured by Shinmaru Enterprises) A non-aqueous dispersion of organic fine particles (F-1) was obtained. The volume average particle diameter measured by LA-920 of (F-1) in this dispersion (the same applies to the following organic fine particles) was 0.4 μm.

Production Example 6 <Preparation of aqueous dispersion of organic fine particles (F-2)>
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 139 parts of styrene, 138 parts of methyl methacrylate When 184 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion of organic fine particles (F-2) (solid content concentration 20% by weight). The volume average particle size of (F-2) in this dispersion was 0.15 μm.

Example 9
In the experimental apparatus of FIG. 2, first, the valves V2 and V3 were closed, carbon dioxide (purity 99.99 wt%) was introduced into the particle recovery tank T6 from the cylinder B3 and the pump P6, and the pressure was adjusted to 14 MPa and 40 ° C. Also, a resin solution tank T3 mixed with a resin solution (L-1) and a colorant dispersion liquid (E-1), and a non-aqueous dispersion liquid of organic fine particles (F-1) were charged into a fine particle dispersion tank T4. . Next, carbon dioxide was introduced into the dispersion tank T5 from the cylinder B2 and the pump P5, adjusted to 9 MPa and 40 ° C., and a non-aqueous dispersion of organic fine particles (F-1) was introduced from the tank T4 and the pump P4. Next, while stirring the inside of the dispersion tank T5 at 2000 rpm, a mixed solution of the resin solution (L-1) and the colorant dispersion (E-1) was introduced into the dispersion tank T5 from the tank T3 and the pump P3. After the introduction, the pressure inside T5 was 14 MPa.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-1) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts The weight of the introduced carbon dioxide is carbon dioxide The density of carbon dioxide was calculated from the temperature equation (40 ° C.) and the pressure (15 MPa) from the state equation described in the following document 2, and this was multiplied by the volume of the dispersion tank T5 (the same applies hereinafter).
Reference 2: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

  A liquid obtained by mixing the resin solution (L-1) and the colorant dispersion (E-1) was introduced, followed by stirring for 1 minute to obtain a dispersion (X-1). After opening the valve V2 and introducing carbon dioxide into T6 from P6, the dispersion (X-1) was introduced into T6, and the opening degree of V3 was adjusted so that the pressure was kept constant during this time. This operation was performed for 30 seconds and V2 was closed. By this operation, the solvent was extracted from the resin solution introduced into T6. Further, T6 was heated to 60 ° C. and held for 15 minutes. By this operation, the organic fine particles (F-1) were fixed to the surface of the resin particles (H-1) formed from the resin solution (L-1), and resin particles (I-1) were generated. Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T7 by holding the pressure at 14 MPa by the pressure adjusting valve V3 while introducing carbon dioxide into the particle recovery tank T6 from the pressure cylinder B3 and the pump P6. At the same time, the resin particles (I-1) were captured by the filter F1. The operation of introducing carbon dioxide into the particle recovery tank T6 from the pressure cylinder B3 and the pump P6 is to introduce carbon dioxide when 5 times the weight of carbon dioxide introduced into the dispersion tank T5 is introduced into the particle recovery tank T6. Stopped. At the time of this stop, the operation of replacing the carbon dioxide containing the solvent with carbon dioxide not containing the solvent and capturing the resin particles (I-1) in the filter F1 was completed. Further, the pressure regulating valve V3 is opened little by little, the inside of the particle recovery tank is reduced to atmospheric pressure, and the coating derived from the organic fine particles (F-1) on the surface of the resin particles (H-1) supplemented by the filter F1. Was obtained, and resin particles (I-1) having a volume average particle diameter of 5.5 μm by Multisizer III (the same applies to the following resin particles), which were uniformly colored with a phthalocyanine pigment, were obtained.

