WO2004058844A1

WO2004058844A1 - Resin particle, resin microcapsule, and methods for producing them

Info

Publication number: WO2004058844A1
Application number: PCT/JP2003/016301
Authority: WO
Inventors: Kukwon Seo; Kijeong Hong
Original assignee: E-Tec Co., Ltd.
Priority date: 2002-12-25
Filing date: 2003-12-19
Publication date: 2004-07-15

Abstract

A method for producing polyaddition resin particles from a monomer (a) and a monomer (b) is characterized by having a first step wherein a solution (A) containing the monomer (a) and a solution (B) containing the monomer (b) are prepared and a second step wherein the solution (A) and the solution (B) are mixed and reacted with each other so that resin particles are precipitated. Polyaddition resin particles produced by such a method are also disclosed.

Description

Specification

Resin fine particles and resin micro force cells, and their manufacturing methods

The present invention relates to resin fine particles and resin microcapsules, and a method for producing them. Background technology

Resin microcapsules containing resin microparticles and functional substances include carbon-free paper, pressure measurement films, recording materials such as photosensitive and heat-sensitive recording materials, pharmaceuticals, spacers, adhesives, separation materials, organic pigments, and toner particles. It is widely used in the fields of industrial materials, such as agricultural materials, display materials, fragrances, cosmetics, and foods.

As a conventional method for producing a resin fine particle and a resin microphone mouth capsule, a method mainly using suspension polymerization, dispersion polymerization or emulsion polymerization is known. However, when the suspension polymerization method is used, since the particle size distribution of the obtained resin fine particles is wide, a complicated classification operation must be performed to make the particle sizes uniform. Furthermore, precise classification is actually difficult. When the dispersion polymerization method is used, the control of the polymerization conditions that does not cause agglomeration between the particles is strict, and it is necessary to precisely cope with the component ratio between chemical parameters during polymerization. In addition, it is difficult to control the average diameter of the resin fine particles formed by dispersion polymerization, and to increase the particle size, the polymerization must be repeated. In order to solve this problem, fine particles having a different particle size from the resin fine particles are added to the reaction system, and the resin fine particles absorb the monomer, and the unabsorbed monomer is absorbed by the fine particles having a different particle size. After the polymerization, a method of removing fine particles having different particle diameters after the polymerization has been proposed (Japanese Patent Application Laid-Open No. Hei 8-1000). However, according to this method, a classification operation for removing fine particles having different particle sizes after polymerization is required. Furthermore, although the emulsion polymerization method produces fine resin particles having a fine average particle size, it was very difficult to completely remove the milking agent from the generated fine particles. An addition condensation method of a monomer and formaldehyde is also used to make the resin fine particles uniform in size.However, the dispersed soot and the resin prepolymer are contacted via a hard porous membrane having a uniform pore diameter. Then, there is a method in which the resin prepolymer liquid is extruded from the hard porous film into the dispersion medium in the form of droplets to be hardened, thereby forming spherical particles (Japanese Patent Application Laid-Open No. H11-11616). No. 49).

However, the above-mentioned method uses a membrane milking apparatus in which porous glass tubes are arranged, emulsifies in the above-described dispersion medium under pressure, and agitates the obtained emulsion to perform a curing reaction. It is a complicated method of completing. Furthermore, since the particle size of the obtained particles depends on the pores of the porous glass tube, fine particles such as submicron and nano-order particles cannot be obtained.

Furthermore, the biggest problem with the above four polymerization methods is the low purity of the fine particles. Since the product always contains a dispersant or an emulsifier, it is not possible to obtain pure resin fine particles while the process is simple. Therefore, it is difficult to use in various cutting-edge fields such as separation materials and electrical and electronic materials that require high purity and high precision. If the resin fine particles and the functional resin fine particles have a high purity and a simpler manufacturing method and can further control the average particle size, the particle size distribution, and the like, it can be applied to various functional materials. Disclosure of the invention

An object of the present invention is to provide a resin fine particle and a resin microcapsule having excellent monodispersibility, and to provide a method for producing a resin fine particle and a resin micro force capsule capable of freely controlling an average particle size and a particle size distribution. It is in.

Other objects and features of the present invention will become apparent from the following description. The present inventors have conducted intensive studies and as a result, have found that the above object can be achieved by a method including a specific step, and have completed the present invention.

That is, the present invention provides a resin fine particle and a resin microcapsule as described below, and a method for producing the same.

1. A method for producing polyaddition resin fine particles from a monomer a and a monomer b, wherein a solution (A) containing a monomer a and a solution (B) containing a monomer b are respectively A first step of preparing; and a second step of mixing and reacting the solution (A) and the solution (B) to precipitate the weight-added resin fine particles. Production method.

2. The monomer according to the above item 1, wherein the monomer a is at least one selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and bisketene. the method of.

3. The method according to the above item 1, wherein the monomer b is at least one selected from the group consisting of a polyol, a polyamine, and a polycarboxylic acid.

4. Solvents in solution (A) and solution (B) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, respectively. Phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic Aliphatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides , Aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic 2. The method according to the above item 1, which is at least one selected from the group consisting of N-oxide, sulfate compound, phosphorus compound, steroid, indole alkaloid, alkyne, oxine, imine, silane, polan, and organometallic. .

5. Resin fine particles having an average particle diameter of 0.01 to 100 m, obtained by the method described in the above item 1.

6. A resin gel having an average particle size of 0.01 to 100 m, obtained by the method described in the above item 1.

7. A method for producing a polyaddition-type resin microphone mouth capsule from a monomer a and a monomer b as a continuous phase and a functional substance as a disperse phase, wherein a solution (A) containing a monomer a and a monomer (I) a first step of preparing a solution (B) containing b and a solution (C) containing a functional substance, respectively, and mixing and reacting the solution (A), the solution (B), and the solution (C); Has a second step of precipitating polyaddition type resin microcapsules A method for producing a polyaddition-type resin microphone mouth capsule, comprising:

8. The monomer according to the above item 7, wherein the monomer a is at least one selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and bisketene. Method.

9. The method according to the above item 7, wherein the monomer is at least one selected from the group consisting of a polyol, a polyamine, and a polycarboxylic acid.

10. The solvents in the solution (A), the solution (B) and the solution (C) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, and fatty acids, respectively. Aliphatic and aromatic ethers, phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds , Aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and Aromatic anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, hetero Item 7. The above item 7 which is at least one selected from the group consisting of cyclic N-oxide, sulfate compounds, phosphorus compounds, steroids, indole alkaloids, alkynes, oxines, imines, silanes, polans, and organometallics. Method.

11. A microresin having an average particle diameter of 0.01 to 100 Hm, obtained by the method described in the above item 7.

12. A functional resin gel having an average particle size of 0.001 to 100 m, obtained by the method described in the above item 7.

13. A method for producing polycondensation-type resin fine particles from monomer d and monomer e, and preparing a solution (D) containing monomer d and a solution (E) containing monomer e, respectively. A method for producing polycondensation type resin fine particles, comprising: a first step; and a second step of mixing and reacting the solution (D) and the solution (E) to precipitate polycondensation type resin fine particles.

1 4. When monomer d is an aliphatic dicarboxylic acid halide or an aromatic dicarboxylic acid halide Item 13. The method according to Item 13, wherein the method is at least one selected from the group consisting of amides and alicyclic dicarboxylic acid octylides.

15. The method according to the above item 13, wherein the monomer e is at least one selected from the group consisting of an aliphatic polyamine, an aromatic polyamine, an aliphatic polyol, and an aromatic polyol.

1 6. Solvents in solution (D) and solution (E) are respectively aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, Phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic aldehydes, Aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides, aliphatic and Aromatic acid octylides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic Item 13. The above item 13 which is at least one selected from the group consisting of N-oxide, a sulfate compound, a phosphorus compound, a steroid, an indole alkaloid, an alkyne, an oxine, an imine, a silane, a polan, and an organosilicate. Method.

17. Resin fine particles having an average particle diameter of 0.001 to 10 O ^ m, obtained by the method described in the above item 13.

18. A resin gel having an average particle diameter of 0.001 to 100 m, obtained by the method described in the above item 13.

