JP2006111720A - Method for producing resin or resin particle and the resultant resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a resin or resin particles through inhibiting decomposition reaction and through mitigating the burden on the environment, and to provide the resultant resin particles. <P>SOLUTION: The method for producing the resin or resin particles comprises the following process: A polycondensation reaction progress is accomplished by removing byproducts out of the reaction system in a fluid comprising a supercritical fluid and/or subcritical fluid. The resin particles are produced by the method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  The resin particles are generally formed of a polymer, and are a display, a rear projection screen for viewing a film, a magnetic recording medium, a liquid crystal display spacer, a light diffusing agent for various lighting fixtures, a column filler, a diagnostic agent Polymer particles used for carriers, drug delivery systems, bioreactors, etc .; seed particles for producing polymer fine particles; electrophotographic image forming particle matrix; external additives, etc.

  Conventionally, in order to produce resin particles, a method of physically pulverizing using a pulverizer or the like has been used. According to this method, resin particles can be easily produced at low cost. However, the shape of the resin particles is indefinite, low in sphericity, and large in particle size. For this reason, in order to produce resin particles having a narrow particle size distribution, a process such as classification is required, but there is a problem that the strength of the resin particles tends to be weak.

  As an alternative to physical pulverization, a method of producing resin particles by a polymerization method such as emulsion polymerization, dispersion polymerization, seed polymerization or suspension polymerization is known. For example, after preparing a monomer dispersion liquid containing droplets of a desired size in advance, this dispersion liquid is introduced into a polymerization tank, and polymerization is carried out under normal stirring, so that the particle size and particle size distribution of the resin particles can be reduced. A control method is known (see Patent Document 1). According to this method, resin particles having a high sphericity and a narrow particle size distribution can be produced. However, this method has a limited range of application to polymers obtained from radical-reactive monomers, and it is practically impossible to completely react the monomers during the polymerization process. There is a problem that a small amount of monomer remains on the surface. When the monomer remains, the resin particles have hygroscopicity.

  In contrast, resins obtained by polycondensation, such as polyester resins, polyamide resins, and polyimide resins, are excellent in heat resistance, chemical resistance, and mechanical properties, and are functionally modified in the structure of the main chain and side chains. By changing the type of the group, various performances are expected, and since the material is inexpensive, it is expected that the application will be dramatically expanded by making particles.

  As a method for forming a polycondensation polymer into particles, a resin such as nylon is heated and dissolved using ethylene glycol and a polar solvent in a dissolution tank and then cooled (see Patent Document 2), and a solution of nylon 11 is in a molten state. There are known a method of spraying and cooling (see Patent Document 3), a method of bringing a molten molded product of a thermoplastic resin and a water-soluble resin into contact with water (see Patent Document 4), and the like. However, these methods have a problem that a melting step is required, the operation is complicated, and the physical properties of the resin are lowered.

Also, a method of dissolving and precipitating a polyamide resin in a solvent that dissolves for the first time under high temperature and high pressure (see Patent Document 5), or generating a supercritical state or a subcritical state and dissolving a polyester resin at normal temperature A method of depositing polyester resin particles by returning to a pressure (see Patent Document 6) is known. However, the temperature and pressure conditions applied to dissolve the resin are excessive as compared with the energy required for the precipitation of the particles, so that the polymer decomposition reaction may occur or the polymer may be discolored.
JP-A-3-131603 Japanese Patent No. 3165184 JP-A-5-70598 JP-A-9-165457 JP-A-9-316206 JP 2004-143406 A

  The present invention has been made in view of the above-described problems of the prior art. Resin capable of suppressing decomposition reaction, reducing the burden on the environment, and efficiently producing the resin, the resin particle production method, and production of the resin particle It aims at providing the resin particle manufactured by the method.

  According to the first aspect of the present invention, in the resin production method, a polycondensation reaction is allowed to proceed by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid. And producing a resin.

  According to the first aspect of the present invention, a resin is produced by advancing the polycondensation reaction by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid. Therefore, it is possible to provide a method for producing a resin that can suppress the decomposition reaction, reduce the burden on the environment, and can be efficiently produced.

  According to a second aspect of the present invention, in the method for producing a resin according to the first aspect, the by-product is separated and removed from the reaction system.

  According to invention of Claim 2, since the said by-product is removed out of a reaction system by isolate | separating, the reaction rate of a polycondensation reaction can be improved.

  The invention according to claim 3 is the method for producing a resin according to claim 1, wherein the by-product is removed from the reaction system by reacting with a substance that reacts with the by-product. .

  According to the third aspect of the present invention, since the by-product is removed from the reaction system by reacting with the substance that reacts with the by-product, the reaction rate of the polycondensation reaction can be improved.

  According to a fourth aspect of the present invention, in the method for producing a resin according to the first aspect, the by-product is removed from the reaction system by adsorbing the by-product to an adsorbing substance. .

  According to the fourth aspect of the present invention, since the by-product is removed from the reaction system by adsorbing the by-product to the adsorbing substance, the reaction rate of the polycondensation reaction can be improved.

  According to a fifth aspect of the present invention, in the method for producing resin particles, a polycondensation reaction proceeds by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid. To produce resin particles.

  According to the fifth aspect of the present invention, in the fluid containing at least one of the supercritical fluid and the subcritical fluid, the polycondensation reaction is advanced by removing the by-products out of the reaction system, so that the resin particles Since it manufactures, the decomposition reaction can be suppressed, the burden on the environment can be reduced, and the manufacturing method of the resin particle which can be manufactured efficiently can be provided.

  According to a sixth aspect of the present invention, in the method for producing resin particles according to the fifth aspect, the by-product is removed from the reaction system by separation.

  According to the invention described in claim 6, since the by-product is separated and removed from the reaction system, the reaction rate of the polycondensation reaction can be improved.

  Invention of Claim 7 is a manufacturing method of the resin particle of Claim 5, It is characterized by removing the said by-product out of a reaction system by making it react with the substance which reacts with the said by-product. To do.

  According to the seventh aspect of the invention, since the by-product is removed from the reaction system by reacting with the substance that reacts with the by-product, the reaction rate of the polycondensation reaction can be improved.

  The invention according to claim 8 is the method for producing resin particles according to claim 5, wherein the by-product is removed from the reaction system by adsorbing the by-product to the adsorbing substance. To do.

  According to the eighth aspect of the present invention, since the by-product is removed from the reaction system by adsorbing the by-product to the adsorbing substance, the reaction rate of the polycondensation reaction can be improved.

  The invention according to claim 9 is the method for producing resin particles according to any one of claims 5 to 8, wherein the fluid contains carbon dioxide.

  According to invention of Claim 9, since the said fluid contains a carbon dioxide, a part or all of the fluid can be vaporized by returning to normal temperature normal pressure.

  A tenth aspect of the present invention is the method for producing resin particles according to any one of the fifth to ninth aspects, wherein the fluid contains an organic solvent.

  According to invention of Claim 10, since the said fluid contains the organic solvent, reaction conditions can be set more widely.

  Invention of Claim 11 is a manufacturing method of the resin particle as described in any one of Claim 5 thru | or 10. WHEREIN: The said by-product is water, The said resin particle is a polyester resin and polyether resin. It contains at least one of these.

