JP2012031270A - Method for producing infrared absorber-containing resin particle, infrared absorber-containing resin particle and electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method which provides infrared absorber-containing resin particles having excellent fixability when being used as the host particles of an electrophotographic toner.SOLUTION: The method for producing infrared absorber-containing resin particles includes a step of mixing a dissolved liquid or a fluid dispersion (L) obtained by dissolving or dispersing a resin (G) and an infrared absorber (A) into a solvent (C) with a fluid dispersion obtained by dispersing organic fine particles (F) into a dispersing medium (B) and dispersing the (L) into the (B), thus forming resin particles (I) in which the organic fine particle (F) are fixed to the surfaces of the resin particles (H) containing the resin (G), the infrared absorber (A) and the solvent (C), and then removing the dispersing medium (B) and the solvent (C).

Description

  The present invention relates to resin particles containing an infrared absorber and a method for producing the same.

Conventionally, as a method of fixing resin particles, there is a hot-pressure fixing method (heat roll method) in which a fixing member is pressed and heated and pressed. When resin particles are used as base particles for electrophotographic toner, in this method, a printed material such as paper imaged with toner is passed between heating rolls, and the toner is thermocompression bonded to the printed material. There are problems such as clogging at the fixing unit or reduction in resolution due to the image being crushed, and limited types of printed materials.
Further, as a method for improving the above-described problems, a method of containing an infrared absorbent in the toner and melting and fixing the xenon flash lamp light, particularly infrared light, absorbed by the infrared absorbent in the toner. A flash fixing method is proposed (see, for example, Patent Document 1), but the fixing property is not always sufficient.

JP 2000-147824 A

  The problem to be solved by the present invention is to find a production method for obtaining infrared absorbent-containing resin particles having excellent fixing properties when used as base particles of an electrophotographic toner.

  According to the present invention, a solution or dispersion (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C), and the organic fine particles (F) in the dispersion medium (B). The surface of the resin particle (H) containing the resin (G), the infrared absorber (A) and the solvent (C) by mixing the dispersed dispersion and dispersing (L) in (B). Forming resin particles (I) to which organic fine particles (F) are fixed, and then removing the dispersion medium (B) and the solvent (C). Is provided, and the above-mentioned problems are solved.

  Moreover, according to this invention, the infrared absorber containing resin particle obtained by said manufacturing method is provided.

  Furthermore, according to the present invention, there is provided an electrophotographic toner containing the infrared absorbent-containing resin particles obtained by the above production method.

  According to the method for producing the infrared absorbent-containing resin particles of the present invention, it is possible to obtain infrared absorbent-containing resin particles that are excellent in fixability when used as base particles of an electrophotographic toner and have a sufficiently narrow particle size distribution. In addition, resin particles having a narrow particle size distribution can be stably produced.

It is the experimental apparatus used for preparation of the infrared absorber containing resin particle.

The present invention is described in detail below.
Examples of the resin (G) include a thermoplastic resin (G1), a resin (G2) obtained by finely crosslinking the thermoplastic resin, and a polymer blend (G3) having the thermoplastic resin as a sea component and a cured resin as an island component. Two or more types may be used in combination.
Examples of the thermoplastic resin (G1) include vinyl resin, polyester resin, polyurethane resin, and 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.

In the present invention, Mn of the resin (G) 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 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.

  The infrared absorber (A) can be used without particular limitation as long as it has an absorption maximum wavelength λmax in the wavelength range of 650 nm to 1300 nm, and conventionally known ones can be used.

  Examples of the infrared absorber (A) include indium oxide metal oxides, tin oxide metal oxides, zinc oxide metal oxides, cadmium stannate, specific amide compounds, lanthanoid compounds, cyanine compounds, merocyanine compounds, Examples thereof include a benzenethiol metal complex, a mercaptophenol metal complex, an aromatic diamine metal complex, a diimonium compound, an aminium compound, a nickel complex compound, a phthalocyanine compound, an anthraquinone compound, and a naphthalocyanine compound. These may be used alone or in combination.

  Specifically, nickel metal complex infrared absorber (Mitsui Chemical Co., Ltd .: SIR-130, SIR-132), bis (dithiobenzyl) nickel (Midori Chemical Co., Ltd .: MIR-101), bis [1,2- Bis (p-methoxyphenyl) -1,2-ethylenedithiolate] nickel (Midori Chemical Co., Ltd .: MIR-102), tetra-n-butylammonium bis (cis-1,2-diphenyl-1,2-ethylenedithio) Rate) Nickel (Midori Chemical Co., Ltd .: MIR-1011), Tetra-n-butylammonium bis [1,2-bis (p-methoxyphenyl) -1,2-ethylenedithiolate] Nickel (Midori Chemical Co., Ltd .: MIR) -1021), bis (4-tert-1,2-butyl-1,2-dithiophenolate) nickel-tetra-n-butylammonium (Sumitomo Seika Chemicals Co., Ltd .: BBDT-NI), cyanine infrared absorbers (Fuji Film Co., Ltd .: IRF-106, IRF-107), cyanine infrared absorbers (Yamamoto Kasei Co., Ltd., YKR2900), aminium, diimonium series Infrared absorber (Nagase Chemtech Co., Ltd .: NIR-AM1, IM1), Imonium compound (Nippon Carlit Co., Ltd .: CIR-1080, CIR-1081), Aminium compound (Nippon Carlit Co., Ltd .: CIR-960, CIR-961), Anthraquinone compounds (Nippon Kayaku Co., Ltd .: IR-750), aminium compounds (Nippon Kayaku Co., Ltd .: IRG-002, IRG-003, IRG-003K), polymethine compounds (Nippon Kayaku Co., Ltd .: IR- 820B), diimonium compounds (manufactured by Nippon Kayaku Co., Ltd .: IRG-022, IRG-023), di Nin compound (manufactured by Nippon Kayaku Co., Ltd.: CY-2, CY-4, CY-9), soluble phthalocyanine (produced by Nippon Shokubai Co., Ltd.: TX-305A), naphthalocyanine (Yamamoto Chemicals Inc.: YKR5010), and the like.