19. A method for producing a polycondensed resin microforce cell from a monomer d and a monomer e as a continuous phase and a functional substance as a dispersed phase, comprising: a solution (D) containing the monomer d; A first step of preparing a solution (E) containing the monomer e and a solution (C) containing the functional substance, respectively, and mixing and reacting the solution (D) with the solution (E) and the solution (C) A method for producing polycondensation resin microcapsules, comprising a second step of depositing polycondensation resin microcapsules.

20. The monomer d is at least one selected from the group consisting of aliphatic dicarboxylic acid halides, aromatic dicarboxylic acid halides, and alicyclic dicarboxylic acid halides. Item 19. The method according to Item 19, which is a species.

21. The method according to the above item 19, wherein the monomer e is at least one selected from the group consisting of an aliphatic polyamine, an aromatic polyamine, an aliphatic polyol, and an aromatic polyol.

22. Solvents in solution (C), solution (D) and solution (E) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, and fatty acids, respectively. Aliphatic and aromatic ethers, phenols, acetates, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amamines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso Compounds, aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, fats Aliphatic and aromatic anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, Item 19, which is at least one selected from the group consisting of cyclic N-oxides, sulfate compounds, phosphorus compounds, steroids, indole alkaloids, alkynes, thyminexins, imines, silanes, polans, and organometallics. The method described.

23. Resin microcapsules having an average particle diameter of 0.01 to 100, obtained by the method described in the above item 19.

2 4. A functional resin gel having an average particle diameter of 0.001 to 100, obtained by the method described in the above item 19.

25. A method for producing addition condensation type resin fine particles from a monomer f and formaldehyde, comprising heating a solution (F) containing a monomer; f and formaldehyde in the presence of an alkali catalyst to obtain a monomer f-formaldehyde prevolima. A first step of preparing one solution, and a second step of mixing the solvent (G) and the prepolymer solution, reacting by adding heat and an acid catalyst, and precipitating addition condensation type resin fine particles. For producing addition condensation type resin fine particles.

26. The above item 25, wherein the monomer f is at least one member selected from the group consisting of phenol, urea, melamine, acid amide, and diphenyl ether. Method.

27. The solvent and the solvent (G) in the solution (F) are an aliphatic and an aromatic hydrocarbon, an aliphatic and an aromatic chlorinated carbon, an aliphatic and an aromatic alcohol, an aliphatic and an aromatic, respectively. Ethers, phenols, acetates, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic compounds, aliphatic and aromatic compounds Oral compounds, aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, fatty Aliphatic and aromatic acid anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic Item 25, which is at least one selected from the group consisting of N-oxide, sulfate compound, phosphorus compound, steroid, indole alkaloid, alkyne, oxine, imine, silane, polan, and organometallic. Method.

28. Resin fine particles having an average particle diameter of 0.001 to 100 ^ m obtained by the method described in the above item 25.

29. A resin gel having an average particle size of 0.001 to 100 m, obtained by the method described in the above item 25.

30. A method for producing an addition condensation type resin microcapsule from a monomer f, formaldehyde, and a functional substance, wherein a solution (F) containing the monomer f and formaldehyde is heated in the presence of an alkali catalyst to obtain a monomer f. —The first step of preparing a formaldehyde prepolymer solution, and the solution (C) containing a functional substance and the prepolymer solution are mixed, and heat and an acid catalyst are added to cause a reaction. A method for producing an addition condensation type resin microcapsule, comprising a second step of precipitating a mouth capsule.

31. The method according to the above item 30, wherein the monomer f is at least one selected from the group consisting of phenol, urea, melamine, acid amide, and diphenyl ether.

3 2. Solvents in solution (C) and solution (F) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, respectively. Aliphatic and aromatic ethers, phenols, acetals, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic compounds, aliphatic and aromatic compounds Liposomes, aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, Aliphatic and aromatic anhydrides, aliphatic and aromatic octylides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N-oxides, sulfate compounds, phosphorus compounds , Steroids, indole alkaloids, alkynes, oxines, imines, silanes, polans, and organometa Item 34. The method according to Item 30, wherein the method is at least one selected from the group consisting of rickets.

33. Resin microcapsules having an average particle size of 0.001 to 100 m, obtained by the method described in the above item 30.

3 4. A functional resin gel having an average particle diameter of 0.001 to 1 Oum, obtained by the method described in the above item 30.

35. A method for producing polymer resin fine particles from a polymer resin, comprising a first step of preparing a solution (H) containing a polymer resin, and mixing the solution (H) with the solvent (I) to produce a polymer. A method for producing polymer resin fine particles, comprising a second step of producing resin fine particles.

36. The polymer resin is polygen, polyacetylene, polyalkene, acryl resin, methyl acryl resin, polyvinyl ether, polyvinyl alcohol, polyacetal, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polystyrene, polyphenylene. Ren, polyoxide, polycarbonate, polyester, polyanhydride, polyurethane, polysulfone, polysiloxane, polysulfide, polyamide, polyhydrazine, polyurea, polyurepimide, polyphosphazene, polysilane, polybenzoxazole, polyoxadiazole, polyoxazol Azolidine, polydithiazole, polybenzothiazole, polyimide, polyquinokialine, polybenzoimidazole, polypi Jin, Porichiofen, and methods according to item 35 is a least one is also selected from the group consisting of formaldehyde resins. 3 7. The solvent and the solvent (I) in the solution (H) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, respectively. Phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic aldehydes, Aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides, aliphatic and Aromatic acid octides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N 35. The method according to the above item 35, wherein the method is at least one selected from the group consisting of an oxide, a sulfate compound, a phosphorus compound, a steroid, an indole alkaloid, an alkyne, an oxine, an imine, a silane, a polan, and an organosilicate. .

38. Resin fine particles having an average particle diameter of 0.01 to 100 m, obtained by the method described in the above item 35.

3 9. A resin gel having an average particle size of 0.001 to 100 m, obtained by the method described in the above item 35.

40. A method for producing a polymer resin microcapsule from a polymer resin as a continuous phase and a functional substance as a disperse phase, wherein a solution containing the polymer resin is provided.

(H) and a first step of preparing a solution (C) containing a functional substance, and mixing the solution (H), the solvent (I) and the solution (C) to form a polymer resin microcapsule. A method for producing a polymer resin microphone mouth capsule, comprising a second step of producing the capsule.

4 1. The polymer resin is polygen, polyacetylene, polyalkene, acryl resin, methacrylic resin, polyvinyl ether, polyvinyl alcohol, polyacetal, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polystyrene, polyphenylene, polyoxide. , Polycarbonate, Polyester, Polyanhydride, Polyurethane, Polysulfone, Polysiloxane, Polysulfide, Polyamide, Polyhydrazine, Polyurea, Polyolefin, Polyphosphazene, Polysilane, Polybenzoxazole, Poly Item 4 which is at least one selected from the group consisting of oxadizazole, polyoxadiazolidine, polydithiazole, polybenzothiazole, polyimide, polyquinokialine, polybenzoimidazole, polypirazine, polythiophene, and formaldehyde resin. The method according to 0.

42. The solvent and the solvent (I) in the solution (C) and the solution (H) are, respectively, aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, Aliphatic and aromatic ethers, phenols, acetals, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso Compounds, aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic And aromatic acid anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, Item 40, which is at least one selected from the group consisting of telocyclic N-oxide, sulfate compounds, phosphorus compounds, steroids, indole alkaloids, alkynes, oxines, imines, silanes, polans, and organometallics The described method.

43. Resin microcapsules having an average particle diameter of 0.001 to 100 m, obtained by the method described in the above item 40.

4 4. A functional resin gel obtained by the method described in the above item 40, having an average particle size of 0.01 to 100 im.

Hereinafter, the present invention will be described in detail.

In the following, polyaddition type resin microparticles or polyaddition type resin microcapsules, polycondensation type resin microparticles or polycondensation type resin microcapsules, addition condensation type resin microparticles or addition condensation type resin microcapsules, polymer resin particles Alternatively, each step of the production method will be described separately for polymer-resin microcaps.

1. Polyaddition type resin fine particles or polyaddition type resin micro force

In the present invention, a polyaddition type resin fine particle or resin microcapsule, and a resin gel or a functional resin gel are produced from a mixture of the monomer a, the monomer b, or the functional substance. I do.

[First step]

In the first step, a solution (A) containing monomer a and a solution (B) containing monomer b are separately prepared. When producing resin microcapsules or functional resin gels, a solution (C) containing a functional substance is further prepared individually.

