JP5375053B2 - Epoxy resin cured fine particles, dispersion thereof, and production method - Google Patents

Abstract

The invention discloses an epoxy resin micro-particle. The micro-particle is prepared by curing epoxy resin under the function of a curing agent, and has an average grain size of between 50 and 400nm.The invention also discloses a dispersion liquid for the epoxy resin micro-particle consisting of the epoxy resin micro-particle, a surfactant, the curing agent and water. The invention also discloses a method for preparing the dispersion liquid for the epoxy resin micro-particle. The method uses polyethenoxy ether and a derivative thereof as the surfactant for the epoxy resin; since the surfactant has a more appropriate HLB value (a hydrophobicity-hydrophilicity balance value), through the interaction between the surfactant and the epoxy resin micro-particle, the prepared aqueous dispersionliquid has long-term dispersion stability and can be widely applied in the fields such as coatings, adhesives and fine chemical additives. The epoxy resin micro-particle prepared by the method has small granularity and narrow particle size distribution.

Description

  The present invention relates to fine particles of cured epoxy resin, a dispersion thereof, and a production method, and more particularly to fine particles of cured epoxy resin having a fine particle size and good dispersibility, a dispersion thereof and a production method thereof.

  The resin fine particles are fine particles made of a polymer material or a polymer composite material having a spherical shape or a shape close to a spherical shape, and the diameter thereof is from the nano level to the micron level. In recent years, resin fine particles have been applied to advanced technology fields such as medical applications and electronic information materials by changing the specific surface area, adjusting the particle size distribution, and modifying the surface according to their special dimensions and shapes. Has been. The required performance required for such resin fine particles includes heat resistance and solvent resistance, and as a form in which resin fine particles can be easily used, a dispersion of fine particles having these functions is required.

  On the other hand, epoxy resins have excellent properties such as high adhesion, high hardness after curing, wear resistance, and chemical resistance, and are widely used in the industrial field. Conventionally, fine particles made of a cured epoxy resin have been developed taking advantage of the characteristics of the epoxy resin, such as high hardness after curing, heat resistance and chemical resistance (see, for example, Patent Documents 1 and 2). However, these epoxy resin cured fine particles are all micron level (μm order) particles, that is, only particles having a particle diameter of 0.5 μm or more are obtained, and nano level fine particles can be obtained. I couldn't.

In recent years, especially in the movement of higher precision and fine pitch of electronic information materials, there has been a demand for further reduction in particle size of these materials, and development of unprecedented fine resin particles has been required. Yes. These fine particles are not only handled as powders, but in some cases, it is preferable to disperse them in a dispersion medium and apply them, so that the resin fine particles are also well dispersed in the dispersion medium. The development of dispersions has been strongly desired. However, since the dispersion of resin fine particles tends to agglomerate as the particle size becomes smaller, the dispersion of resin fine particles is difficult to disperse uniformly in the dispersion medium and is particularly stable for a long period of time. It was difficult to get.
JP-A-4-249536 JP 59-170114 A

  An object of this invention is to provide the epoxy resin hardened | cured material fine particle which has a fine particle diameter and favorable dispersibility, its dispersion liquid, and a manufacturing method.

The epoxy resin cured product fine particles of the present invention that achieve the above object are:
(1) Fine particles of cured epoxy resin obtained by curing an epoxy resin and a curing agent, the average particle diameter of which is 50 to 400 nm, and the curing agent is piperazine, hydrazine, hexanedioic acid dihydrazide, diethylenetriamine, triethylene tetramine, 4,4'-diaminodicyclohexylmethane, a, cured epoxy resin particles, characterized in that at least one element selected from the group consisting of diamino diphenyl sulfone and diaminodiphenylmethane.

The dispersion of the epoxy resin cured product fine particles of the present invention that achieves the above object is as follows.
(2) (1) Symbol placement of cured epoxy resin particles, a surfactant and a dispersion of cured epoxy resin particles are dispersed in a dispersion medium,
( 3 ) The dispersion of fine particles of cured epoxy resin according to ( 2 ), wherein the surfactant is polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether or a derivative thereof,
( 4 ) A dispersion of fine particles of cured epoxy resin according to ( 2 ) or ( 3 ), wherein the surfactant is polyoxyethylene alkylphenyl ether.