  According to the invention of claim 11, the by-product is water, and the resin particles contain at least one of a polyester resin and a polyether resin, and thus have excellent transparency and various functions. Resin particles that can be obtained can be obtained.

  Invention of Claim 12 is a manufacturing method of the resin particle as described in any one of Claim 5 thru | or 10, The said by-product is water, The said resin particle is a polyamide resin, a polyimide resin, and It contains at least one polyamideimide resin.

  According to the invention of claim 12, the by-product is water, and the resin particles contain at least one of a polyamide resin, a polyimide resin, and a polyamide-imide resin. Resin particles capable of adding various functions can be obtained.

  The invention according to claim 13 is the method for producing resin particles according to any one of claims 5 to 12, wherein the resin particles are further aggregated or fused in an aqueous solvent or in the fluid. Features.

  According to the invention described in claim 13, since the resin particles are further aggregated or fused in an aqueous solvent or the fluid, the particle diameter of the resin particles can be controlled.

  The invention described in claim 14 is characterized in that the resin particles are manufactured by the method for manufacturing resin particles according to any one of claims 5 to 13.

  According to the invention of the fourteenth aspect, since the resin particle is produced by the method for producing a resin particle according to any one of the fifth to thirteenth aspects, resin particles with little decomposition can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the resin particle manufactured by the resin, the manufacturing method of resin, and the manufacturing method of this resin particle which can suppress a decomposition reaction, reduce the burden on an environment, and can manufacture efficiently Can be provided.

  Next, the best mode for carrying out the present invention will be described.

  The resin and resin particle production method of the present invention allows a polycondensation reaction to proceed by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid. Resin particles are produced. Thereby, the decomposition reaction can be suppressed, the load on the environment can be reduced, and the production can be efficiently performed. Here, removing out of the reaction system means moving from the fluid phase in which the reaction proceeds to another phase.

  Specific examples of the polycondensation reaction include etherification reaction of diol, esterification reaction of dicarboxylic acid and diol, esterification reaction of acid chloride and diol, amidation reaction of dicarboxylic acid and diamine, and acid anhydride. Examples include imidization reaction with diamine. These reactions may be performed simultaneously or sequentially. At this time, a catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, magnesium acetate, or manganese acetate can be used as necessary.

  Specific examples of the diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, triethylene glycol, and tetraethylene. Glycol, 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), 1,2-hexanediol, 2, Aliphatic diols such as 5-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol; 4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxycyclohexyl) Le) alkylene oxide adducts of propane, 1,4-cyclohexane diol, alicyclic diols such as 1,4-cyclohexanedimethanol.

  Specific examples of dicarboxylic acids include o-phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octyl succinic acid, cyclohexanedicarboxylic acid, naphthalenedicarboxylic acid, fumaric acid, maleic acid, itacone Examples include acids, decamethylene carboxylic acids, anhydrides and lower alkyl esters thereof.

  Specific examples of diamines include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl. 1,4′-bis (4-aminophenoxy) benzene, 1,3′-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, o-phenylenediamine, m-phenylene Diamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis ( 2-chloroaniline), 3,3′-dimethyl-4,4′-diaminobiphenyl, 4, '-Diaminodiphenyl sulfide, 2,6'-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobibenzyl, R (+)-2,2′-diamino-1,1′-binaphthalene, S (+)-2,2′-diamino-1, 1'-binaphthalene; 1, n-bis such as 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane (4-aminophenoxy) alkane (n is an integer of 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] Aromatic diamines such as tan, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobenzanilide; 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5 -Aliphatic diamines such as diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminododecane, 1,11-diaminoundecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane Alicyclic diamines such as bis (4-aminocyclohexyl) methane and 4,4′-diaminodicyclohexylmethane; 3,4-diaminopyridine, 1,4-diamino-2-butanone and the like can be used. These diamines can be used alone or as a mixture of two or more. In particular, when one or more diamines selected from the group consisting of 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone are used, Since heat resistance and monodispersibility improve, it is preferable. In the present invention, amines such as monoamines and polyamines can be used in addition to diamines. By these, the characteristic of a polyamide resin can be changed.

  Specific examples of acid chlorides include oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride, muconic acid dichloride, sebacic acid dichloride, nonanoic acid dichloride, undecanoic acid dichloride, etc. Aliphatic dicarboxylic acid dichloride; 1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acid dichlorides such as acid dichloride; phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 1,5- (9-oxofur Len) dicarboxylic acid dichloride, 1,4-anthracene dicarboxylic acid dichloride, 1,4-anthraquinone dicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5-biphenylenedicarboxylic acid dichloride, 4,4'-biphenyldicarbonyl Chloride, 4,4′-methylene dibenzoic acid dichloride, 4,4′-isopropylidene dibenzoic acid dichloride, 4,4′-bibenzyldicarboxylic acid dichloride, 4,4′-stilbene dicarboxylic acid dichloride, 4,4 ′ -Transidicarboxylic acid dichloride, 4,4'-carbonyldibenzoic acid dichloride, 4,4'-oxydibenzoic acid dichloride, 4,4'-sulfonyldibenzoic acid dichloride, 4,4'-dithiodibenzoic acid dichloride, p-phenylenediacetic acid dichloride, 3,3 ′ Aromatic dicarboxylic acid dichloride such as p- phenylene acid dichloride can be mentioned. These acid chlorides can be used alone or as a mixture of two or more.

  Specific examples of acid chlorides include trimellitic acid chloride, pyromellitic acid chloride, oxydiphthalic acid chloride, biphenyl-3,4,3 ′, 4′-tetracarboxylic acid chloride, benzophenone-3,4,3 ′, 4 ′. -Tetracarboxylic acid chloride, diethylpyromellitate diacyl chloride, diphenylsulfone-3,4,3 ', 4'-tetracarboxylic acid chloride, 4,4'-(2,2-hexafluoroisopropylidene) phthalic acid chloride, m (p) -phenyl-3,4,3 ′, 4′-tetracarboxylic acid chloride, cyclobutane-1,2,3,4-tetracarboxylic acid chloride, 1-carboxymethyl-2,3,5-cyclopentane And tricarboxylic acid chloride. These acid chlorides may be any of dichloride, trichloride, and tetrachloride. Moreover, when manufacturing polyamideimide resin, in addition to acid chloride, trimellitic anhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, biphenyl-3,4,3 as acid anhydride ', 4'-tetracarboxylic dianhydride, benzophenone-3,4,3', 4'-tetracarboxylic dianhydride, diethyl pyromellitate diacyl dianhydride, diphenylsulfone-3,4,3 ' , 4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, m (p) -phenyl-3,4,3 ′, 4′-tetra Carboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic dianhydride can be used. Furthermore, when manufacturing a polyimide resin, an acid dianhydride is used.

  Furthermore, divinylbenzene, divinylbiphenyl, divinylnaphthalene, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Polyfunctional monomers such as methylol methane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, diallyl phthalate and its isomers, triallyl isocyanurate and its derivatives may be added. By adding such a polyfunctional monomer, it is possible to crosslink as necessary to change physical properties such as strength and various properties such as thermoplasticity. These polyfunctional monomers may be used independently and may use 2 or more types together.