Example 10
In Example 9, resin particles (H--) were used in the same manner as in Example 9, except that the colorant dispersion (E-2) dispersion was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 2), and resin particles (I-2) having a volume average particle diameter of 4.8 μm, which were uniformly colored with an azo lake pigment, were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-2) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 11
In Example 9, resin particles (H--) were used in the same manner as in Example 9, except that the colorant dispersion (E-3) was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 3), and resin particles (I-3) having a volume average particle size of 4.9 μm, which were uniformly colored with a carbon black pigment, were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-3) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 12
In Example 9, resin particles (H--) were used in the same manner as in Example 9 except that the colorant dispersion (E-4) was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 4), and resin particles (I-4) having a volume average particle size of 5.4 μm, which were uniformly colored with a benzimidazolone pigment, were obtained. .
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-4) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 13
In Example 9, resin particles (H--) were used in the same manner as in Example 9 except that the colorant dispersion (E-5) was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 5), and resin particles (I-5) having a volume average particle diameter of 5.3 μm, which were uniformly colored with a quinacridone pigment, were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-5) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 14
In Example 9, resin particles (H--) were used in the same manner as in Example 9 except that the colorant dispersion (E-7) dispersion was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 6), and resin particles (I-6) having a volume average particle diameter of 5.0 μm, which were uniformly colored with a phthalocyanine pigment, were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-7) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 15
In Example 9, resin particles (H--) were used in the same manner as in Example 9 except that the colorant dispersion (E-8) was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 7), and resin particles (I-7) having a volume average particle size of 4.9 μm, which were uniformly colored with an azo lake pigment, were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-8) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 16
A non-aqueous dispersion of normal decane and organic fine particles (F-1) was put into a beaker and mixed with a homomixer (manufactured by Primex) at a rotation speed of 16000 rpm for 10 seconds, and then the resin solution (L-1) and A liquid obtained by mixing the dispersion liquid (E-1) of the colorant was added at once and dispersed for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and organic fine particles (F− 1) A resin particle (I-8) having a volume average particle size of 5.5 μm, which was formed with a film derived from it and was uniformly colored with a phthalocyanine pigment, was obtained.
The weight ratio of the charged composition in Example 16 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-1) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Normal decane 120 parts

Example 17
In Example 16, resin particles (H--) were used in the same manner as in Example 16 except that the colorant dispersion (E-2) dispersion was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-1) was formed on the surface of 9), and resin particles (I-9) having a volume average particle diameter of 5.0 μm, which were uniformly colored with an azo lake pigment, were obtained.
The weight ratio of the charged composition in Example 17 is as follows.
Resin solution (L-1) 270 parts Colorant dispersion (E-2) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Normal decane 120 parts

Example 18
In a beaker, 11 parts of an aqueous dispersion of organic fine particles (F-2), 80 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 300 parts of ion-exchanged water were mixed and stirred, and then the resin solution (L-1 ) After mixing 150 parts and 60 parts of the colorant dispersion (E-1), TK homomixer (manufactured by Tokushu Kika) was used and mixed for 10 minutes at 12,000 rpm. After mixing, the mixture is poured into a reaction vessel equipped with a stirrer and a thermometer, desolvated at 50 ° C. for 2 hours, then filtered and dried, and organic fine particles are formed on the surface of the resin particles (H-10). A film derived from (F-2) was formed, and resin particles (I-10) having a volume average particle size of 5.6 μm and uniformly colored with a phthalocyanine pigment were obtained.
The weight ratio of the composition charged into the beaker in Example 18 is as follows.
Resin solution (L-1) 150 parts Colorant dispersion (E-1) 60 parts Aqueous dispersion of organic fine particles (F-2) 11 parts 48.5 wt% aqueous solution of sodium dodecyl diphenyl ether disulfonate
80 parts Ion exchange water 300 parts

Example 19
In Example 18, resin particles (H--) were used in the same manner as in Example 18 except that the colorant dispersion (E-2) was used instead of the colorant dispersion (E-1). A film derived from organic fine particles (F-2) was formed on the surface of 11), and resin particles (I-11) having a volume average particle diameter of 5.1 μm and uniformly colored with an azo lake pigment were obtained.
The weight ratio of the composition charged into the beaker in Example 19 is as follows.
Resin solution (L-1) 150 parts Colorant dispersion (E-2) 60 parts Aqueous dispersion of organic fine particles (F-2) 11 parts 48.5 wt% aqueous solution of sodium dodecyl diphenyl ether disulfonate
80 parts Ion exchange water 300 parts

Comparative Example 3
In Example 9, resin particles (H) were obtained in the same manner as in Example 9 except that instead of the colorant dispersion (E-1), a comparative colorant dispersion (E′-1) was used. A coating derived from organic fine particles (F-1) was formed on the surface of '-1) and colored with a phthalocyanine pigment to obtain comparative resin particles (I'-1) having a volume average particle size of 5.0 µm. .
The comparative resin particles (I′-1) were poor in dispersibility of the phthalocyanine pigment, and as a result of confirmation with an optical microscope, aggregation of the pigment was confirmed, and particles in which the pigment was not contained in the resin particles were also observed.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Comparative colorant dispersion (E'-1) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Comparative Example 4
In Example 9, resin particles (H) were obtained in the same manner as in Example 9 except that instead of the colorant dispersion (E-1), a comparative colorant dispersion (E′-2) was used. A coating derived from organic fine particles (F-1) was formed on the surface of '-2) and colored with a phthalocyanine pigment to obtain comparative resin particles (I'-2) having a volume average particle size of 5.4 µm. .
The comparative resin particles (I′-2) were poor in dispersibility of the phthalocyanine pigment, and as a result of confirmation with an optical microscope, aggregation of the pigment was confirmed, and particles in which the pigment was not contained in the resin particles were also observed.
In addition, the weight ratio of the preparation composition to the dispersion tank T5 is as follows.
Resin solution (L-1) 270 parts Comparative colorant dispersion (E'-2) 60 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