The monomer a contained in the solution (A) is not particularly limited, and may be a known polyaddition type resin, for example, those used in the synthesis of polyurethane, polyurea, polyamide and the like. That is, an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, bisketene, or the like can be used.

First, the aromatic polyisocyanate compound is not particularly limited, and examples thereof include liquid diphenylmethane diisocyanate or a partial prevolimer of diphenylmethane diisocyanate obtained by carpoimide modification, and 2,4-tolylenediene. Isocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-1,4,4'-diisocyanate, xylylenediisocyanate, crude tolylenediisocyanate, polymethylenepolyphenylisocyanate and these And modified carpoimidized, purified, and prepolymerized products.

The aliphatic polyisocyanate compound and the alicyclic polyisocyanate compound are not particularly limited, and include, for example, dicyclohexylmethane 1,4,4′-diisocyanate, isocyanurate-modified product, carpoimidization-modified product, Modified prevolimerized substances can be exemplified.

As the polyisocyanate compound, commercially available compounds can be used. For example, Millionet MLT (manufactured by Nippon Polyurethane Industry Co., Ltd.), Millionet MTL-S (Nippon Polyurethane Industry Co., Ltd.) And Coronate MX (manufactured by Nippon Polyurethane Industry Co., Ltd.).

The solvent used in the solution (A) is such that the monomer a is substantially dissolved and the solvent is used in the second step. There is no particular limitation as long as the resulting polyaddition resin does not completely dissolve. For example, aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, phenols, acetal, epoxides, aliphatic and aromatic mercaptans, Aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and Aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides , Aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N-oxides, sulfate compounds, phosphorus compounds, Roy de, indole alkaloids, alkynes, Okishin, Imin, silane, Pollan and Organometallic and the like, can be used at least one of these.

The concentration of the monomer a in the solution (A) may be appropriately set according to the type of the monomer and the solvent to be used, the concentration of the solution (B), and the like. Degree, preferably about 0.01 to 0.5 mol Z liter. The monomer b used in the solution (B) is not particularly limited, and a monomer used for synthesizing a known polyaddition resin can be used. That is, polyols, polyamines, polycarboxylic acids, and the like can be used.

Polyols are classified into ether-based, ester-based, and the like, and may be appropriately selected depending on the application.

Examples of ether-based polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and low-molecular-weight polyhydric alcohols such as pentaerythritol. Polyhydric alcohols such as polyoxypropylene polyols obtained by adding one or more of oxoxide, butylene oxide, styrene oxide and the like, and the above polyhydric alcohols to which tetrahydrofuran is added by ring-opening polymerization. And polyoxytetramethylene polyols obtained by the above method. Examples of the ester polyols include low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, and pentaerythryl I-yl. One or more of the above, and low-molecular dicarboxylic acids such as daltaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, hydrogenated dimer acid, or oligomeric acid And polyols such as ring-opening polymers of ring-opening esters such as propiolactone, thioprolactone and valerolactone.

In the acrylic copolymer, 3-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, iS-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, iS-hydroxybutyl acrylate —Hydroxypentyl and other hydroxyalkyl esters of acrylic acid or similar hydroxyalkyl esters of methacrylic acid; and acrylic acid monoesters of polyhydric alcohols such as glycerin and trimethyl monopropane or methacrylic acid similar thereto An acrylyl polyol having two or more hydroxyl groups in one molecule using a monoethylenically unsaturated monomer having a hydroxyl group such as a monoester, N-methylolacrylamide or N-methylolmethacrylamide as a copolymerization monomer can be used. Other polyols include phenolic resin polyols, epoxy polyols, polybutadiene polyols, polyisoprene polyols, polyester-polyether polyols, polymer-polyols obtained by adding or dispersing polymers such as acrylonitrile and styrene to vinyl polyols, urea-dispersed polyols, Forceponate polyols and the like can also be used for the desired product physical properties.

As a polyol compound other than those described above, copolymers of these, for example, a block copolymer of polyoxytetramethylene glycol (PTMG) and force prolactone can also be used. In addition, not only a bifunctional polyol but also a polyfunctional polyol compound can be used in combination. The above polyols may be used alone or in combination of two or more.

Examples of polyamines include those in which an amino group is bonded to at least one of an aliphatic carbon atom, an alicyclic carbon atom, an aromatic aliphatic carbon atom, and an aromatic carbon atom. I can do it. It can also be divided into low molecular weight polyamines and high molecular weight polyamines.

Preferred low molecular weight polyamines include, for example, ethylenediamine, 1,2- or 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3- or 1, 4,1-butanediamine., 1,3- or 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexandiamine, 2, 2,4-di- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1, 11-decanediamine, 1,12-dodecanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 2,4- or 2,6-hexahydrotoluylenediamine 2,4,1 or 4,4, diaminodicyclohexylmethane, 3,3'dialkyl-1,4,4'diamino-dicyclohexylmethane (for example, 3,3,1dimethyl-4,4, -diamino-1 dicyclo Hexylmethane and 3,3,1-ethyl-4,4'-diamino-dicyclohexylmethane), 1,3- or 1,4-cyclohexanediamine, 1,3-bis (methylamino) -cyclohexane, 1,8 — P-Methanediamine, hydrazine, hydrazide of semicarbazidecarboxylic acid, bis-hydrazide, bis-semicarbazide, phenylenediamine, 2,4- or 2,6-toluylenediamine, 2,3- or 3,4-tol ^ / Polyfunctional polyphenylene obtained by the condensation reaction of diylenediamine, 2,4,1 or 4,4,1-diaminodiphenylmethane, aniline Z-formaldehyde Nylenepolymethylenepolyamine, N, N, N-tris- (2-aminoethyl) amine, guanidine, melamine, N- (2-aminoethyl) 1-1,3-propanediamine, 3,3'-diamino Examples include benzidine, polyoxypropyleneamine, polyoxyethylenamine, 2,4-bis- (4, -aminobenzyl) -aniline, and mixtures thereof. Among them, 1-amino-1-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine), bis-1 (4-aminocyclohexyl) monomethane, bis-1 (4-amino-3-methylcyclohexyl) Lulu)) 11-metatantan, 11, 66

And ethylene and ethylenediamine. .

The preferred high and high molecular weight molecular weight of popolilia ammine is not particularly limited. For example, for example, Bivisus ((44-Aminomibenobenzozoateto)) ,, Popoririechirenrenguringurikokorurubibibis ((22-—va55 Miminonobenbenzozoate)) ,, Popoririechirenrenguringurikokorurubibisusu .. ((33-—amimininobenbenzozoateto)), Poporilitetetrarametichirenrenguringurikoarurubibisu ((44——amimininobeben)ゾ,）,）, ポリ, ポ, ポ, ポ, ポ, ポ, ポ, ポ, ポ, ポ, ポ, ポ)),, Poporilipopropipirirendaridariko Coco 11 rubibibis ((44 ーァミノミノミノト) 22—— amimininobenbenzozoetoto)),, popolili ((oxokisshiechitirenren) —— oxokissipproropipireren)

1100 Bivisus ((44-Family-Mino-No-Benzo-Zo-E-T-R)), Poporily ((Oxy-X-Echi-M-I-No-H-B-N-Z-O-E-T-R-H)一トポポポポポリポリポリルルルルポリル（ルルルルルポリポリルル（（ルル（（（（（ポリ（ルルルル（ルル（ル（ Lulubibiss ((33,, 55——Djiamimininobenbenzozoeato)), Poporilipropropropypyrenrenate atetellurugugliriserororurutotoririsus ((44-amiamiminonobenbenzozoate)) ,, Popolilipopropirile Yeah Lilith scan Ririto toe over Lulu Tete Toto Lara

1155 Kissus ((44-amimininobenbenzozoateto)), Poporiliooxysitiichirenrenbibisu ((44-amimininobenbenzusamiamidodo)) ,, popoliriooxysipropropirirenbibis ((44-amimininobenbenzuzuamimidodo)) ,, popoliriooxyshibutuchirenrenguringurikokorurubibissu ((44-amiamiminonobenbenzuzuamitototo)) ,, popo This can be achieved by listing Lirio-Oxycipipropipyirelen Bibis (33, 55-amimininobenbenzuzuamimidodo) and the like. . At least a few of these can be used and used. .