  In order to enhance the toughness of the polyester resin, the charged molar amount of the diol is preferably 1.3 times or less, more preferably 1.2 times or less, relative to the charged molar amount of the dicarboxylic acid. Furthermore, from the viewpoint of adding a function to the resin particles, the resin particles preferably contain a polyol resin.

  The supercritical fluid used in the present invention exists as a non-condensable high-density fluid in a temperature / pressure region exceeding the limit (critical point) at which a gas and a liquid can coexist. The supercritical fluid can be appropriately selected according to the purpose as long as it is a fluid at a critical temperature (hereinafter also referred to as Tc) or higher and a critical pressure (hereinafter also referred to as Pc). Preferably the temperature is low.

  The subcritical fluid used in the present invention can be appropriately selected according to the purpose as long as it exists as a high-pressure liquid in the temperature / pressure region near the critical point. The subcritical fluid is a fluid in a state of 0.5Pc <P <Pc, 0.5Tc <T, or 0.5Pc <P, 0, where P and T are the pressure and temperature during the reaction, respectively. Means a fluid in a state of 5Tc <T <Tc. The subcritical fluid is preferably a fluid in a state of 0.6Pc <P <Pc and 0.6Tc <T or a fluid in a state of 0.6Pc <P and 0.6Tc <T <Tc. Here, the unit of T and Tc is ° C., and the above-described formula representing the subcritical state is applied when Tc is a positive number. The critical temperature is preferably from −273 ° C. to 400 ° C., more preferably from 0 ° C. to 200 ° C. The critical pressure is preferably 1 MPa or more, and more preferably 7.2 MPa or more.

  Examples of the fluid used in the present invention include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, and dimethyl ether. Among these, carbon dioxide is particularly preferable in that the critical temperature is close to room temperature and the handleability is excellent. Supercritical carbon dioxide and supercritical carbon monoxide having a critical temperature of 30 ° C. or more and 40 ° C. or less are preferably used in a temperature / pressure region of 25 ° C. or more and 300 ° C. or less and 5 MPa or more and 100 MPa or less. At temperatures below 25 ° C. and pressures below 5 MPa, carbon dioxide and carbon monoxide are less likely to become supercritical fluids. In addition, in a temperature range higher than 300 ° C., there is a resin that generates gas or decomposes. Furthermore, in a pressure region higher than 100 MPa, the operation of the device including the fluid pump may be hindered. Incidentally, carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.53 MPa, and carbon monoxide has a critical temperature of 37 ° C. and a critical pressure of 7.26 MPa. In addition, the fluid used by this invention may be used independently and may be used as a 2 or more types of mixture.

  The fluid used in the present invention may contain a fluid other than the supercritical fluid and the subcritical fluid. Examples of such a fluid include nitric oxide, ethane, propane, ethylene, and the like. The content rate of such a fluid can be suitably selected according to the purpose.

  The fluid used in the present invention preferably contains an organic solvent as an entrainer. An entrainer is an additive that mixes a low-concentration organic solvent with a fluid to change the solubility or diffusibility of the composition dissolved or dispersed in the fluid. Thereby, reaction conditions in the fluid can be set more widely. The organic solvent can be appropriately selected according to the purpose, and examples thereof include methanol, ammonia, melamine, urea, thiodiethylene glycol and the like.

  When the fluid used in the present invention contains another fluid or an organic solvent, the solubility of the resin and the resin particles in the fluid and the change in the phase formation state can be controlled.

  In the present invention, the by-product soluble in the fluid generated by the progress of the reaction needs to be removed out of the reaction system. Thereby, the reaction rate of a polycondensation reaction can be improved. By-products include water, acids such as hydrochloric acid, alkalis such as sodium hydroxide, etc., but water is preferable in view of solubility in supercritical fluids and subcritical fluids, and handling is relatively easy. When the by-product is water, the reaction rate can be improved by dehydration.

  Examples of the method for removing the by-product include a method in which a separation tank that can be cooled or decompressed is provided in a part of the reaction apparatus, the by-product is separated in the separation tank, and removed from the reaction system. When cooled or depressurized in the separation layer, the fluid is vaporized or liquefied. When the fluid is liquefied, it is preferable that the by-product is insoluble in the fluid and other components are dissolved or dispersed in the fluid. At this time, if the specific gravity of the fluid and the by-product are different, it can be easily separated, which is more preferable. Moreover, when a fluid vaporizes, it is preferable that a by-product and other components are phase-separated.

  As another method for removing the by-product, there are a method of adding a substance that reacts with the by-product into the fluid and a method of adding a substance that adsorbs the by-product into the fluid. Note that a substance that reacts with the by-product and a substance that adsorbs the by-product can be used in combination.