  The amount of the infrared absorber (A) used is preferably 0.02 wt% or more and 3.0 wt% or less, and 0.05 wt% or more and 2.5 wt% or less with respect to the resin (G). More preferably. When the content of the infrared absorber (A) is less than 0.02% by weight, the amount of heat generated by the absorption of the infrared absorber when irradiated with infrared rays is reduced. May decrease. If the content of the infrared absorber (A) exceeds 3.0% by weight, the amount of visible light absorbed by the infrared absorber may increase. When used as an electrophotographic toner, the color of the formed image may be increased. The degree may decrease.

Solvent solubility parameter (SP value) of (C) is 9-16 ^{[(cal / cm 3) 1/} 2, the same applies hereinafter], more preferably an 10-15. The SP value is expressed by the square root of the ratio between the cohesive energy density and the molecular volume, as shown below.
SP = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science, Vol. 14, pages 147-154.

  Specific examples of the solvent (C) include, for example, ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, cyclic ether, etc.), ester solvents (acetic acid, etc.). Esters, pyruvic acid esters, 2-hydroxyisobutyric acid esters, lactic acid esters, etc.), amide solvents (dimethylformamide, etc.), alcohols (methanol, ethanol, fluorine-containing alcohols, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.) And aliphatic hydrocarbon solvents (octane, decane, etc.). A mixed solvent of two or more of these solvents or a mixed solvent of these organic solvents and water can also be used.

From the viewpoint of ease of particle formation, the single solvent is preferably a cyclic ether, pyruvate, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, 2-hydroxyisobutyrate, lactic acid ester, or fluorine-containing alcohol. .
Examples of the cyclic ether include 1,4-dioxane and 1,3-dioxolane.
Examples of pyruvate esters include methyl pyruvate and ethyl pyruvate.
Examples of the ethylene glycol monoalkyl ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Examples of 2-hydroxyisobutyric acid ester include methyl 2-hydroxyisobutyrate.
Examples of the lactic acid ester include methyl lactate and ethyl lactate.
Examples of the fluorine-containing alcohol include 2,2,3,3-tetrafluoropropanol and trifluoroethanol.
As the mixed solvent, 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 a mixed solvent of methyl ethyl ketone and water are preferable.

  The solution (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C) is dissolved in the resin (G) and the infrared absorber (A) in the solvent (C). Or it is manufactured by dispersing. The concentration of the resin (G) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight with respect to the weight of the solution or dispersion (L).

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

  The organic fine particles (F) used in the method for producing the infrared absorbent-containing resin particles of the present invention may be any material that can be dispersed in the dispersion medium (B) and fixed to the surface of the resin particles (H).

  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 an 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 the dispersion medium (B) 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 (a12) 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 (a12).
From the viewpoint of storage stability, aliphatic polyurethane and / or polyurea has a carbon number of alkylene chain of diol and / or diamine (when a mixture of diol and diamine is used, carbon of alkylene chain averaged by the weight ratio). Number) and the total number of carbon atoms of the alkylene chain of the diisocyanate is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more. Further, from the viewpoint of fixability, it is preferably 52 or less, more preferably 45 or less, particularly preferably 40 or less, and most preferably 30 or less.