2200 In addition, in order to use the above-mentioned popolyria ammin, there is a product that can be used and sold on the market. For example, for example, Eerarassumama 11 11 00 00 00 ((equivalent equivalent of about 66 2200, manufactured by Ihaharara Kekimikamikaru Co., Ltd.)), eerarassumama 11 00 00 00 PP ((equivalent amount of about 55 55 00, manufactured by Ihaharara Kemi Mikakarl Co., Ltd.)) and the like can be obtained. .

Furthermore, in the present invention, the purpose of the present invention is to change the characteristic characteristics of the weight-addition-addition-type resin resin fine particles produced and formed. In addition to the Gami 2255 amimin compound, a momononoamin compound, a polyvalent amamine compound, and the like can also be used together. And can be completed. . According to these, it is possible to change the characteristic characteristics of the obtained weight-addition-addition-type resin resin fine particle particles obtained by the method described above. .

The solvent medium used in the solution solution ((BB)) is such that the momonomamer bb is practically substantially dissolved and dissolved, and In particular, if the weight-addition addition-type resin resin fine particles produced by biogenesis do not completely and completely dissolve and dissolve, the restriction is particularly limited. Don't be That is, at least one selected from the group consisting of the same solvents as those used for the solution (A) can be used.

The concentration of the monomer b in the solution (B) may be appropriately set according to the type of the monomer and the solvent to be used, the concentration of the solution (A), and the like, but is usually 0.01 to 1 mol liter. Degree, preferably about 0.01 to 0.5 mol Z liter.

On the other hand, functional substances are used to produce polyaddition type resin microcapsules. The functional substance contained in the solution (C) is not particularly limited, and the life of known functional substances, for example, industrial functional substances such as dyes, pigments, toners, liquid crystals, fragrances, antibacterial agents, deodorants, etc. Functional substances, genes, bio- or medical functional substances such as insulin, etc., and at least one of them can be used.

The solvent used in the solution (C) is not particularly limited as long as the functional substance is substantially dissolved or dispersed and the polyaddition resin microcapsules generated in the second step are not dissolved. That is, at least one selected from the group consisting of the same solvents as those used in the solution (A) can be used.

The concentration of the functional substance in the solution (C) may be appropriately set according to the type of the substance to be used, the type of the solvent, etc., but is usually about 0.01 to 1 mol Z liter, preferably 0 It is about 0.1 to 0.5 mol / l.

[Second step]

In the second step, the solution (A) containing the monomer a and the solution (B) containing the monomer b are mixed and reacted to precipitate polyaddition-type resin fine particles. In addition, in order to produce a polyaddition-type resin microcapsule capsule, a solution (C) containing a functional substance may be mixed with a solution containing a monomer and reacted.

The mixing ratio of the solution (A) and the solution (B) may be appropriately set depending on the type and concentration of both monomers, or the type and concentration of each solution, but usually a monomer a: a monomer b = l : About 0.5 to 1.5 (molar ratio), preferably about 1: 0.9 to 1.1 (molar ratio).

The mixing ratio of the functional substance in the production of the polyaddition type resin microcapsules is usually 0.01 to 10 times, preferably 0.1 to 5 times the total weight of the used monomers. What is necessary is just to mix so that it may become.

As a mixing method in the second step, constant dropping or jetting is preferable, and the particle size can be reduced also depending on the addition speed of each solution and the nozzle diameter.

Further, fine resin particles can be miniaturized by a normal stirring method using a homogenizer or the like. Known stirrers and operating conditions can be employed as they are. The stirring speed may be appropriately set according to the desired particle size and the like, and is usually about 100 to 20,000 rpm, preferably about 500 to 10,000 rpm.

Further, when the stirring is performed by the ultrasonic wave, it is possible to achieve finer particles having a higher degree of monodispersion than the ordinary stirring method. For the stirring by the ultrasonic wave, a known ultrasonic device such as a washing machine and operating conditions can be employed as they are. The frequency of the ultrasonic wave may be appropriately set according to the desired particle size, the concentration of the mixture, and the like. Usually, the frequency is set to about 20 to about 00 kHz, preferably about 23 to 68 kHz.

The reaction temperature in the second step is not particularly limited, and is usually about -20 to 180 ° C, preferably about 0 ° C to 150 ° C, and more preferably about 20 ° C to 100 ° C. good. The reaction time may be set so that the precipitation of the polyaddition resin fine particles or the resin microcapsules is substantially completed, and is usually about 1 to 24 hours, but may be outside this range.

When the monomer b is a poorly reactive polyol or polycarboxylic acid, any of the catalysts commonly used in the reaction can be used. For example, amine catalysts include triethylamine, tripropylamine, tributylamine, N, N, N ', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, and dimethylcycloamine. Organometallic catalysts such as hexylamine, bis [2- (dimethylamino) ethyl] ether, triethylenediamine and triethylendiamine salts, include tin acetate, tin octoate, tin oleate, tin laurate, Examples include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate and cobalt naphthenate.

These catalysts can be arbitrarily mixed and used, and the amount of use is 0.0001 to 10.0 parts by weight based on 100 parts by weight of the monomer component. Also, catalyst May be added after mixing the solution (A) and the solution (B), and the time of addition is not particularly limited.

The polyaddition resin fine particles or the resin microphone opening capsules generated in the second step may be separated and dried by a known method such as centrifugation and collected. The polyaddition resin fine particles or resin microcapsules obtained in the second step generally have an average particle diameter of 0.001 to L0 m (preferably 0.05 to 50 urn). Therefore, it is an excellent monodisperse material.

Further, the reaction solution obtained in the second step is not limited to the one having a dispersed phase of fine particles, and may be a gel. Depending on the purpose of use, it may be used in powder or gel form.

2. Polycondensation resin particles or polycondensation resin micro force

In the present invention, polycondensation type resin fine particles or resin microcapsules, and a resin gel or a functional resin gel are produced from a mixture of the monomer d, the monomer e, or the functional substance.

[First step]

In the first step, a solution (D) containing the monomer d and a solution (E) containing the monomer e are separately prepared. When producing resin microcapsules or functional resin gels, a solution (C) containing a functional substance is further prepared individually.

The monomer d contained in the solution (D) is not particularly limited, and known polycondensation type resins, for example, those used in the synthesis of polyamide, polyester and the like can be used. That is, aliphatic dicarponic acid halides, aromatic dicarponic acid halides, and alicyclic dicarponic acid halides can be used. These dicarboxylic acid halides are not particularly limited, and include aliphatic dicarbonic acid halides such as aziboyl chloride, azelaoyl chloride, sebacyl chloride, isophthaloyl chloride, terephthalic acid ilucide, and aromatic rings thereof. Aromatic dicarboxylic acid halides in which one or more hydrogens have been substituted with a halogen, a nitro group or an alkyl group. These dicarponic acid halides may be used alone or in combination of two or more.

The monomer e contained in the solution (E) is not particularly limited, and may be a known polycondensation type resin. Fats, for example, those used in the synthesis of polyamide, polyester and the like can be used. That is, aliphatic polyamines, aromatic polyamines, aliphatic polyols, aromatic polyols and the like can be used. The monomer e used may be the same as the polyamine and the polyol used as the monomer b.

The solvent used in the solutions (D) and (E) is not particularly limited as long as the monomers d and e are substantially dissolved and the polycondensation type resin fine particles generated in the second step are not completely dissolved. . That is, at least one selected from the group consisting of the same solvents as those used for the solution (A) can be used.

The concentrations of the monomers d and e in the solutions (D) and (E) may be appropriately set according to the type of the monomer and the solvent to be used, but are usually about 0.01 to 1 mol liter, It is preferably about 0.01 to 0.5 mol Z liter.

On the other hand, functional materials are used to produce polycondensation-type resin microcapsules. The functional substance contained in the solution (C) is not particularly limited, and the life of known functional substances, for example, industrial functional substances such as dyes, pigments, toners, liquid crystals, fragrances, antibacterial agents, deodorants, etc. Functional substances, genes, bio- or medical functional substances such as insulin, etc., and at least one of them can be used.

The solvent used in the solution (C) is not particularly limited as long as the functional substance is substantially dissolved or dispersed, and the polycondensation type resin microcapsules generated in the second step are not completely dissolved. That is, at least one selected from the group consisting of the same solvents as those used for the solution (A) can be used.