  A specific example of a method for adding a substance that reacts with water into a fluid when the by-product is water is to add a substance that forms a hydrate so that the generated water does not return to the fluid. The method of trapping is mentioned. Substances that form hydrates include DL-asparagine, L-asparagine, monosodium L-aspartate, acetylacetone calcium, acetylacetone cobalt, acetylacetone cerium, acetylacetone nickel, acetylacetone barium, acetylacetone manganese, acetylacetone lanthanum, sodium selenite Adenine hydrochloride, disodium adenosine-5′-triphosphate, sodium tellurite, iron arsenite, iron amidosulfate, nickel amidosulfate, 5-amino-1H-tetrazole, aminoguanidine sulfate, ammonium sulfite, Calcium sulfite, sodium sulfite, magnesium sulfite, disodium phosphite, potassium aluminate, alloxan, magnesium benzoate, ammonium Reineke salt, iso Sodium Scorbate, Inosine-5′-Sodium phosphate, Disodium iminodiacetic acid, ouabain, Ethylenediamine, Disodium ethylenediaminediacetate, Trisodium ethylenediaminetetraacetate, Dipotassium ethylenediaminetetraacetate, Dipotassium ethylenediaminetetraacetate, Ethylenediaminetetra Disodium acetate dihydrogen acetate, disodium ethylenediaminetetraacetate, calcium disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, copper disodium ethylenediaminetetraacetate, lead ethylenediaminetetraacetate disodium, ethylenediaminetetraacetic acid disodium nickel, ethylenediamine Disodium magnesium tetraacetate, ethylenediamine disodium manganese tetraacetate, ethylenediamine Tetrasodium acetate, ergosterol, ergotamine tartrate, aluminum chloride, ytterbium chloride, yttrium chloride, indium chloride, erbium chloride, osmium chloride, cadmium chloride, gadolinium chloride, calcium chloride, sodium chloride gold, sodium chloride chloride, chromium chloride, chloride Cobalt, samarium chloride, dysprosium chloride, scandium chloride, tin chloride, strontium chloride, cetylpyridinium chloride, cerium chloride, iron chloride, terbium chloride, copper chloride, copper (II) ammonium chloride, diammonium copper chloride, nickel chloride, neodymium chloride , Platinum chloride, barium chloride, 1,10-phenanthrolinium chloride, praseodymium chloride, berberine chloride, holmium chloride, magnesium chloride, manganese chloride, europium chloride, lanthanum chloride Tan, lithium chloride, lutetium chloride, ruthenium chloride, rhodium chloride, basic aluminum acetate, L-cysteine hydrochloride, cinchonine hydrochloride, piperazine hydrochloride, fadrozole hydrochloride, barium chlorate, zirconium oxychloride, zirconium oxynitrate, oxytetracycline, orthosilicic acid Sodium, orotic acid, cobalt perchlorate, mercury perchlorate, cerium perchlorate, iron perchlorate, sodium perchlorate, lead perchlorate, lithium perchlorate, sodium cacodylate, L-canavanine sulfate, Galactose-6-phosphate phosphate, calcein, zinc formate, copper formate, xanthosine, nickel formate, lithium formate, 8-quinolinol sulfate, guanosine-5'-disodium phosphate, zinc citrate, citric acid, calcium citrate , Three citrate , Trisodium citrate, iron citrate, copper citrate, lead citrate, magnesium citrate, lithium citrate, glycyl-L-tyrosine, disodium β-glycerophosphate, dipotassium D-glucose-6-phosphate , Glucose-1-dipotassium phosphate, D-glucose-6-barium phosphate, calcium gluconate, sodium L-glutamate, creatine, calcium chromate, sodium chromate, magnesium chromate, lithium chromate, chromotropic acid Disodium, sodium chloroaurate, 4-chlorobenzenesulfonic acid, aluminum silicate, magnesium silicate, zinc silicofluoride, calcium silicofluoride, iron silicofluoride, nickel silicofluoride, magnesium silicofluoride, manganese silicofluoride, sodium cholate , Sodium succinate, zinc acetate, ytterbium acetate, yttrium acetate, erbium acetate, cadmium acetate, calcium acetate, chromium acetate, cobalt acetate, samarium acetate, dysprosium acetate, strontium acetate, cerium acetate, thulium acetate, terbium acetate, copper acetate, Sodium acetate, lead acetate, nickel acetate, neodymium acetate, magnesium acetate, manganese acetate, lanthanum acetate, lithium acetate, lutetium acetate, sodium saccharin, calcium salicylate, vanadium oxide sulfate, ruthenium oxide, 3,3′-diaminobenzidine tetrahydrochloride, Sodium hypophosphite, potassium nickel (II) cyanide, 4,4′-diantipyrylmethane, sodium N, N-diethyldithiocarbamate, 2,6-dichloroindophenol Lithium, 2,6-dichlorophenol-indophenol sodium, L-cysteine hydrochloride, L-cysteic acid, sodium dithionate, β-sitostanol, ammonium tetraborate, ammonium tetraborate, sodium tetraborate, 2,9 -Dimethyl-1,10-phenanthroline, cadmium bromide, calcium bromide, chromium bromide, cobalt bromide, strontium bromide, cetylpyridinium bromide, cerium bromide, nickel bromide, barium bromide, magnesium bromide, Manganese bromide, lithium bromide, sodium dichromate, zinc oxalate, aluminum oxalate, ammonium oxalate, erbium oxalate, potassium oxalate, calcium oxalate, cobalt oxalate, dysprosium oxalate, cerium oxalate, oxalate Potassium titanate, Ammonium iron oxalate, iron oxalate, copper oxalate, oxalic acid, nickel oxalate, vanadyl oxalate, barium oxalate, praseodymium oxalate, magnesium oxalate, manganese oxalate, lanthanum oxalate, antimonyl potassium tartrate, tartaric acid Antimonyl (III) potassium, potassium antimony tartrate, potassium antimony tartrate, calcium tartrate, (+)-sodium hydrogen tartrate, copper tartrate, (+)-potassium sodium tartrate, (+)-sodium tartrate, L-(+)-tartaric acid Nicotine, nickel tartrate, zinc nitrate, aluminum nitrate, ytterbium nitrate, yttrium nitrate, indium nitrate, uranyl nitrate, erbium nitrate, cadmium nitrate, gadolinium nitrate, gallium nitrate, calcium nitrate, chromium nitrate, cobalt nitrate Tort, samarium nitrate, mercury nitrate, scandium nitrate, cerium nitrate, thallium nitrate, iron nitrate, copper nitrate, nickel nitrate, neodymium nitrate, bismuth nitrate, praseodymium nitrate, holmium nitrate, magnesium nitrate, manganese nitrate, europium nitrate, lanthanum nitrate, Lutetium nitrate, strontium hydroxide, cesium hydroxide, cerium hydroxide, barium hydroxide, lithium hydroxide, rubidium hydroxide, sodium hydrosulfide, scopolamine hydrobromide, potassium stannate, sodium stannate, sodium sulfanilate, Nickel sulfamate, 5-sulfosalicylic acid, copper selenate, serotonin creatinine sulfate, dibasic sodium phosphate, ammonium tungstate, sodium tungstate, 12-tungstophosphate, ytterbium carbonate , Yttrium carbonate, samarium carbonate, dysprosium carbonate, cerium carbonate, sodium carbonate, manganese carbonate, europium carbonate, lanthanum carbonate, calcium thiocyanate, nickel thiocyanate, magnesium thiocyanate, sodium thiosulfate, thymidine-5′-monophosphate Sodium, sodium deoxycholate, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, sodium tetrachloroaurate (III), tetrachloroaurate (III), sodium dehydroacetate, sodium dehydroacetate, Potassium tellurate, docetaxel, 1,1,1-trichloro-2-methyl-2-propanol, trichloroacetaldehyde, 1,3,5-trihydroxybenzene, toluylene blue, p-toluenesulfone Sodium rhoamide, D (+)-trehalose, hexaammonium heptamolybdate, sodium naphthionate, monosodium 1-naphthyl phosphate, pyridoxamine dihydrochloride, sodium dichromate, ruthenium dioxide, potassium trihydrogen dioxalate, nitrilotriacetic acid Trisodium, disodium p-nitrophenyl phosphate, zinc lactate, calcium lactate, iron lactate, nickel lactate, magnesium lactate, sodium diphosphate, neocuproine, disodium arsenate, magnesium arsenate, bis (dihydrogen phosphate) Calcium, bis [(+)-tartrate] diantimony (III) dipotassium, D-histidine monohydrochloride, L-histidine hydrochloride, hydrazine, hydrazine dihydrobromide, hydrindantin, pipemidic acid, piperazine , Zinc pyrophosphate, pyrroline Copper, sodium pyrophosphate, phenylhydrazine-4-sulfonic acid, 2-phenylphenol sodium, disodium phenyl phosphate, zinc phenolsulfonate, sodium p-phenolsulfonate, potassium ferrocyanide, sodium ferrocyanide, zinc fluoride, Chromium fluoride, copper fluoride, nickel fluoride, flavin adenine dinucleotide disodium, brucine, brucine sulfate, protocatechuic acid, phloroglucin, hexachloroplatinic acid, tetrapotassium hexacyanoferrate (II), potassium hexacyanoferrate (II) , Hexafluoroacetone, hematoxylin, sodium peroxoborate, benzenesulfonic acid, sodium benzenesulfonate, sodium pentacyanonitrosyl iron (III), lead borate, borohydride Manganese, sodium foscarnet, sodium phosphinate, maltose, disodium maleate, sodium metasilicate, 3-methyl-2-benzothiazolinone hydrazone hydrochloride, 5-methyl-1,10-phenanthroline, methylene blue, D (+)-melibiose, ammonium molybdate, sodium molybdate, calcium iodide, cobalt iodide, potassium iodide (II), cerium iodide, nickel iodide, barium iodide, magnesium iodide, lithium iodide , Calcium iodate, rhineke salt, lactose, D-(+)-raffinose, D-(+)-raffinose, α-L-rhamnose, sodium riboflavin phosphate, sodium sulfide, zinc sulfate, adenine sulfate, atropine sulfate, sulfuric acid Armini , Ammonium ferrous sulfate, ammonium iron sulfate, ytterbium sulfate, yttrium sulfate, indium sulfate, gadolinium sulfate, calcium sulfate, quinine sulfate, chromium sulfate, cobalt sulfate, zirconium sulfate, sodium hydrogen sulfate, scandium sulfate, cerium sulfate, ammonium iron sulfate , Iron sulfate, titanium sulfate, copper sulfate, sodium sulfate, diammonium cobalt sulfate, nickel ammonium sulfate, nickel sulfate, neodymium sulfate, vanadyl sulfate, beryllium sulfate, 8-hydroxyquinoline sulfate, praseodymium sulfate, holmium sulfate, magnesium sulfate, sulfuric acid Manganese, tetraammonium cerium sulfate, lithium sulfate, DL-sodium malate, DL-disodium malate, zinc phosphate, monosodium phosphate, chromium phosphate, phosphoric acid Baltic, triammonium phosphate, sodium ammonium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, iron phosphate, copper phosphate, calcium dihydrogen phosphate, sodium dihydrogen phosphate, 5-pyridoxal phosphate, phosphorus Examples include magnesium oxide, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, phosphomolybdic acid, sodium phosphomolybdate, harmaline hydrochloride, gallic acid, etc., but they must not be decomposed even at high temperatures and pressures. Therefore, an inorganic salt that becomes a hydrate is preferable, a sulfate is more preferable, and magnesium sulfate and sodium sulfate are particularly preferable.