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

As the crystalline vinyl resin having an alkyl (meth) acrylate as an essential constituent unit, a crystalline vinyl resin (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. 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 production method of the organic fine particles (F) may be any production method. Specific examples thereof include a dry production method [the resin (f) constituting the organic fine particles (F) is a known dry pulverizer such as a jet mill. A method of dry pulverization by the above], a method of producing by a wet method [a method of dispersing the powder of the resin (f) in an organic solvent and wet pulverizing with a known wet disperser such as a bead mill or a roll mill, and a solvent solution of (f) A method of spray drying with a spray dryer, a method of supersaturating the solvent solution of (f) by adding a poor solvent or cooling, a method of dispersing the solvent solution of (f) in water or an organic solvent, a precursor of (f) A method of polymerizing the body in water by emulsion polymerization, soap-free emulsion polymerization, seed polymerization, suspension polymerization, etc., and a method of polymerizing the precursor of (f) by dispersion polymerization in an organic solvent]. It is.
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 dispersion medium (B) may be any medium as long as it can disperse the organic fine particles (F), and examples thereof include a compressive fluid, an organic solvent, and an aqueous medium (Z).
Examples of the compressible fluid include methane, ethylene, and alternative chlorofluorocarbon. From the viewpoint of safety and ease of handling, carbon dioxide (X) in a liquid state or a supercritical state is preferable.
Carbon dioxide in a liquid state is a triple point of carbon dioxide (temperature = −57 ° C., pressure of 0.5 MPa) and a critical point of carbon dioxide (temperature = temperature = temperature) on a phase diagram represented by a temperature axis and a pressure axis of carbon dioxide. This represents carbon dioxide, which is the temperature / pressure condition of the portion surrounded by the gas-liquid boundary line passing through the solid-liquid boundary line, and the gas-liquid boundary line passing through the solid-liquid boundary line. Represents carbon dioxide which is a temperature / pressure condition above the critical temperature (however, the pressure represents the total pressure in the case of a mixed gas of two or more components).
Examples of the organic solvent include the same solvents as the solvent (C). In view of the dispersibility of the organic fine particles (F), the non-aqueous organic solvent (N) is preferable. Examples of the non-aqueous organic solvent (N) include aliphatic hydrocarbon solvents (decane, hexane, heptane, etc.), and ester solvents (ethyl acetate). , Butyl acetate, etc.). The non-aqueous organic solvent (N) is preferably an organic solvent having a solubility of the resin (G) of 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.
Examples of the aqueous medium (Z) include water or water containing an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) in addition to water. 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 hinder, but 40% or less of the total amount of water and the organic solvent is used to dry the resin particles (I What is not left in is preferable.

From the selection of the dispersion medium (B), the following (1) to (3) are preferable as the method for producing the infrared absorbent-containing resin particles of the present invention.
When the infrared absorbent-containing 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 production method (1) is as follows. It is preferable.
Manufacturing method (1)
A solution or dispersion (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C), and carbon dioxide (X) in which the organic fine particles (F) are in a liquid state or a supercritical state Of the resin particles (H) containing the resin (G), the infrared absorber (A) and the solvent (C) by mixing the dispersion liquid dispersed in (X) and dispersing (L) in (X). The resin particles (I) having the organic fine particles (F) fixed on the surface are formed, and then carbon dioxide (X) and the solvent (C) in a liquid state or a supercritical state are removed to obtain resin particles containing an infrared absorber. Manufacturing method to obtain.

Moreover, when manufacturing an infrared absorber containing resin particle in a non-aqueous organic solvent (N), it is preferable that it is the following manufacturing methods (2).
Manufacturing method (2)
Resin (G) and infrared absorber (A) dissolved or dispersed in solvent (C) or dispersion (L) and organic fine particles (F) dispersed in non-aqueous organic solvent (N) By mixing the dispersion and dispersing (L) in (N), organic fine particles are formed on the surface of the resin particles (H) containing the resin (G), the infrared absorber (A) and the solvent (C). A method for producing infrared absorbent-containing resin particles by forming resin particles (I) to which (F) is fixed, and then removing the non-aqueous organic solvent (N) and the solvent (C).

Moreover, when manufacturing an infrared absorber containing resin particle in an aqueous medium (Z), it is preferable that it is the following manufacturing methods (3).
Manufacturing method (3)
A solution or dispersion (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C), and a dispersion in which the organic fine particles (F) are dispersed in the aqueous medium (Z). And (L) is dispersed in (Z), whereby organic fine particles (F) are formed on the surface of the resin particles (H) containing the resin (G), the infrared absorber (A) and the solvent (C). ) Is formed, and then the aqueous medium (Z) and the solvent (C) are removed to obtain infrared absorbent-containing resin particles.

  In the production method (1), when carbon dioxide (X) in a liquid state or a supercritical state is used as the dispersion medium (B), the organic fine particles (F) have a glass transition temperature (hereinafter referred to as Tg). Or the degree of swelling with carbon dioxide (X) (hereinafter referred to as the degree of swelling) is preferably 16% or less, more preferably 10% or less, and particularly preferably 5% or less. is there. 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. Org. Supercritical Fluids. 19, 187-198 (2001).

  In the production method (1), any method may be used to disperse the organic fine particles (F) in carbon dioxide (X). For example, (F) and (X) are charged in a container, and stirring, ultrasonic irradiation, etc. The method of dispersing (F) directly in (X), the method of introducing a dispersion liquid in which the organic fine particles (F) are dispersed in the solvent (C), and the like.

  In the production method (1), 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 0.1%. 20% by weight. If it is this range, a resin particle can be manufactured efficiently.

  In the production method (1), the weight ratio between the organic fine particles (F) and the solvent (C) is not particularly limited, but the organic fine particles (F) are preferably 50% by weight or less with respect to the solvent (C). Preferably it is 30 weight% or less, Most preferably, it is 20 weight% or less. Within this range, the organic fine particles (F) can be efficiently introduced into (X).