The concentration of the functional substance in the solution (C) may be appropriately set according to the type of the substance to be used, the type of the solvent, and the like, but is usually about 0.01 to 1 mol Z liter, preferably 0 It is about 0.1 to 0.5 mol / l.

[Second step]

In the second step, the solution (D) containing the monomer d and the solution (E) containing the monomer e are mixed and reacted to precipitate polycondensation-type resin fine particles. In addition, in order to produce a polycondensation type resin microcapsule capsule, the solution (C) containing the functional substance may be mixed with the solution containing the monomer and reacted.

The mixing ratio between solution (D) and solution (E) depends on the type and concentration of both monomers, and May be appropriately set depending on the type and concentration of each solution, but usually, monomer d: monomer e = l: about 0.5 to 1.5 (molar ratio), preferably 1: 0.9 to 1. What is necessary is just to mix so that it may become about 1 (molar ratio).

In addition, the mixing ratio of the functional substance in the production of the polycondensed resin microphone mouth capsule is usually 0.01 to 10 times, preferably 0.1 to 5 times the total weight of the monomers used. good.

Further, fine resin particles can be miniaturized by a normal stirring method using a homogenizer or the like. Known stirrers and operating conditions can be employed as they are. The stirring speed may be appropriately set depending on the desired particle size and the like, and is usually about 100 to 20,000 rpm, preferably about 500 to 10,000 rpm.

Further, when the stirring is performed by the ultrasonic wave, it is possible to achieve finer particles having a higher degree of monodispersion than the ordinary stirring method. For the stirring by the ultrasonic wave, a known ultrasonic device such as a washing machine and operating conditions can be employed as they are. The frequency of the ultrasonic wave may be appropriately set according to the desired particle size, the concentration of the mixture, and the like, and is usually 20 to: about 00 kHz, preferably about 23 to 68 kHz.

The reaction temperature in the second step is not particularly limited and is usually about −20 ° C. to 250 ° C., preferably about 0 ° C. to 200, more preferably about 20 ° C. to 150 ° C. Good. The reaction time may be set so that the precipitation of polycondensation type resin fine particles or resin microcapsules is substantially completed, and is usually about 4 to 24 hours, but may be outside this range.

The polycondensation type resin microparticles or resin microcapsules generated in the second step may be separated and dried by a known method such as centrifugation and collected. The polycondensation-type resin fine particles or resin microcapsules obtained in the second step generally have an average particle size of 0.01 to 100 m (preferably 0.05 to 50 xm), and have an excellent monodispersed belongs to.

Further, the reaction solution obtained in the second step is not limited to the one having a dispersed phase of fine particles, and may be a gel. Depending on the purpose of use, it may be used in powder or gel form. 3. Addition condensation type resin fine particles or addition condensation type resin microphone mouth capsule

In the present invention, an addition-condensation type resin fine particle or a resin microphone opening capsule, and a resin gel or a functional resin gel are produced from a mixture of a monomer; f, formaldehyde, or a functional substance.

[First step]

In the first step, after preparing a solution (F) containing the monomer: f and formaldehyde, the solution (F) is heated in the presence of an alkali catalyst to prepare a monomer f-formaldehyde polymer solution.

The monomer f contained in the solution (F) is not particularly limited, and may be a known addition condensation type resin, for example, those used in the synthesis of a phenol resin, a urea resin, a melamine resin, an acid amide resin, a diphenyl ether resin, and the like. Can be used. That is, phenol, urea, melamine, acid amide, diphenyl ether and the like can be used. Formaldehyde is usually used as formalin. Formalin is the _{Weight, CH 2 0 = 37~37 5%} , CH 3 〇_H = 6~:.. L 5% , HCOOH = 0. 02~0 1%, the remainder is a composition of H ₂ 0 . Methanol is used to prevent highly polymerized formaldehyde.

The concentration of the monomer f and formaldehyde in the solution (F) may be appropriately set according to the monomer used, but is usually about 0.01 to 5.0 mol liter, preferably 0.1 to 2.0 mol. It is on the order of liters.

Heat and an alkali catalyst are added to the solution (F) prepared as described above to obtain a low molecular weight prepolymer polymer solution (primary resin). The alkali catalyst is not particularly limited, and those used in the synthesis of known addition condensation type resins, for example, phenol resin, urea resin, melamine resin, acid amide resin, diphenyl ether resin and the like can be used. Here, sodium hydroxide is desirable. There are no particular restrictions on the amount of catalyst added, but it is only necessary that the pH of the solution be in the alkaline range.

The reaction temperature in the first step is not particularly limited as long as the monomer f and the water of formalin do not undergo phase separation. Usually, it should be about 30 ° C to 100 ° C, preferably about 50 to 80 ° C.

[Second step] In the second step, a dispersion solution is prepared by mixing a solvent (G) or a solution containing a functional substance (C) that can control the aggregation of the generated particles with the prepolymer solution obtained in the first step . Heat and an acid catalyst are further added thereto to cure and condense, thereby precipitating addition-condensation-type fine resin particles or resin microcapsules having excellent monodispersibility.

The solvent (G) is not particularly limited as long as it can prevent aggregation of precipitated particles and can control the size of generated fine particles. That is, at least one selected from the group consisting of the same solvents as those used in the solution (A) can be used.

The acid catalyst is not particularly limited, and known addition condensation type resins, for example, those used in the synthesis of phenol resin, urea resin, melamine resin, acid amide resin, diphenyl ether resin and the like can be used. The addition of a small amount of acid catalyst will double the speed of the condensation reaction compared to the addition reaction, so if the acidity is stronger, this ratio will be even greater.Here, weak acids such as citric acid and acetic acid are used. Is desirable.

Further, fine resin particles can be miniaturized by a normal stirring method using a homogenizer or the like. Known stirrers and operating conditions can be employed as they are. The stirring speed may be appropriately set according to the desired particle size and the like, and is usually about 100 to 200,000 rpm, preferably about 500 to 100,000 rpm. It is good.

Further, when the stirring is performed by the ultrasonic wave, it is possible to achieve finer particles having a higher degree of monodispersion than the ordinary stirring method. For the stirring by the ultrasonic wave, a known ultrasonic device such as a washing machine and operating conditions can be employed as they are. The frequency of the ultrasonic wave may be appropriately set according to the desired particle size, the concentration of the mixture, etc., and is usually about 20 to 100 kHz, preferably 23 to 68 kHz. It should be about z. ^One

The reaction temperature in the second step is not particularly limited, and may be any temperature that is equal to or higher than the temperature at which the primary resin becomes hardened and subsequently becomes insoluble after condensation with an acid catalyst. Usually, it should be about 30 ° C. to 100 ° C., preferably about 50 ° C. to 80 ° C.

On the other hand, functional substances are used to manufacture addition condensation type resin microcapsules. It is. The functional substance contained in the solution (C) is not particularly limited, and is a known functional substance, for example, an industrial functional substance such as a dye, a pigment, a toner, and a liquid crystal, a fragrance, an antibacterial agent, a deodorant, etc. Functional substances, genes, bio or medical functional substances such as insulin and the like can be mentioned, and at least one of them can be used.

The solvent used in the solution (C) is not particularly limited as long as the functional substance is substantially dissolved or dispersed and the addition condensation type resin microcapsules generated in the second step are not completely dissolved. That is, at least one selected from the group consisting of the same solvents as those used in the solution (A) can be used. The concentration of the functional substance in the solution (C) may be appropriately set according to the type of the substance to be used, the type of the solvent, and the like, but is usually about 0.01 to 1 mol Z liter, preferably 0 0.1 to 0.5 mol Z liters.

In addition, the mixing ratio of the functional substance in the production of the addition condensation type resin microphone mouth capsule is usually 0.1 to 10 times, preferably 0.1 to 5 times the total weight of the monomers used. Just do it.

The addition condensation type resin microparticles or resin micro force cells generated in the second step may be separated and dried by a known method such as centrifugation and collected. The addition condensation type resin fine particles or resin microcapsules obtained in the second step generally have an average particle size of 0.001 to 100 m (preferably 0.05 to 50 m), Excellent monodisperse form.