  Specific examples of substances that adsorb water include activated carbon, molecular sieves, silica gel, polyvinyl alcohol, starch / polyacrylonitrile hydrolyzate, starch / polyacrylate cross-linked product, cross-linked carboxymethyl cellulose, vinyl acetate / methyl acrylate co-polymer. Among them, activated carbon, molecular sieves, and silica gel are preferable, and molecular sieves are particularly preferable. Molecular sieves are crystalline zeolites and are aluminosilicate crystalline materials.

  Further, when the by-products are an acid and a base, it is preferable to add a solid base and a solid acid, respectively, because a salt is formed by a neutralization reaction and is not easily decomposed.

  The substance that reacts with the by-product can be dispersed in the fluid. However, the substance that reacts with the by-product is separated from the substance that reacts with the by-product and the resin and the resin particles because of ease of separation. It is preferable that the fluid is circulated in a part.

  In addition, a part of by-product remains in the fluid, and the solubility of the monomer, the resin, and the resin particles in the fluid and the change in the phase formation state can be controlled.

  In the present invention, the polycondensation reaction in the fluid is preferably carried out with stirring. By stirring and applying a shearing force, the reaction system can be made uniform. Although it is possible to circulate the reaction system, it is preferable to stir using various dispersers and apply a shearing force. Stirring can be performed using a known method, specifically, a known stirrer; K. A stirrer having a high shearing force such as homomixer (made by Special Machine Industry Co., Ltd.), Claremix (made by M Technique Co., Ltd.), or the like. Can be mentioned. The stirring blade of the stirrer is preferably a turbine type rather than a paddle type. In addition, there may be mentioned a method in which a hard ball such as a steel ball that is stable in a fluid is placed in a pressure vessel in advance, and the pressure vessel is shaken and stirred.

  The reaction is started with the fluid set to a predetermined temperature and pressure and the reaction system made uniform. Specifically, in the esterification reaction, the temperature of the reaction system is usually 60 ° C. or higher and 280 ° C. or lower, preferably 180 ° C. or higher and 250 ° C. or lower, and more preferably 210 ° C. or higher and 245 ° C. or lower. Furthermore, the pressure of the reaction system is usually a pressure at which the fluid is at least one of a supercritical state and a subcritical state, preferably 0.5 MPa or more, and more preferably 7.2 MPa or more. In the amidation reaction, the temperature and pressure in the reaction system are the temperature and pressure at which the fluid becomes at least one of a supercritical state and a subcritical state. Such conditions are preferable because they are highly active environments and promote chemical reactions. Since the decomposition reaction occurs when the resin and the resin particles are placed under high temperature and high pressure for a long time, it is preferable that the time in which the resin and the resin particles exist in the fluid is not decomposed.

  As a reaction method, first, a monomer is charged into a pressure vessel, a fluid containing at least one of a supercritical fluid and a subcritical fluid is placed in the pressure vessel by a pressure pump, and a by-product soluble in the fluid is added to the reaction system. It removes outside and produces | generates resin and a resin particle. Then, the fluid is returned to normal temperature and pressure. At this time, if the fluid is a substance that is a gas at normal temperature and pressure, the fluid is vaporized. The apparatus for removing the by-product can be appropriately selected according to the purpose, and includes a separation tank having a pressure reducing valve for separating the by-product and the fluid, or a tank storing a substance that reacts with the by-product. . When using a separation tank, you may recycle the fluid which pressure-reduced with the pressure reduction valve and isolate | separated from the by-product.

  In addition, after maintaining at least one of the supercritical state and the subcritical state for a predetermined time, it is preferable to quickly lower the temperature of the fluid and open the pressure. In addition, after predetermined time passes, reaction of resin and a resin particle can be stopped by rapidly cooling with a sealed state and returning to normal temperature normal pressure. Examples of the method for rapidly cooling the pressure vessel include air cooling and water cooling.

  In the method for producing resin particles of the present invention, the by-product is water, and the resin particles preferably contain at least one of a polyester resin and a polyether resin. Thereby, the resin particle which is excellent in transparency and can add various functions can be obtained. The by-product is water, and the resin particles preferably contain at least one of a polyamide resin, a polyimide resin, and a polyamideimide resin. Thereby, the resin particle which is excellent in heat resistance and can add various functions can be obtained.

  In the method for producing resin particles of the present invention, the resin particles are preferably further aggregated or fused in an aqueous solvent or fluid. Thereby, the particle diameter of the resin particles can be controlled. If necessary, resin particles different from the resin particles of the present invention may be mixed. Examples of such resin particles include resin particles finely pulverized by a fine pulverizer using a jet stream, a mechanical pulverizer, etc., an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, etc. in an aqueous solvent. Examples thereof include resin particles obtained. Moreover, you may mix multiple types of resin particles of this invention.

  In order to aggregate or fuse the resin particles, an organic solvent, an aggregating agent, or the like can be added. When the resin particles are aggregated or fused, it is preferable to produce resin particles by mixing with a dispersion of additives. Here, aggregation or fusion means that a plurality of resin particles are associated. In addition, when using the substance which is gas at normal temperature and normal pressure as a fluid, a resin particle can also be aggregated by making aggregation energy larger than kinetic energy by pressure reduction and cooling. Moreover, the fluid can be removed by returning to normal temperature and pressure.