  In the production method (1), the method for dispersing the organic fine particles (F) in the solvent (C) is not particularly limited. However, the organic fine particles (F) are charged into the solvent (C), and stirred, ultrasonically irradiated, or the like. Examples thereof include a method of directly dispersing and a method of crystallization by dissolving organic fine particles 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 in which the solution (L) in which the resin (G) and the infrared absorbent (A) are dissolved or dispersed in the solvent (C) is dispersed in carbon dioxide (X) A compound having at least one of a dimethylsiloxane group and a functional group containing fluorine can be used as the dispersion stabilizer (J). The dispersion stabilizer (J) preferably has a chemical structure having an affinity for the resin (G) together with a dimethylsiloxane group and a fluorine-containing group having an affinity for carbon dioxide.

  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 production method (1) [the same applies to later-described production methods (2) and (3). ] In the resin particles (H) containing the resin (G), the infrared absorber (A) and the solvent (C), other additives (coloring agent, filler, antistatic agent, release agent, charge control) Agents, antioxidants, antiblocking agents, heat stabilizers, flame retardants, etc.). As a method for adding other additives to the resin particles (H), a solution or dispersion in which the resin (G) or (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C) in advance. After mixing the liquid (L) and the additive, the mixture is preferably added and dispersed in (X). For example, when the resin particles are used as resin particles for an electrophotographic toner, a colorant is added. If necessary, a release agent is added to the resin particles.

  Resin (G) and infrared absorber (A) are dissolved or dispersed in solvent (C), or dispersion (L) is dispersed in organic fine particles (F) dispersed in carbon dioxide (X) ( When dispersing in X0), the solvent (C) solution (L0) of the infrared absorber (A) and the resin (G) may be mixed in advance, and then the mixed solution may be introduced and dispersed in (X0). These may be separately introduced and dispersed in (X0), but it is preferable that the infrared absorbers (A) and (L0) are mixed in advance and then dispersed in (X0). If it does so, an infrared absorber (A) can be disperse | distributed more uniformly in resin (G).

  In the production method (1), a solution or dispersion (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C), and the organic fine particles (F) in carbon dioxide (X). Any method may be used as the method of dispersing in the dispersion (X0) in which is dispersed. Specific examples include a method of dispersing the dissolved or dispersed liquid (L) with a stirrer or a dispersing machine, the dissolved or dispersed liquid (L), and the dispersion (X0) in which (F) is dispersed in (X). A method in which droplets are formed by spraying through a spray nozzle, the resin in the droplets is supersaturated, and resin particles are precipitated (ASES: known as Aerosol Solvent Extraction System), coaxial multiple tube Dissolve or disperse liquid mixture (L) and dispersion (X0) together with high-pressure gas, entrainer, etc. from different pipes simultaneously (double pipe, triple pipe, etc.) to apply external stress to the droplets In addition, a method of obtaining particles by promoting division (SEDS: Solution Enhanced Dispersion by Supercritical Fluids) And a method of irradiating ultrasonic waves.

Thus, the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C) in the dispersion (X0) in which the organic fine particles (F) are dispersed in carbon dioxide (X). The resin (G) and the infrared absorbent (A) are dispersed by dispersing the dissolved or dispersed liquid (L) and growing the dispersed resin (G) while adsorbing the organic fine particles (F) on the surface. Resin particles (I) having organic fine particles (F) fixed thereon are formed on the surfaces of the resin particles (H) containing the solvent (C). 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, when the dissolved or dispersed liquid (L) is used, 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 or dispersion (L) in the dispersion (X0) so that the solvent phase does not separate. 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 infrared absorber (A) and the solvent (C) is preferably 10 to 90% by weight, more preferably 20 to 20%. 70% by weight.
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 the infrared absorbent-containing 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 the infrared absorbent-containing 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). , Tg or a temperature below the melting point.

  In the method (1) for producing the infrared absorbent-containing 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 the infrared absorbent-containing resin particles of the present invention, the temperature and pressure of the operation performed in carbon dioxide (X) are such that the resin (G) does not dissolve in (X) and (G) Is preferably set within a range where aggregation and coalescence are possible. 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 infrared absorbent-containing resin particles of the present invention, physical property values (viscosity, diffusion coefficient, dielectric constant, solubility, interfacial tension, etc.) as a dispersion medium are adjusted. In addition, other substances (Y) may be included as appropriate, 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.

  Carbon dioxide (X) is usually removed under reduced pressure from the dispersion (X1) in which the resin particles (I) are dispersed to obtain infrared absorbent-containing 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.

  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 the infrared absorbent-containing resin particles of the present invention, the organic fine particles (F) are once fixed on the surfaces of the resin particles (H), but the (F) is crystallized. When the crystalline resin (f1) is contained, 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 of H).
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, (F) A part of the film may be formed into a film, but in order for the infrared absorbent (A) contained in the resin (G) to function more easily, the resin particles (H) Those having organic fine particles (F) fixed on the surface or those having a part of (F) formed into a film are preferred. 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).

  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) as a further step, if necessary. That is, when (I) contains the solvent (C) in the dispersion (X1) dispersed in (X), if the container is decompressed as it is, the solvent dissolved in (X1) condenses 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, the dispersion (X1) obtained by dispersing the dissolved or dispersed liquid (L) in which the infrared absorber (A) is dissolved or dispersed in the solvent (C), Further, carbon dioxide (X) is mixed to extract the solvent (C) from the resin particles (I) into the phase of carbon dioxide (X). Next, (X) containing the solvent (C) is removed from the solvent (C). It is preferable to replace with (X) not contained, and then reduce the pressure.