By the method for producing a dispersion of the present invention, dispersoids such as solid particles are finely dispersed in a dispersion solvent, and a dispersion useful for various applications can be produced quickly and with less power.
In addition, the colored resin particles obtained by using the dispersion obtained by the production method of the present invention have the colorant finely and uniformly dispersed, so that the base particles of the electrophotographic toner, the additive for coating, the additive for cosmetics Additive for paper coating, resin for slush molding, powder paint, spacer for manufacturing electronic components, standard particles for electronic measuring equipment, particles for electronic paper, medical diagnostic carrier, particles for electroviscosity, other resin particles for molding Useful as.

T1: Mixing tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T2: Dispersion tank B1: Carbon dioxide cylinder P1: Solution pump P2: Carbon dioxide pump M1: Static mixer V1: Valve

T3: Resin solution tank T4: Solution tank T5: Dispersion tank (maximum operating pressure 20 MPa, maximum operating temperature 200 ° C., with stirrer)
T6: Particle recovery tank (maximum operating pressure 20 MPa, maximum operating temperature 100 ° C.)
T7: Solvent trap F1: Ceramic filter (mesh: 0.5 μm)
B2, B3: Carbon dioxide cylinder P3, P4: Solution pump P5, P6: Carbon dioxide pump V2: Valve V3: Pressure adjustment valve

Claims (8)

Dispersoid (A), dispersant (B) having a total acid value and amine value (mgKOH / g) of 20 or more and 250 or less, solvent (C), and compressive fluid (D) having a pressure of 2 MPa or more Mixing in a pressure vessel or in-line mixer , and then expanding under reduced pressure to atmospheric pressure to vaporize and remove the compressive fluid (D), so that the dispersoid (A) having a median diameter of 1 μm or less is contained in the solvent (C). A method for producing a dispersion characterized by obtaining a dispersed dispersion (E) , wherein the dispersant (B) has an acidic group and a basic group, and is a polymerized polymer and / or polymer compound And a solvent (C) dissolves the dispersant (B), and the compressive fluid (D) is carbon dioxide in a liquid state or carbon dioxide in a supercritical state .   The method for producing a dispersion according to claim 1, wherein the dispersant (B) has a peak in the range of at least 1,000 or more and 1,000,000 or less in the molecular weight distribution. The method for producing a dispersion according to claim 1 or 2 , wherein the dispersant (B) is dissolved in a mixture of the compressive fluid (D) and the solvent (C). Dispersoid (A), dispersant (B), solvent (C), and compressible fluid (D) mixing method compresses mixture of dispersoid (A), dispersant (B), and solvent (C) The method for producing a dispersion according to any one of claims 1 to 3, wherein the dispersion is a method of introducing into the fluid (D) and mixing by line blending. Dispersoid (A) is a coloring agent, The manufacturing method of the dispersion liquid in any one of Claims 1-4 . The dispersion (E) obtained by the production method according to claim 5, the liquid state or supercritical carbon dioxide (X) in which the organic fine particles (F) are dispersed, and the resin (G) is the solvent (C). The resin particles (H) containing the resin (G), the colorant and the solvent (C) are mixed by mixing the solution (L) dissolved in the solution and dispersing (E) and (L) in (X). Of the colored resin particles including the step of forming resin particles (I) having organic fine particles (F) fixed on the surface thereof, and then removing carbon dioxide (X) and solvent (C) in the liquid state or supercritical state. Production method. A dispersion (E) obtained by the production method according to claim 5 , a non-aqueous dispersion in which organic fine particles (F) are dispersed in a non-aqueous organic solvent (N), and a resin (G) containing a solvent (C And (E) and (L) are dispersed in the non-aqueous dispersion of (F), whereby the resin (G), the colorant, and the solvent (C) are mixed. Colored resin particles comprising a step of forming resin particles (I) having organic fine particles (F) fixed on the surface of the resin particles (H) contained, and then removing the non-aqueous organic solvent (N) and the solvent (C) Manufacturing method. The dispersion liquid (E) obtained by the production method according to claim 5 , the aqueous dispersion liquid in which the organic fine particles (F) are dispersed in the aqueous medium (W), and the resin (G) are dissolved in the solvent (C). The resin particles containing the resin (G), the colorant and the solvent (C) by mixing the solution (L) thus prepared and dispersing (E) and (L) in the aqueous dispersion of (F) A method for producing colored resin particles, comprising the steps of forming resin particles (I) having organic fine particles (F) fixed on the surface of (H) and then removing the aqueous medium (W) and solvent (C).

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