  Specific examples of the method using an aqueous solvent include the methods described in JP-A-5-265252, JP-A-6-329947, JP-A-9-15904, and the like. What is stated in these methods is a method of associating a plurality of dispersed particles of constituent materials such as resin particles or particles composed of a resin or the like, in particular, after being dispersed using an emulsifier in an aqueous solvent, At the same time as adding a flocculant above the critical agglomeration concentration and salting out, the particle size is gradually increased while forming the fused particles by heating and fusing above the glass transition temperature of the polymer itself. When the particle size is reached, a large amount of water is added to stop particle size growth, and the shape is controlled by smoothing the particle surface while heating and stirring, and the resulting particles are heated in a fluidized state while still containing water. In this method, resin particles are formed by drying. When adding the flocculant, an organic solvent that is infinitely soluble in water may be added.

  The particle size of the resin particles may be any particle size that is less than or equal to the target non-spherical particle size, but the particle size of commonly used resin particles is preferably 0.01 μm or more and 10 μm or less.

  The flocculant is not particularly limited, but a metal salt is preferable. Specifically, alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium and magnesium, divalent metal salts such as manganese and copper, and trivalent metals such as iron and aluminum Specific examples of the salt include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. In addition, a flocculant can be used individually or in mixture of 2 or more types.

  These flocculants are preferably added in an amount equal to or higher than the critical aggregation concentration. The critical flocculation concentration is an index relating to the stability of the aqueous dispersion, and indicates a concentration at which flocculation occurs when a flocculant is added. This critical coagulation concentration varies greatly depending on the emulsified components and the dispersant. For example, it is described in Seizo Okamura et al., “Polymer Chemistry 17, 601 (1960) edited by Japan Society of Polymer Science”, and the like, and a detailed critical aggregation concentration can be obtained. As another method, a desired salt is added to the target particle dispersion at different concentrations, the ζ (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is the critical aggregation concentration. Can also be sought.

  The addition amount of the flocculant is usually not less than the critical aggregation concentration, but is preferably 1.2 times or more of the critical aggregation concentration, and more preferably 1.5 times or more of the critical aggregation concentration.

  The aqueous solvent used in the present invention is preferably a solvent that does not dissolve the resin particles. Specifically, alcohols such as methanol, ethanol, propanol, isopropanol, t-butanol, methoxyethanol, and butoxyethanol, acetonitrile, and the like And ethers such as nitriles and dioxane. Among these, ethanol, propanol, and isopropanol are preferable.

  In order to make the shape uniform, it is preferable to fluidly dry a slurry in which 10% by weight or more of water is present with respect to the resin particles after preparing, filtering, and washing the resin particles. The resin particles preferably contain a resin having a polar group. The reason for this is that the resin having a polar group swells with water, and the shape is easily uniformed.

  In the association of the resin particles, a normal stirrer, T.I. K. The associated particles are formed by dispersing the resin particles with a stirrer having a high shearing force such as a homomixer (made by Tokushu Kika Kogyo Co., Ltd.) or Claremix (made by M Technique Co., Ltd.). In order to adjust the particle size of the associated particles, it is necessary to control the temperature, pH, stirrer rotation speed, etc. in the system. The granulation time is not particularly limited, but is preferably 5 minutes or more and 1 hour or less.

  In order to uniformly disperse the resin particles, a surfactant or a dispersion stabilizer can be added to the aqueous medium.

  The surfactant is preferably 0.001% by weight or more and 0.1% by weight or less based on the weight of the polymerizable monomer. As the surfactant, an ionic surfactant is preferable, and sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol- Sodium 6-sulfonate, o-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc. Sulfonates: sulfate salts such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate; sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearic acid Helium, and the like fatty acid salts such as calcium oleate. Nonionic surfactants can also be used, such as polyethylene oxide, polypropylene oxide, mixtures of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher Examples include esters of fatty acids and polypropylene oxide, sorbitan esters, and the like.

  As the dispersion stabilizer for the inorganic compound, a metal such as cobalt, iron, nickel, aluminum, copper, tin, lead, magnesium, or an alloy thereof (particularly, the particle diameter is preferably 1 μm or less); Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Inorganic compound fine powders of oxides such as titania, iron oxide, copper oxide, nickel oxide, zinc oxide; pigments such as carbon black, nigrosine dye, aniline blue, chrome yellow, phthalocyanine blue, rose bengal; dyes, etc. Can be mentioned. Examples of dispersion stabilizers for organic compounds include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride; acrylic acid β -Hydroxyethyl, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid, 3-chloro-2-hydroxypropyl , Methacrylic acid, 3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N -Acrylic monomers containing hydroxyl groups such as methylol methacrylamide; vinyl alcohol or ethers with vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, etc. Esters of compounds containing vinyl alcohol and a carboxyl group; acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene Homopolymer or copolymer of a monomer having a nitrogen atom such as imine or a heterocyclic ring thereof; polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, poly Polyoxyethylenes such as xylpropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Celluloses such as methylcellulose and hydroxypropylcellulose; copolymers of the above hydrophilic monomers and monomers having a benzene ring such as styrene, α-methylstyrene and vinyltoluene or derivatives thereof; the above hydrophilic monomers and acrylonitrile, methacrylo; Copolymers of acrylic acid derivatives or methacrylic acid derivatives such as nitrile and acrylamide; the above hydrophilic monomers and ethylene glycol dimethacrylate , Copolymers with crosslinkable monomers such as diethylene glycol methacrylate, allyl methacrylate, divinylbenzene, and the like.

  As the dispersion stabilizer, an acrylic resin having a long-chain fluorine substituent on the side chain can also be used. An acrylic resin having a long-chain fluorine substituent in the side chain can be used as a copolymer such as styrene depending on the solvent type used, temperature and pressure conditions (DeSimon.JM, et.al, Science). , 256, 356 (1994)).

  Furthermore, resin particles can also be used as a dispersion stabilizer. Such resin particles can be appropriately selected from known resin particles capable of forming an aqueous dispersion in an aqueous solvent according to the purpose, and may be thermoplastic resins or thermosetting. Resin may be used. Specifically, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like can be given. These may be used alone or in combination of two or more. The volume average particle diameter of the resin particles is not particularly limited as long as it is a particle diameter that can ensure emulsifiability, but is preferably 1 nm or more and 1 μm or less, and more preferably 10 nm or more and 500 nm or less.

  The resin particles of the present invention are produced by the method for producing resin particles of the present invention.

  When forming resin particles, antioxidants, lubricants, mold release agents, plasticizers, pigments, pigment dispersants, dyes, dyeing assistants, anti-fading agents, foaming agents, foaming nucleating agents, inorganic fillers as necessary In addition, a known additive such as a charge control agent, an antistatic agent, a sliding agent, a pore forming agent, a pharmaceutical composition, an enzyme, a coenzyme, an antibody, a binding protein, a lectin, or a hormone receptor may be contained. Furthermore, the resin particles of the present invention can also be used in combination with known resins such as GP-PS, HI-PS, MS resin, MBS resin, AS resin, ABS resin, PE, PP, and PPO.

  Applications of resin particles include rear projection screens for viewing displays and films, magnetic recording media, liquid crystal display spacers, light diffusing agents for various lighting fixtures, column fillers, diagnostic agents, drug delivery systems, biotechnology Seed particles (monodispersed particles) when producing resin particles used in reactors, etc .; adhesives; alternative materials for metals or ceramics; image forming particles used for electrophotography, electrostatic recording, electrostatic printing, etc. Resin particles used in the above. The resin particles can be used as they are, or, if necessary, mixing with additives to modify the surface, immobilizing additives, adding in the presence of supercritical fluid or subcritical fluid Treatments such as immersion, extraction, and coating of the agent can also be added.