  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 production method (2) of the infrared absorbent-containing 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 production method (2), any method may be used to disperse the organic fine particles (F) in the non-aqueous organic solvent (N). For example, (F) and (N) are charged in a container, stirred, sprayed, Examples thereof include a method of directly dispersing (F) in (N) by ultrasonic irradiation and a method of introducing the solvent dispersion of (F) into (N). 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 the infrared absorbent-containing resin particles of the present invention is preferably in the range of 9.5 to 20, and more preferably. Is 10-19. When the SP value of the solvent (C) is within this range, when the dissolved or dispersed liquid (L) is dispersed in the non-aqueous organic solvent (N), (C) is not extracted into (N). The particle size distribution of the resin particles (I) is preferable because it is not wide.
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 can be used for preparing the solution (L0) 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.

  Since the solution (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C) is dispersed in (N), it is preferable to have an appropriate viscosity. From the viewpoint of particle size distribution, it is preferably 100 Pa · s or less, more preferably 10 Pa · s or less.

  In the method (2) for producing infrared absorbent-containing 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), a resin (G) and an infrared absorbent (A) is dissolved or dispersed in the solvent (C) or mixed with the dispersion (L), (L) is dispersed in the non-aqueous dispersion of (F), and (F) is non-aqueous. By forming resin particles (H) containing (G), an infrared absorber (A) and a solvent (C) in the dispersion, the organic fine particles (F) are fixed on the surfaces of the resin particles (H). A non-aqueous dispersion of resin particles (I) having a structure is obtained.

  Resin (G) and infrared absorber (A) dissolved or dispersed in solvent (C) are dissolved or dispersed liquid (L), and organic fine particles (F) are dispersed in nonaqueous organic solvent (N). Examples of the method of dispersing in the aqueous dispersion include a method of introducing (L) into the non-aqueous dispersion of (F) and dispersing.

  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 dissolved or dispersed liquid (L) is dispersed in the non-aqueous dispersion of (F), a dispersing device can be used.
The dispersion apparatus used in the method (2) for producing the infrared absorbent-containing resin particles of the present invention is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. The thing of -284881 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 production method (3) of the infrared absorbent-containing resin particles of the present invention will be described in detail.
Examples of the resin (f), resin (G), and solvent (C) constituting the organic fine particles (F) used in the production method (3) are the same as those used in the production method (1).

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 in the presence of an appropriate dispersant if necessary, and then A method for producing an aqueous dispersion of organic fine particles (F) by curing the precursor by heating to a temperature or adding a curing agent.
[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 water in the presence of an appropriate dispersant.
[5] A method of obtaining resin particles by spraying a resin solution prepared by previously dissolving a resin prepared by a polymerization reaction in an organic solvent in a mist, and then dispersing the resin particles in water in the presence of an appropriate dispersant.
[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 obtaining resin particles by removing the solvent, and then dispersing the resin particles in water in the presence of a suitable dispersant.
[7] A method in which a resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction in an organic solvent is dispersed in an aqueous medium in the presence of a suitable 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 the infrared absorbent-containing resin particles of the present invention, the aqueous dispersion of organic fine particles (F), the resin (G) and the infrared absorbent (A) are dissolved or dispersed in the solvent (C). In the aqueous dispersion of (F), the resin (G) and the infrared absorbing agent (L) are dispersed by mixing the dissolved or dispersed liquid (L) and dispersing the (L) in the aqueous dispersion of (F). By forming the resin particles (H) containing A) and the solvent (C), an aqueous dispersion of the resin particles (I) having a structure in which (F) is fixed to the surface of (H) can be obtained. .

  As a method of dispersing the dissolved or dispersed liquid (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C) in the aqueous dispersion of the organic fine particles (F), Examples thereof include a method of introducing the dispersion liquid (L) into the aqueous dispersion liquid (F) and dispersing it.

  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 dissolved or dispersed liquid (L) is dispersed in the aqueous dispersion (F), a dispersing device can be used. Examples of the dispersing device include those described above.

As a method of removing the aqueous medium 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.

  The volume average particle size of the resin particles (I) obtained by the production methods (1) to (3) of these infrared absorber-containing resin particles is preferably 1 to 10 μm, more preferably 2 to 8 μm.

According to the method for producing infrared absorbent-containing resin particles of the present invention [particularly production methods (1) to (3)], resin particles having a narrow particle size distribution can be stably produced regardless of the type of infrared absorbent (A). Can be manufactured.
Further, the infrared absorbent resin particles (I) obtained by the method for producing the infrared absorbent-containing resin particles of the present invention are excellent in fixability and have a sufficiently narrow particle size distribution and are useful for electrophotographic toners. Further, as other applications, it is also useful as a coating additive, an adhesive additive, a slush molding resin, a powder coating, an electrostatic recording toner, an electrostatic printing toner, and the like.