4. Polymer resin fine particles or polymer resin micro force

In the present invention, a polymer resin fine particles or resin microcapsules, and a resin gel or a functional resin gel are produced by mixing a solution (H) containing a polymer resin h and a solvent (I) to precipitate fine particles. I do.

[First step]

As a first step, a solution (H) containing the polymer resin h is prepared. In the case of producing a resin microcapsule or a functional resin gel, separately prepare a solution (C) containing a functional substance. The polymer resin h contained in the solution (H) is not particularly limited, and known polymer resins such as polygen, polyacetylene, polyalkene, acrylic resin, methacrylic resin, polyvinyl ether, polyvinyl alcohol, polyacetal, polypinyl ketone, polyvinyl halide, Polyvinyl nitrile, Polyvinyl ester, Polystyrene, Polyphenylene, Polyoxide, Polycarbonate, Polyester, Polyanhydride, Polyurethane, Polysulfone, Polysiloxane, Polysulfide, Polyamide, Polyhydrazine, Polyurea, Polyphenolimide, Polyphosphazene, Polysilane , Polybenzoxazole, polyoxadiazole, polyoxadiazolidine, polydithiazole, polybenzothiazole, polyimid , It can be used Porikinokiarin, Poribe Nzoimidazoru, Poripi Bae Rajin, Porichiofen, a formaldehyde resin.

The solvent used in the solution (H) is not particularly limited as long as the polymer resin h is substantially dissolved. That is, at least one selected from the group consisting of the same solvents as those used for the solution (A) can be used.

The concentration of the polymer resin h in the solution (H) may be appropriately set depending on the type of the polymer resin used, the molecular weight, and the like, but is usually about 0.01 to 30% by weight, preferably 1.0. It is about 0 to 20% by weight.

On the other hand, functional materials are used to produce polymer resin microcapsules. The functional substance contained in the solution (C) is not particularly limited, and the life of known functional substances, for example, industrial functional substances such as dyes, pigments, toners, liquid crystals, fragrances, antibacterial agents, deodorants, etc. Functional substances, genes, bio- or medical functional substances such as insulin, etc., and at least one of them can be used.

The solvent used in the solution (C) is not particularly limited as long as the functional substance is substantially dissolved or dispersed, and the polymer resin microcapsules generated in the second step are not completely dissolved. That is, at least one selected from the group consisting of the same solvents as those used for the solution (A) can be used.

The concentration of the functional substance in the solution (C) may be appropriately set according to the type of the substance to be used, the type of the solvent, and the like, but is usually about 0.01 to 1 mol Z liter, preferably 0 0.1 to 0.5 mol Z liters. [Second step]

In the second step, the solution (H) containing the polymer resin h and the solvent (I) are mixed to precipitate polymer resin fine particles. Further, in order to produce the polymer-resin microcapsules, the solution (C) containing the functional substance, the solution (H) and the solvent (I) may be mixed.

The solvent (I) has substantially an affinity for the solvent used in the solution (H), does not dissolve the polymer resin h, and controls the aggregation of polymer-resin fine particles precipitated in the second step. It is not particularly limited as long as it is a product. That is, at least one selected from the group consisting of the same solvents as those used in the solution (A) can be used.

The mixing ratio between the solution (H) and the solvent (I) may be appropriately set depending on the type and concentration of the polymer resin h, but is usually about 1: 1 to: L00 (weight ratio), preferably 1: 1. : About 5 to 20 (weight ratio) should be mixed.

In addition, the mixing ratio of the functional substance in the production of the polymer resin microphone mouth capsule is usually 0.01 to 10 times, preferably 0.1 to 5 times the weight of the used polymer resin.

As the mixing method in the second step, constant dropping or jetting is preferable, and the particle diameter can be reduced by the addition speed of each solution and the nozzle diameter.

Further, fine resin particles can be miniaturized by a normal stirring method using a homogenizer or the like. Known stirrers and operating conditions can be employed as they are. The stirring speed may be appropriately set according to the desired particle size and the like, and is usually about 100 to 20,000 rPm, preferably about 500 to 10, OOOrpm.

Further, when the stirring is performed by the ultrasonic wave, it is possible to achieve finer particles having a higher degree of monodispersion than the ordinary stirring method. For the stirring by the ultrasonic wave, a known ultrasonic device such as a washing machine and operating conditions can be employed as they are. The frequency of the ultrasonic wave may be appropriately set according to the desired particle size, the concentration of the mixture, and the like, and is usually about 20 to 100 kHz, preferably about 23 to 68 kHz.

The reaction temperature in the second step is not particularly limited and is usually about -20: to about 180 ° C, preferably about 0 to 150 ° C, more preferably about 20 t: to about 100 ° C. Just do it. The reaction time may be set so that the precipitation of the polymer-resin fine particles or the resin microcapsules is substantially completed, and is usually about 2 to 24 hours, but may be outside this range.

The polymer-resin microparticles or the resin microforce formed in the second step may be separated and dried by a known method such as centrifugation and collected. The polymer resin fine particles or resin microcapsules obtained in the second step generally have an average particle size of 0.001 to 100 ° (preferably 0.05 to 50 °), and have excellent properties. Monodisperse.

In addition, the reaction solution obtained in the second step is not limited to the dispersion phase of fine particles, but may be a gel. Depending on the purpose of use, it may be used in powder or gel form. The resin fine particles or resin microcapsules obtained according to the present invention can be widely used for various applications in addition to conventional applications. For example, industrial parts such as various coating materials, lining materials, hammers, gears, packings, dust covers, sports shoe soles, watch bands, Cass Yuichi, hoses, tubes, belt conveyors, wire cables, etc. Paints, coatings, rubber: Modifiers for resins, resin paints dissolved in solvents, resin paints, materials for synthetic leather, adhesives, coloring agents when colored, powder inks (toners), etc. Also useful for filter materials, chromatographic materials, various spacer materials, various fillers, film additives, composite material additives, polymer varnish additives, cosmetic materials, electric and electronic materials, medical materials, etc. is there.

According to the present invention, spherical resin fine particles or resin microcapsules having excellent monodispersibility can be produced. The average particle size and the particle size distribution can be freely controlled by appropriately changing the production conditions. Furthermore, since there is no need for any impurities (eg, emulsifier, dispersant, etc.) in the manufacturing process, there is an advantage that very high-purity resin fine particles and resin microcapsules can be obtained. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an electron micrograph of the polyurethane fine particles obtained in Example 1. FIG. 2 shows the electron of the white pigment-containing polyurea microphone opening capsule obtained in Example 2. It is a micrograph.

FIG. 3 is an electron micrograph of the polyamide fine particles obtained in Example 3. FIG. 4 is an electron micrograph of the white pigment-containing polyamide microphone opening capsule obtained in Example 4.

FIG. 5 is an electron micrograph of the urea resin fine particles obtained in Example 5.

FIG. 6 is an electron micrograph of the white pigment-containing urea resin microphone opening capsule obtained in Example 6.

FIG. 7 is an electron micrograph of the polymethyl methacrylate fine particles obtained in Example 7.

FIG. 8 is an electron micrograph of the white pigment-containing polymethyl methacrylate microphone capsule obtained in Example 8. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

[Manufacture of polyaddition type resin microparticles and polyaddition type resin micro force plate]

Example 1

Diphenylmethane 1,4'-diisocyanate containing 0.005mol (diethyl ether: hexane = 2: 1) 100ml (solution A) and 2,6-hexahydrotoluylenediamine (methanol: Trahydrofuran = 1: 1) 100 ml (solution B) were prepared respectively. Next, the solution (A) and the solution (B) were mixed at 20 ° C., and reacted by stirring with ultrasonic waves of 23 kHz for 3 hours to produce polyurea fine particles. Thereafter, the product was recovered by centrifugation while washing with the reaction solvent. The obtained cake-like polyurea fine particles were dried under reduced pressure to obtain powdery polyurea fine particles. The number average particle diameter of the obtained polyurea fine particles was 0.05 m. Fig. 1 shows an electron micrograph of the obtained polyurea fine particles.

Example 2

10 ml of methanol containing 0.002 g of a commercially available titanium oxide-based white pigment (solution C) was added thereto, and a white pigment-containing polyurea microphone opening capsule was obtained in the same manner as in Example 1 except that the reaction was carried out by stirring with a homogenizer for 3 hours at 3,000 rpm. The number average particle diameter of the obtained polyurea microphone mouth capsule was 0.5 zm. FIG. 2 shows an electron micrograph of the obtained white pigment-containing polyester micromic mouth capsule.