  Further, as a method of adding a known additive or resin to the resin particle, there is a method of kneading the resin particle with a known additive or resin, and a method of kneading the resin particle after mixing the known additive or resin. Preferably, after kneading, a pulverization step, a molding step, a classification step, and the like can be added as necessary.

  Specifically, resin particles and known additives and resins are mixed by a mixer such as a Henschel mixer, and then a batch type two roll, a Banbury mixer, a continuous type twin screw extruder (for example, KTK type twin screw). Extruder (manufactured by Kobe Steel), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), TEX type twin screw extruder (manufactured by Nippon Steel Works), PCM type twin screw extruder (manufactured by Ikegai Iron Works), When the constituent materials are kneaded using a KEX type twin screw extruder (manufactured by Kurimoto Iron Works), a continuous single screw kneader (for example, a thermal kneader such as Ko Kneader (manufactured by Buss)), etc. Depending on the case, the resin particles can be made to contain a known additive or resin by forming into pellets or sheets with various injectors and cooling. If necessary, the resin is coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier using a swirl stream or classification using the Coanda effect It can also be classified to a predetermined particle size by a machine.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
Example 1
10 g of a mixture of terephthalic acid, trimellitic acid, ethylene glycol and bisphenol A ethylene oxide adduct in a molar ratio of 90: 10: 55: 50, 0.075% by weight of dibutyltin oxide based on the total acid components, Structural formula of 1.0% of the total number of moles of the mixture

で示される有機系分散安定剤Ａ（ｍ／ｎ＝１５／８５）を１ｌ耐圧容器内に仕込み、超臨界流体として、二酸化炭素を選択し、２２０℃、２０ＭＰａの条件で耐圧容器内を３時間保持し、エステル化反応を行った。次に、減圧バルブと加圧ポンプを組み合わせた分離槽に超臨界流体を通して、５ＭＰａで分離槽から水を除去しながら、水を除去した二酸化炭素を加圧ポンプで２０ＭＰａまで加圧し、系内に戻す操作を２時間行った。さらに、急冷減圧させて、粒子径が０．８４μｍ、数平均分子量が５６００の変色していない樹脂粒子１を得ることができた。このことから、分解反応を抑制し、環境への負荷を軽減し、効率的に製造することができることがわかる。
（実施例２）
テレフタル酸、トリメリット酸、エチレングリコール及びビスフェノールＡエチレンオキサイド付加物をモル比でそれぞれ９０：１０：５５：５０となるようにした混合物１０ｇ、全酸成分の０．０７５重量％の酸化ジブチルスズ、上記混合物の全モル数の１．０％の有機系分散安定剤Ａ、綿布に包んだ硫酸マグネシウム１００ｇを１ｌ耐圧容器内に仕込み、超臨界流体として、二酸化炭素を選択し、２２０℃、２０ＭＰａの条件で耐圧容器内を５時間保持し、エステル化反応を行った。次に、急冷減圧させて、粒子径が０．９３μｍ、数平均分子量が６２００の変色していない樹脂粒子２を得ることができた。このことから、分解反応を抑制し、環境への負荷を軽減し、効率的に製造することができることがわかる。
（実施例３）
テレフタル酸、トリメリット酸、エチレングリコール及びビスフェノールＡエチレンオキサイド付加物をモル比でそれぞれ９０：１０：５５：５０となるようにした混合物１０ｇ、全酸成分の０．０７５重量％の酸化ジブチルスズ、１，４−ジオキサン０．６ｇ、綿布に包んだ硫酸マグネシウム１００ｇを１ｌ耐圧容器内に仕込み、超臨界流体として、二酸化炭素を選択し、２４０℃、５０ＭＰａの条件で耐圧容器内を５時間保持し、エステル化反応を行った。次に、急冷減圧させて、粒子径が０．８８μｍ、数平均分子量が４２００の変色していない樹脂粒子３を得ることができた。このことから、分解反応を抑制し、環境への負荷を軽減し、効率的に製造することができることがわかる。
（実施例４）
テレフタル酸、トリメリット酸、エチレングリコール及びビスフェノールＡエチレンオキサイド付加物をモル比でそれぞれ９０：１０：５５：５０となるようにした混合物１０ｇ、全酸成分の０．０７５重量％の酸化ジブチルスズ、１，４−ジオキサン０．６ｇ、綿布に包んだ硫酸マグネシウム１００ｇを１ｌ耐圧容器内に仕込み、超臨界流体として、二酸化炭素を選択し、二酸化炭素の重量の０．２５重量％のアンモニアを添加した。２４０℃、５０ＭＰａの条件で耐圧容器内を５時間保持し、エステル化反応を行った。次に、急冷減圧させて、粒子径が０．５６μｍ、数平均分子量が３３００の変色していない樹脂粒子４を得ることができた。このことから、分解反応を抑制し、環境への負荷を軽減し、効率的に製造することができることがわかる。
（比較例１）
実施例１の水を除去する工程を行わないこと以外は、実施例１と同様に操作を行った。しかし、水を除去しなかったため、反応は進行しなかった。
（比較例２）
ペレット状のテレフタル酸、トリメリット酸、エチレングリコール及びビスフェノールＡエチレンオキサイド付加物の共重合体（数平均分子量：７４００）１０ｇを１ｌ耐圧容器内に仕込み、超臨界流体として、二酸化炭素を選択し、２２０℃、２０ＭＰａの条件で耐圧容器を振動させ、１５分後に急冷して常温常圧に戻し、樹脂粒子５を得た。このとき、樹脂粒子５の粒子径は、２．４６μｍで、粒子径分布は、実施例１より広い分布となった。また、数平均分子量は、３０００であった。
（比較例３）
比較例２において、超臨界流体として、メタノールを選択し、４００℃、３０ＭＰａの条件で耐圧容器を振動させた以外は、比較例２と同様の操作を行い、樹脂粒子の懸濁液を得た。この懸濁液からメタノールを分離し、３０℃で減圧乾燥させ、樹脂粒子６を得た。樹脂粒子６の粒子径は、１．３８μｍであった。また、数平均分子量は、２０００で、得られた粒子の色は、茶褐色であった。
（測定方法）
実施例及び比較例で記載されている粒子径及び数平均分子量の測定方法を以下に示す。