  When resin particles are used as resin particles for electrophotographic toners, known dyes and pigments can be widely used as colorants to be added. Specifically, carbon black, Sudan Black SM, First Yellow-G, Benzidine Yellow , Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Examples include green, phthalocyanine green, oil yellow GG, kaya set YG, orazole brown B, and oil pink OP.

When using resin particles as resin particles for electrophotographic toner, in addition to the colorant, if necessary, a release agent is further added to the resin particles. Examples of the mold release agent include wax. Specific examples include synthetic waxes and natural waxes. Examples of synthetic waxes include polyolefin waxes, and examples of natural waxes include paraffin wax, microcrystalline wax, carnauba wax, carbonyl group-containing wax, and mixtures thereof.
In some cases, a modified wax grafted with a vinyl polymer chain may be contained for the purpose of improving the dispersibility of the wax.

  Examples of the wax used for the modified wax include the same waxes as those described above. Examples of the vinyl monomer constituting the vinyl polymer chain include the same monomers as the monomers (1) to (10) constituting the vinyl resin. The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

  The modified wax is prepared by, for example, dissolving or dispersing a wax in an organic solvent (for example, toluene or xylene), heating to 100 to 200 ° C., and then converting a vinyl monomer into a peroxide initiator (benzoyl peroxide, ditertiary butyl peroxide, tertiary oxide). It can be obtained by dropping together with butyl peroxide benzoate etc.) and polymerizing, and then distilling off the organic solvent.

  As a method of mixing the wax and the modified wax, [1] a method of melt-kneading at a temperature equal to or higher than the melting point of each, and [2] by dissolving or suspending in an organic solvent, cooling crystallization, solvent crystallization, etc. Examples of the method include precipitation in a liquid or precipitation in a gas by spray drying and the like, and [3] a method of dissolving or suspending in an organic solvent and then performing mechanical wet pulverization with a disperser. Among these, the method [2] is preferable.

  The electrophotographic toner used in the electrophotographic process is temporarily attached to an image carrier such as a photosensitive member on which an electrostatic charge image is formed in the developing process, and then transferred from the photosensitive member to the transfer paper in the transferring step. After being transferred to a transfer medium such as, it is fixed on the paper surface in a fixing step. In general, electrophotographic toners are used by mixing resin particles for toner and inorganic powders such as various metal oxides in order to impart flow characteristics. These inorganic powders are called external additives. Yes. As the electrophotographic toner of the present invention, the infrared absorbent-containing resin particles (resin particles for electrophotographic toner) obtained by the production method of the present invention can be used as they are, but an external additive is added to the resin particles for electrophotographic toner. Those added are preferred.

  As external additives, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known. In particular, silica particles obtained by reacting silica or titanium oxide fine particles with an organosilicon compound such as dimethyldichlorosilane, hexamethyldisilazane, or silicone oil and replacing the silanol groups on the surface of the silica fine particles with organic groups are preferably used. .

  The use amount (% by weight) of the external additive is not particularly limited, but is preferably 0.01 to 5% with respect to the weight of the resin particles for an electrophotographic toner from the viewpoint of compatibility between fixability and fluidity. More preferably, it is 0.1 to 4%, and particularly preferably 0.5 to 3%.

  In the production method (2), the dispersion in which the infrared absorbent-containing resin particles are dispersed in the non-aqueous organic solvent (N) by removing only the solvent (C) from the non-aqueous dispersion of the resin particles (I). A liquid can also be obtained. When obtaining a dispersion in which the infrared absorbent-containing resin particles are dispersed in the non-aqueous organic solvent (N), a solvent having a boiling point lower than that of the non-aqueous organic solvent (N) is selected as the solvent (C), and the above solvent removal is performed. It is preferable to dry by the method [1] at a temperature at which only the solvent (C) can be removed.

  The dispersion in which the infrared absorbent-containing resin particles are dispersed in the non-aqueous organic solvent (N) can be used as a raw material for a liquid developer, a liquid toner and the like. In this case, it is preferable to add the colorant.

  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.

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 tetrabutoxy titanate as a condensation catalyst The mixture was allowed to react for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the propylene glycol and water produced under a nitrogen stream, and the reaction was further carried out under a reduced pressure of 5 to 20 mmHg. The recovered propylene glycol was 172 parts. When the softening point reached 160 ° C., 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 (L0-1)>
In a container equipped with a stirrer, 243 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 (L0-1). It was.

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 Corporation)], methyl methacrylate 22.5 parts, (2-perfluorodecyl) ethyl acrylate (Wako Pure Chemical Industries) 7.5 parts Then, 10 parts of AIBN (azobisisobutyronitrile) was charged, stirred and mixed at 20 ° C. to prepare a monomer solution, and charged into a dropping funnel. The monomer solution was added dropwise at 80 ° C. for 2 hours under hermetically sealed, 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 a resin (f− ) Was obtained. The melting point of the resin is 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% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion (solid content concentration 20%) of organic fine particles (F-2). The volume average particle size of (F-2) in this dispersion was 0.15 μm.