[Manufacture of polycondensation type resin fine particles and polycondensation type resin microphone opening capsule]

Example 3

Contains 0.003 mol of adipoyl chloride (p-chlorophenol: dioxan = 1: 1) 100 ml (solution D) and 2,4-bis- (4, aminobenzyl) -aniline 0.003 mol 1 (Dioxane: methanol = 1: 2) and 100 ml (solution E), respectively. Next, the solution (D) and the solution (E) were mixed at 20 and reacted with stirring with a homogenizer for 6 hours at 3, OO Orpm for 6 hours to produce polyamide fine particles. Thereafter, the product was recovered by centrifugation while washing with the reaction solvent. The obtained cake-like polyamide fine particles were dried under reduced pressure to obtain powdery polyamide fine particles. The number average particle diameter of the obtained polyamide fine particles was 0.7 m. Fig. 3 shows an electron micrograph of the obtained polyamide fine particles.

Example 4

Example 3 was repeated except that a solution (C) obtained by dispersing 0.002 g of a commercially available titanium oxide-based white pigment in 1 Om1 of methanol was added, and the mixture was stirred and reacted with ultrasonic waves of 23 kHz for 3 hours. Similarly, a polyamide mic opening capsule containing a white pigment was obtained. The number average particle diameter of the obtained polyamide microcapsules was 1. FIG. 4 shows an electron micrograph of the obtained white pigment-containing polyamide microforce capsule.

[Manufacture of addition condensation type resin fine particles and addition condensation type resin microphone opening capsule] Example 5

Contains 0.055 urea and 1 Oml of 37% formaldehyde (water: methanol = 7: 3) (Solution F) After preparing 10 Oml, adjust the solution (F) to pH 9 with sodium carbonate, and add 65 ° C To prepare a urea-formaldehyde prevolimer solution. Then, (ethanol: acetone = 3: 1) 5 Oml of solvent (G) Then, 10 ml of a urea-formaldehyde prepolymer solution was added to the mixture, and the mixture was stirred with a 23 kHz ultrasonic wave for 1 hour to prepare a dispersion solution. Further, citric acid was added, and the mixture was cured and condensed at 70 ° C to produce thermosetting urea resin fine particles. Thereafter, the product was recovered by centrifugation while washing with the reaction solvent. The obtained cake-like thermosetting urea resin fine particles were dried under reduced pressure to obtain powdery urea resin fine particles. The number average particle diameter of the obtained thermosetting urea resin fine particles was 0.25 m. FIG. 5 shows an electron micrograph of the obtained urea resin fine particles.

Example 6

A white pigment was prepared in the same manner as in Example 5, except that 10 ml of ethanol (solution C) containing 0.002 g of a commercially available titanium oxide-based white pigment was synthesized by adding the solvent (G) and 10 ml of a urea-formaldehyde prevolimer solution. A thermosetting urea resin microcap capsule was obtained. The number average particle size of the obtained urea resin microphone mouth capsule was 0.38 m. FIG. 6 shows an electron micrograph of the obtained white pigment-containing urea resin microcapsules.

[Manufacture of polymer resin fine particles and polymer resin micro force plate]

Example 7

10 ml of 2% by weight (methyl ethyl ketone: tetrahydrofuran = 3: 1) containing polymethyl methacrylate resin (solution H) and 10 ml of solvent (I) (trifluoroethanol: cyclohexane = 1: 1) Was mixed with a homogenizer for 3 hours with stirring at 3,000 rpm to produce polymethyl methacrylate fine particles. Thereafter, the product was recovered by centrifugation while washing with the reaction solvent. The obtained cake-like polymethyl methacrylate fine particles were dried under reduced pressure to obtain powdery polymethyl methacrylate fine particles. The number average particle diameter of the obtained polymethyl methacrylate fine particles was 0.15 m. An electron micrograph of the obtained polymethyl methacrylate fine particles is shown in FIG.

Example 8

A white pigment-containing white pigment was prepared in the same manner as in Example 7 except that a solution (C) of a commercially available titanium oxide-based white pigment 0.000 lg dispersed in 10 ml of (tetrahydrofuran: trifluoroethanol = 1: 1) was added and reacted. Polymethylmethacrylate micro force I got Puser. The number average particle size of the obtained polymethyl methacrylate microphone mouth capsule was 0.38 m. FIG. 8 shows an electron micrograph of the obtained white pigment-containing polymethyl methacrylate microcapsules.

Claims

The scope of the claims

1. A method for producing polyaddition resin fine particles from a monomer a and a monomer b, wherein a first step of preparing a solution (A) containing the monomer a and a solution (B) containing the monomer b, And a second step of mixing and reacting the solution (A) and the solution (B) to precipitate the weight-added resin fine particles, the method comprising the steps of:

2. The monomer according to claim 1, wherein the monomer (a) is at least one selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and bisketene. Method.

3. The method according to claim 1, wherein the monomer b is at least one selected from the group consisting of a polyol, a polyamine, and a polycarboxylic acid.

4. Solvents in solution (A) and solution (B) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic solvents, respectively. Ter, phenol, acetal, epoxide, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic nitroso compounds Aromatic aldehydes, aliphatic and aromatic ketones, 7j, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic acids Anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N 2. The method according to claim 1, wherein the method is at least one selected from the group consisting of oxides, sulfate compounds, phosphorus compounds, steroids, indole alkaloids, alkynes, oxines, imines, silanes, polans, and organometallics.

5. The average particle diameter obtained by the method according to claim 1 is from 0.001 to 100. m resin particles.

6. A resin gel obtained by the method according to claim 1 and having an average particle size of 0.01 to 100 mm.

7. A method for producing a polyaddition-type resin microcapsule from a monomer a and a monomer b as a continuous phase and a functional substance as a disperse phase, wherein a solution (A) containing the monomer a and a monomer b are prepared. The first step of preparing the solution (B) containing the functional substance and the solution (C) containing the functional substance, respectively, and mixing and reacting the solution (A), the solution (B) and the solution (C), A method for producing a polyaddition-type resin microcapsule, comprising a second step of depositing the addition-type resin microcapsule.

8. The monomer according to claim 7, wherein the monomer a is at least one selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and bisketene. The described method.

9. The method according to claim 7, wherein the monomer b is at least one selected from the group consisting of a polyol, a polyamine, and a polycarboxylic acid.

10. Solvents in solution (A), solution (B) and solution (C) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, and fatty acids, respectively. Aliphatic and aromatic ethers, phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amamines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, fatty Aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, 7, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic Acid anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, Click Ν- Okishido, sulfuric acid compounds, phosphorus compounds, steroids, India one 8. The method according to claim 7, wherein the method is at least one selected from the group consisting of alkaloids, alkynes, oxines, imines, silanes, porans, and organomelics.

11. A resin microforce cell obtained by the method of claim 7, having an average particle size of 0.001 to 100 am.

12. A functional resin gel obtained by the method according to claim 7, having an average particle size of 0.001 to 100 m.

13. A method for producing polycondensation resin fine particles from monomer d and monomer e, comprising a first step of preparing a solution (D) containing monomer d and a solution (E) containing monomer e, respectively. And a second step of mixing and reacting the solution (D) and the solution (E) to precipitate polycondensed resin fine particles, the method comprising the steps of:

14. The method according to claim 13, wherein the monomer d is at least one selected from the group consisting of an aliphatic dicarboxylic acid halide, an aromatic dicarboxylic acid halide, and an alicyclic dicarboxylic acid halide.

15. The method according to claim 13, wherein the monomer e is at least one selected from the group consisting of an aliphatic polyamine, an aromatic polyamine, an aliphatic polyol, and an aromatic polyol.

16. Solvents in solution (D) and solution (E) are respectively aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, Phenols, acetals, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic Aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides Products, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N-oxides, sulfate compounds, phosphorus compounds, steroids, indole alkaloids 14. The method according to claim 13, wherein the method is at least one selected from the group consisting of de, alkyne, oxine, imine, silane, polan, and organometallic.

17. Resin fine particles having an average particle diameter of 0.01 to 100 m, obtained by the method according to claim 13.