An organic dispersion stabilizer A (m / n = 15/85) represented by the formula (1) is charged into a 1 l pressure vessel, carbon dioxide is selected as a supercritical fluid, and the pressure vessel is kept at 220 ° C. and 20 MPa for 3 hours. The esterification reaction was carried out. Next, the supercritical fluid is passed through a separation tank in which a pressure reducing valve and a pressure pump are combined, while removing water from the separation tank at 5 MPa, the carbon dioxide from which water has been removed is pressurized to 20 MPa with a pressure pump. The returning operation was performed for 2 hours. Furthermore, the resin particles 1 having a particle diameter of 0.84 μm and a number average molecular weight of 5600 and having no discoloration could be obtained by rapid cooling and decompression. This shows that the decomposition reaction can be suppressed, the load on the environment can be reduced, and the production can be efficiently performed.
(Example 2)
10 g of a mixture of terephthalic acid, trimellitic acid, ethylene glycol and bisphenol A ethylene oxide adduct in a molar ratio of 90: 10: 55: 50, 0.075% by weight of all acid components, dibutyltin oxide, An organic dispersion stabilizer A of 1.0% of the total number of moles of the mixture, 100 g of magnesium sulfate wrapped in cotton cloth are charged into a 1 l pressure vessel, carbon dioxide is selected as a supercritical fluid, and the conditions are 220 ° C. and 20 MPa. The pressure vessel was held for 5 hours to carry out the esterification reaction. Next, the resin particles 2 having a particle diameter of 0.93 μm and a number average molecular weight of 6200, which is not discolored, can be obtained by rapid cooling and depressurization. This shows that the decomposition reaction can be suppressed, the load on the environment can be reduced, and the production can be efficiently performed.
(Example 3)
10 g of a mixture of terephthalic acid, trimellitic acid, ethylene glycol and bisphenol A ethylene oxide adduct in a molar ratio of 90: 10: 55: 50, 0.075% by weight of dibutyltin oxide of the total acid component, 1 , 4-dioxane 0.6 g, 100 g of magnesium sulfate wrapped in cotton cloth are charged into a 1 l pressure vessel, carbon dioxide is selected as a supercritical fluid, and the pressure vessel is maintained at 240 ° C. and 50 MPa for 5 hours. An esterification reaction was performed. Next, the resin particles 3 having a particle diameter of 0.88 μm and a number average molecular weight of 4200 and having no discoloration were obtained by quenching and reducing the pressure. This shows that the decomposition reaction can be suppressed, the load on the environment can be reduced, and the production can be efficiently performed.
Example 4
10 g of a mixture of terephthalic acid, trimellitic acid, ethylene glycol and bisphenol A ethylene oxide adduct in a molar ratio of 90: 10: 55: 50, 0.075% by weight of dibutyltin oxide of the total acid component, 1 1,4-dioxane 0.6 g and 100 g of magnesium sulfate wrapped in cotton cloth were charged into a 1 l pressure vessel, carbon dioxide was selected as a supercritical fluid, and 0.25 wt% ammonia of carbon dioxide was added. The inside of the pressure resistant container was maintained for 5 hours under the conditions of 240 ° C. and 50 MPa to carry out the esterification reaction. Next, the resin particles 4 having a particle diameter of 0.56 μm and a number average molecular weight of 3300 and having no discoloration were obtained by quenching and depressurizing. This shows that the decomposition reaction can be suppressed, the load on the environment can be reduced, and the production can be efficiently performed.
(Comparative Example 1)
The operation was performed in the same manner as in Example 1 except that the step of removing the water in Example 1 was not performed. However, the reaction did not proceed because water was not removed.
(Comparative Example 2)
10 g of a pellet-shaped copolymer of terephthalic acid, trimellitic acid, ethylene glycol and bisphenol A ethylene oxide adduct (number average molecular weight: 7400) is charged into a 1 l pressure vessel, and carbon dioxide is selected as a supercritical fluid. The pressure vessel was vibrated under the conditions of 220 ° C. and 20 MPa, rapidly cooled after 15 minutes, and returned to room temperature and normal pressure to obtain resin particles 5. At this time, the particle size of the resin particles 5 was 2.46 μm, and the particle size distribution was wider than that of Example 1. The number average molecular weight was 3000.
(Comparative Example 3)
In Comparative Example 2, methanol was selected as the supercritical fluid, and the same operation as in Comparative Example 2 was performed except that the pressure vessel was vibrated under the conditions of 400 ° C. and 30 MPa to obtain a suspension of resin particles. . Methanol was separated from this suspension and dried under reduced pressure at 30 ° C. to obtain resin particles 6. The particle diameter of the resin particles 6 was 1.38 μm. The number average molecular weight was 2000, and the color of the obtained particles was brown.
(Measuring method)
The measuring method of the particle diameter and the number average molecular weight described in Examples and Comparative Examples is shown below.

The particle diameter of the resin particles was measured by a dynamic light scattering method / laser Doppler method using UPA-EX150 (manufactured by Nikkiso Co., Ltd.). For the measurement, fine dust in the water is removed through a filter, and the number of nonionic surfactant Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd.) is counted in 10 ml of water whose number of particles in the measurement range is 20/10 ⁻³ cm ³ or less. Add 5 mg of the sample to be measured, and disperse for 1 minute with an ultrasonic disperser UH-50 (manufactured by STM) at 20 kHz and 50 W / 10 cm ³ , and then disperse for a total of 5 minutes went. The particle size distribution of particles having a circle-equivalent diameter of 0.8 to 6000 nm was measured using a sample dispersion liquid having a particle concentration in the measurement range of 4000 to 8000 pieces / 10 ⁻³ cm ³ . .

  The number average molecular weight of the resin particles was measured using GPC-150C (manufactured by Waters) and columns KF801-807 (manufactured by Shodex). At this time, THF (tetrahydrofuran) was used as a solvent, and measurement was performed at a temperature of 40 ° C. and a flow rate of 1.0 ml / min. As a sample, 0.05 ml to 0.6% by weight of resin particle solution was used and 0.1 ml was injected. Further, when the insoluble content when adding 1 g of resin particles to 100 ml of THF was 75% by weight or more, DMF (dimethylformamide) was used as a solvent. The number average molecular weight was calculated from a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample.

Claims (14)

  A method for producing a resin, comprising producing a resin by advancing a polycondensation reaction by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid.   The method for producing a resin according to claim 1, wherein the by-product is removed from the reaction system by separation.   The method for producing a resin according to claim 1, wherein the by-product is removed from the reaction system by reacting with a substance that reacts with the by-product.   The method for producing a resin according to claim 1, wherein the by-product is removed from the reaction system by adsorbing the by-product to an adsorbing substance.   Production of resin particles characterized by producing a resin particle by advancing a polycondensation reaction by removing a by-product from the reaction system in a fluid containing at least one of a supercritical fluid and a subcritical fluid Method.   The method for producing resin particles according to claim 5, wherein the by-product is removed from the reaction system by separation.   6. The method for producing resin particles according to claim 5, wherein the by-product is removed from the reaction system by reacting with a substance that reacts with the by-product.   6. The method for producing resin particles according to claim 5, wherein the by-product is removed from the reaction system by adsorbing the by-product to a substance to be adsorbed.   The method for producing resin particles according to any one of claims 5 to 8, wherein the fluid contains carbon dioxide.   The method for producing resin particles according to any one of claims 5 to 9, wherein the fluid contains an organic solvent. The by-product is water;
The method for producing resin particles according to any one of claims 5 to 10, wherein the resin particles contain at least one of a polyester resin and a polyether resin. The by-product is water;
The method for producing resin particles according to claim 5, wherein the resin particles contain at least one of a polyamide resin, a polyimide resin, and a polyamideimide resin.   The method for producing resin particles according to any one of claims 5 to 12, wherein the resin particles are further aggregated or fused in an aqueous solvent or the fluid.   Resin particles produced by the method for producing resin particles according to any one of claims 5 to 13.