Example 1
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from the cylinder B2 and the pump P4, and the pressure was adjusted to 14 MPa and 40 ° C. Further, a resin solution tank L1 mixed with a resin solution (L0-1) and an infrared absorber (A-1; naphthalocyanine (manufactured by Aldrich)), and a non-organic fine particle (F-1) solution in a fine particle dispersion tank T2. An aqueous dispersion was charged. Next, carbon dioxide was introduced into the dispersion tank T3 from the cylinder B1 and the pump P3, adjusted to 9 MPa and 40 ° C., and a non-aqueous dispersion of organic fine particles (F-1) was further introduced from the tank T2 and the pump P2. Next, the liquid mixture of the resin solution (L0-1) and the infrared absorbent (A-1) was introduced into the dispersion tank T3 from the tank T1 and the pump P1, while stirring the inside of the dispersion tank T3 at 2000 rpm. After the introduction, the pressure inside T3 was 14 MPa.
In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L0-1) 270 parts Infrared absorber (A-1) 0.4 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 T3 (the same applies hereinafter).
Reference 2: Journal of Physical and Chemical Reference data, vol. 25, P.I. 1509 to 1596

  After introducing a liquid obtained by mixing the resin solution (L0-1) and the infrared absorbent (A-1), the mixture was stirred for 1 minute to obtain a dispersion (X-1). After opening the valve V1 and introducing carbon dioxide into T4 from P3, the dispersion (X-1) was introduced into T4, and the opening degree of V2 was adjusted so that the pressure was kept constant during this time. This operation was performed for 30 seconds, and V1 was closed. By this operation, the solvent was extracted from the resin solution introduced into T4. Further, T4 was heated to 60 ° C. and held for 15 minutes. By this operation, the organic fine particles (F-1) are fixed to the surface of the resin particles (H-1) formed from the resin solution (L0-1) and the infrared absorber (A-1), and the resin particles (I- 1) was produced. Next, carbon dioxide containing the extracted solvent is discharged to the solvent trap tank T5 by holding the pressure at 14 MPa by the pressure adjusting valve V2 while introducing carbon dioxide into the particle recovery tank T4 from the pressure cylinder B2 and the pump P4. 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 T4 from the pressure cylinder B2 and the pump P4 is to introduce carbon dioxide when 5 times the weight of carbon dioxide introduced into the dispersion tank T3 is introduced into the particle recovery tank T4. 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 adjustment valve V2 is opened little by little, the inside of the particle recovery tank is reduced to atmospheric pressure, and the organic fine particles (F-1) are fixed to the surface of the resin particles (H-1) supplemented by the filter F1. In addition, infrared absorber-containing resin particles (I-1) having a volume average particle diameter of 5.9 μm by Multisizer III (the same applies to the following resin particles) were obtained.

Example 2
In Example 1, instead of the resin solution (L0-1), a colored resin solution in which (L0-1) is mixed with a carbon black processed pigment (“MICROLITH Black C-K” manufactured by Ciba Japan) as a colorant is used. Except that it was used, in the same manner as in Example 1, the organic fine particles (F-1) were fixed to the surface of the resin particles (H-2) and uniformly colored, and the volume average particle diameter was 5.6 μm. Infrared absorber-containing resin particles (I-2) were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L0-1) 270 parts Infrared absorber (A-1) 0.4 part Colorant 5 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Example 3
A non-aqueous dispersion of normal decane and organic fine particles (F-1) was put into a beaker, mixed with a homomixer (manufactured by Primics) at a rotational speed of 16000 rpm for 10 seconds, and then a resin solution (L0-1) with stirring. And a mixture of an infrared absorber (A-1) and a carbon black processed pigment (“MICROLITH Black CK” manufactured by Ciba Japan) as a colorant were added all at once and dispersed for 1 minute to obtain a dispersion. Further, the dispersion was desolvated with an evaporator at 40 ° C. and 0.01 MPa, followed by filtration and drying to remove the solvent in the system, and organic fine particles (F− Infrared absorber-containing resin particles (I-3) having a volume average particle diameter of 5.2 μm, to which 1) was fixed and uniformly colored, were obtained.
The weight ratio of the charged composition in Example 3 is as follows.
Resin solution (L0-1) 270 parts Infrared absorber (A-1) 0.4 part Colorant 5 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Normal decane 120 parts

Example 4
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 (L0-1 ) After mixing 150 parts, infrared absorber (A-1), and carbon black processed pigment (“MICROLITH Black C-K” manufactured by Ciba Japan) as a colorant, use a TK homomixer (manufactured by Tokushu Kika). The mixture was mixed at 12,000 rpm for 10 minutes. After mixing, the mixed solution is put into a reaction vessel equipped with a stirring rod and a thermometer, and the solvent is removed at 50 ° C. for 2 hours, followed by filtration and drying, and organic fine particles on the surface of the resin particles (H-4). Infrared absorbent-containing resin particles (I-4) having a volume average particle size of 4.9 μm, to which (F-2) was fixed and uniformly colored, were obtained. The weight ratio of the composition charged into the beaker in Example 4 is as follows.
Resin solution (L0-1) 150 parts Infrared absorber (A-1) 0.2 parts Colorant 3 parts Aqueous dispersion of organic fine particles (F-2) 11 parts 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate
80 parts Ion exchange water 300 parts