18. A resin gel having an average particle size of 0.01 to 100 m, obtained by the method according to claim 13.

1 9. A method for producing polycondensation-type resin microcapsules from monomer d and monomer e as a continuous phase and a functional substance as a dispersed phase, wherein a solution (D) containing monomer d and a monomer e A first step of preparing a solution (E) containing a functional substance and a solution (C) containing a functional substance, respectively, and mixing and reacting the solution (D), the solution (E) and the solution (C), A method for producing polycondensation-type resin microcapsules, comprising a second step of depositing condensation-type resin microcapsules.

20. The method according to claim 19, wherein the monomer d is at least one selected from the group consisting of an aliphatic dicarboxylic acid halide, an aromatic dicarboxylic acid halide, and an alicyclic dicarboxylic acid halide.

21. The method according to claim 19, wherein the monomer e is at least one selected from the group consisting of an aliphatic polyamine, an aromatic polyamine, an aliphatic polyol, and an aromatic polyol.

2 2. Solvents in solution (C), solution (D) and solution (E) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, and fatty acids, respectively. Aliphatic and aromatic ethers, phenols, acetals, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds , Aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and Aromatic anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, The method according to claim 19, wherein the method is at least one selected from the group consisting of click N-oxide, sulfate compound, phosphorus compound, steroid, indole alkaloid, alkyne, oxine, imine, silane, polan, and organometallic. .

23. Resin microcapsules obtained by the method according to claim 19 and having an average particle size of 0.01 to 100 m.

2 4. A functional resin gel obtained by the method according to claim 19 and having an average particle size of 0.01 to 100 m.

2 5. A method for producing addition condensation type resin fine particles from a monomer f and formaldehyde, wherein a solution (F) containing a monomer f and formaldehyde is heated in the presence of an alkali catalyst to obtain a monomer f-formaldehyde blepolymer. A first step of preparing a solution, and a second step of mixing the solvent (G) and the prepolymer solution, reacting by adding heat and an acid catalyst, and precipitating addition condensation type resin fine particles. The method for producing addition condensation type resin fine particles described above.

26. The method according to claim 25, wherein the monomer f is at least one selected from the group consisting of phenol, urea, melamine, acid amide, and diphenyl ether. Law.

27. The solvent and the solvent (G) in the solution (F) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic, respectively. (Aliphatic ethers, phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, fats) «And aromatic aldehydes, aliphatic and aromatic ketones, 7j, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic Aliphatic anhydrides, aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic N Okishido, sulfuric compounds, phosphorus compounds, steroids, indole alk Roy de, alkynes, Okishin, Imin, silane, Pollan, and method of claim 2 5 is at least one selected from the organo-metallic or Ranaru group.

28. Resin fine particles having an average particle diameter of 0.01 to 100 m, obtained by the method according to claim 25.

2 9. A resin gel having an average particle diameter of 0.001 to 100 m, obtained by the method according to claim 25.

30. A method for producing an addition-condensation resin microcapsule from monomer f, formaldehyde, and a functional substance, comprising heating a solution (F) containing monomer f and formaldehyde in the presence of an alkali catalyst. f—The first step of preparing a formaldehyde prepolymer solution, and mixing the solution (C) containing a functional substance with the prepolymer solution, and reacting by adding heat and an acid catalyst to the addition condensation type resin micro A method for producing an addition-condensation-type resin microphone capsule, comprising a second step of depositing a capsule.

31. The method according to claim 30, wherein the monomer f is at least one selected from the group consisting of phenol, urea, melamine, acid amide, and diphenyl ether.

3 2. Solvents in solution (C) and solution (F) are aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers, respectively. , Phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic compounds, aliphatic and aromatic compounds , Aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic And aromatic acid anhydrides, aliphatic and aromatic acid octylides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclics 30. The method according to claim 30, wherein the compound is at least one selected from the group consisting of N-oxide, sulfate compound, phosphorus compound, steroid, indole alkaloid, alkyne, oxine, imine, silane, polan, and organometallic. Method.

3 3. A resin microcapsule obtained by the method according to claim 30 and having an average particle size of 0.001 to L00m.

3 4. A functional resin gel obtained by the method according to claim 30 and having an average particle size of 0.001 to 100 m.

3 5. A method for producing polymer resin fine particles from a polymer resin, comprising: a first step of preparing a solution (H) containing the polymer resin; and mixing the solution (H) and the solvent (I) to form a polymer. A method for producing polymer resin fine particles, comprising a second step of producing one resin fine particle.

3 6. The polymer resin is polygen, polyacetylene, polyalkene, acrylic Resin, methacrylic resin, polyvinyl ether, polyvinyl alcohol, polyacetal, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polystyrene, polyphenylene, polyoxide, polycarbonate, polyester, polyanhydride, polyurethane, polysulfone , Polysiloxane, polysulfide, polyamide, polyhydrazine, polyurea, polyphenol, polyphosphazene, polysilane, polybenzoxazole, polyoxaziazol, polyoxadiazolidine, polydithiazol, polybenzothiazole, polyimide, polyquinoxyline Selected from the group consisting of benzoimidazole, polypyrazine, polythiophene, and formaldehyde resin The method of claim 35 which is a kind also crying.

3 7. The solvent and the solvent (I) in the solution (H) are, respectively, aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, aliphatic and aromatic ethers. , Phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitroso compounds, aliphatic and aromatic Aromatic aldehydes, aliphatic and aromatic ketones, 7, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic anhydrides , Aliphatic and aromatic acid halides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, heterocyclic 36. The method according to claim 35, wherein the method is at least one selected from the group consisting of -oxide, sulfate compound, phosphorus compound, steroid, indole alkaloid, alkyne, oxine, imine, silane, polan, and organometallic. .

38. Resin fine particles obtained by the method according to claim 35 and having an average particle size of 0.001 to 100 m.

39. A resin gel obtained by the method according to claim 35 and having an average particle size of 0.01 to 1'00 m.

40. A method for producing a polymer-resin microcapsule from a polymer resin as a continuous phase and a functional material as a dispersed phase, comprising a solution (H) containing a polymer resin and a solution (H) containing a functional material ( C) and a second step of mixing the solution (H), the solvent (I) and the solution (C) to produce a polymer resin microcapsule. Manufacturing method of polymer resin microphone mouth capsule.

4 1. The polymer resin is polygen, polyacetylene, polyalkene, acrylic resin, methyl acryl resin, polyvinyl ether, polyvinyl alcohol, polyacetal, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polystyrene, polyphenylene, Polyoxide, Polycarbonate, Polyester, Polyanhydride, Polyurethane, Polysulfone, Polysiloxane, Polysulfide, Polyamide, Polyhydrazine, Polyurea, Polyolefin, Polyphosphimide, Polyphosphazene, Polysilane, Polybenzoxazole, Polyoxazizol, Polyoxaziazo Lysine, polydithiazole, polybenzothiazole, polyimide, polyquinokialine, polybenzoimidazole, polypi Jin, Porichiofen, and method of claim 4 0 is least one is also selected from the group consisting of formaldehyde resins.

42. The solvent and the solvent (I) in the solution (C) and the solution (H) are, respectively, aliphatic and aromatic hydrocarbons, aliphatic and aromatic chlorinated hydrocarbons, aliphatic and aromatic alcohols, and aliphatic alcohols. And aromatic ethers, phenols, acetal, epoxides, aliphatic and aromatic mercaptans, aliphatic and aromatic sulfides, aliphatic and aromatic amines, aliphatic and aromatic nitro compounds, aliphatic and aromatic nitrosated compounds, Aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, water, aliphatic and aromatic carboxylic acids, aliphatic and aromatic amino acids, aliphatic and aromatic esters, aliphatic and aromatic lactones, aliphatic and aromatic Aliphatic anhydrides, aliphatic and aromatic acid octides, aliphatic and aromatic amides, aliphatic and aromatic nitriles, heterocyclic compounds, 40. At least one selected from the group consisting of heterocyclic N-oxides, sulfate compounds, phosphorus compounds, steroids, indole alkaloids, alkynes, oxines, imines, silanes, polans, and organomelics. The method described in. 3. A resin microcapsule obtained by the method according to claim 40 and having an average particle size of 0.001 to 100.

4 4. A functional resin gel obtained by the method according to claim 40, having an average particle size of 0.001 to 100 m.