Comparative Example 1
In Example 2, organic fine particles (F-1) were fixed to the surfaces of the resin particles (H′-1) in the same manner as in Example 2 except that the infrared absorbent (A-1) was not used. Uniformly colored comparative resin particles (RI-1) having a volume average particle size of 5.0 μm were obtained.
In addition, the weight ratio of the preparation composition to the dispersion tank T3 is as follows.
Resin solution (L0-1) 270 parts Colorant 5 parts Non-aqueous dispersion of organic fine particles (F-1) 45 parts Carbon dioxide 550 parts

Comparative Example 2
66 parts of resin (G-1) obtained in Production Example 1, 15 parts of resin (G-2) obtained in Production Example 2, 0.4 part of infrared absorber (A-1), carbon black as a colorant Contains 5 parts of processed pigment (“MICROLITH Black CK” manufactured by Ciba Japan), kneaded using a continuous extruder, pulverized and classified, and contains a comparative infrared absorber having a volume average particle size of 8.3 μm Resin particles (RI-2) were obtained.

<Measurement method of ratio of volume average particle diameter to number average particle diameter (Dv / Dn)>
5 mg of resin particles were dispersed in 10 g of a sodium dodecylbenzenesulfonate aqueous solution (concentration 0.1%) and measured with a Coulter counter [Multisizer III (manufactured by Beckman Coulter)].

  Infrared absorber-containing resin particles (I-1) to (I-4) of the present invention prepared in Examples 1 to 4, resin particles (RI-1) for comparison prepared in Comparative Example 1, and Comparative Examples The ratio (Dv / Dn) of the volume average particle size and the number average particle size of the infrared absorbent-containing resin particles (RI-2) for comparison prepared in 2 was measured by the above method. The results are shown in Table 1.

<Evaluation of fixability>
The fixing temperature was evaluated by the following method.
Infrared absorbent-containing resin particles (I-2) to (I-4) of the present invention prepared in Examples 2 to 4, resin particles (RI-1) for comparison prepared in Comparative Example 1, and Comparative Examples Add 1.0% Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to the infrared absorbent-containing resin particles (RI-2) for comparison prepared in Step 2, and mix well using a mixer. An electrophotographic toner for evaluation adhered uniformly to the surface was prepared.
Next, using these electrophotographic toners for evaluation, a character image was formed by a reversal development type laser printer (printing speed 100 mm / sec) using an organic photoconductor as a photoconductor, and an unfixed image was used. The flash fixability was evaluated.
The flash fixing device was set using a capacitor having a capacity of 160 μF, a charging voltage of 2050 V, and applied to the flash lamp. The light emission time was 1000 μsec.
Using the fixed image, lightly affix a tape (Sumitomo 3M, Scotch Mending Tape) on the image, place a cylindrical weight with a diameter of 5 cm and a weight of 1 kg. The film was peeled off and visually observed for the state of adhesion to the tape, and judged according to the following criteria. The results are shown in Table 1.
○: No deposit on the tape △: Slight deposit on the tape ×: A lot of deposit on the tape

  The resin particles of the present invention of Examples 1 to 4 had a small Dv / Dn and a sufficiently narrow particle size distribution, whereas the resin particles of Comparative Examples 1 and 2 had a large Dv / Dn and a wide particle size distribution. . In addition, the electrophotographic toners produced from the resin particles of Examples 2 to 4 were excellent in fixability, whereas the electrophotographic toners produced from the resin particles of Comparative Examples 1 and 2 were remarkably deteriorated. did.

  Infrared absorber-containing resin particles obtained by the production method of the present invention have excellent fixability and a sufficiently narrow particle size distribution, so that the base particles of electrophotographic toner, paint additives, cosmetic additives, paper coating additives It is useful as an agent, slush molding resin, powder coating material, electronic component manufacturing spacer, standard particles for electronic measuring instruments, electronic paper particles, medical diagnostic carriers, electroviscous particles, and other molding resin particles. In particular, it is useful as a base particle of an electrophotographic toner.

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

Claims (6)

  A solution or dispersion (L) in which the resin (G) and the infrared absorber (A) are dissolved or dispersed in the solvent (C), and a dispersion in which the organic fine particles (F) are dispersed in the dispersion medium (B); Are mixed, and (L) is dispersed in (B), whereby organic fine particles (F) are formed on the surface of resin particles (H) containing resin (G), infrared absorber (A) and solvent (C). A method for producing infrared-absorbing agent-containing resin particles, comprising the steps of forming resin particles (I) to which is fixed, and then removing the dispersion medium (B) and the solvent (C).   The method for producing resin particles containing infrared absorbents according to claim 1, wherein the dispersion medium (B) is carbon dioxide (X) in a liquid state or a supercritical state.   The method for producing infrared-absorbing agent-containing resin particles according to claim 1, wherein the dispersion medium (B) is a non-aqueous organic solvent (N).   The method for producing resin particles containing infrared absorbers according to claim 1, wherein the dispersion medium (B) is an aqueous medium (Z).   The infrared absorber containing resin particle obtained by the manufacturing method in any one of Claims 1-4.   An electrophotographic toner containing the infrared absorbent-containing resin particles according to claim 5.

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