The method for producing a dispersion of cured epoxy resin particles of the present invention is as follows.
( 5 ) Mix the epoxy resin and surfactant, mix by heating and stirring, then change the stirring speed, stir and mix with deionized water to produce an epoxy resin emulsion, this epoxy resin ( 2 ) The method for producing a dispersion of fine particles of cured epoxy resin according to ( 3 ) or ( 4 ), wherein a curing reaction is carried out by adding a curing agent to the emulsion,
( 6 ) The method for producing a cured epoxy resin particle dispersion according to ( 5 ), wherein 2 to 100 parts by weight of the surfactant is blended with 100 parts by weight of the epoxy resin.
( 7 ) The method for producing a dispersion of fine particles of cured epoxy resin according to ( 5 ) or ( 6 ), wherein the temperature of the curing reaction is 35 to 50 ° C.
( 8 ) The stirring speed when mixing the epoxy resin and the surfactant is 300 to 350 rpm, the stirring speed when adding deionized water to the obtained mixture is 400 to 700 rpm, and performing a curing reaction ( 5 ) The manufacturing method of the epoxy resin hardened material fine particle dispersion according to ( 6 ) or ( 7 ), wherein the stirring speed is 300 to 350 rpm.

In addition, the method for producing fine particles of cured epoxy resin of the present invention includes
( 9 ) The cured epoxy resin particles are separated from the dispersion of cured epoxy resin particles obtained by the production method according to any one of ( 5 ) to ( 8 ) above (1 ) the method of manufacturing the serial mounting of the epoxy resin cured product fine particles is.

  The epoxy resin cured product fine particles of the present invention have heat resistance and solvent resistance because the epoxy resin and the curing agent are cured and the average particle size of the cured product is 50 to 400 nm. In addition, the dispersion of fine particles of cured epoxy resin of the present invention is highly dispersed in a dispersion medium such as an organic solvent because the above-described cured epoxy resin particles and surfactant are dispersed in a dispersion medium. it can. For this reason, it can be applied to fine pitch electronic / electrical members, paints, fine chemicals, resin modifiers, etc., which could not be applied in the prior art.

  The epoxy resin in the present invention is a thermosetting resin having an epoxy group in the molecule. As the epoxy resin, for example, a glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group in the molecule and epichlorohydrin, a glycidylamine type epoxy resin obtained from a compound having an amino group in the molecule and epichlorohydrin, A glycidyl ester type epoxy resin obtained from a compound having a carboxyl group in the molecule and epichlorohydrin, an alicyclic epoxy resin obtained by oxidizing a compound having a double bond in the molecule, or 2 selected from these An epoxy resin or the like in which more than one type of group is mixed in the molecule is used.

  Specific examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin obtained by reaction of bisphenol A and epichlorohydrin, bisphenol F type epoxy resin obtained by reaction of bisphenol F and epichlorohydrin, resorcinol and epi Resorcinol type epoxy resin obtained by reaction of chlorohydrin, phenol novolac type epoxy resin obtained by reaction of phenol and epichlorohydrin, other polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin, naphthalene type epoxy resin, and these These are the positional isomers of these groups, and substituted groups with alkyl groups or halogens.

  Commercially available bisphenol A type epoxy resins include “EPON” (registered trademark) 825, “jER” (registered trademark) 826, “jER” (registered trademark) 827, “jER” (registered trademark) 828 (above, Japan). Epoxy Resin Co., Ltd.), “Epicron” (registered trademark) 850 (Dainippon Ink Chemical Co., Ltd.), “Epototo” (registered trademark) YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332 (Dow) "Bakelite" (registered trademark) EPR154, "Bakelite" (registered trademark) EPR162, "Bakelite" (registered trademark) EPR172, "Bakelite" (registered trademark) EPR173, and "Bakelite" (registered trademark) EPR174 (Above, manufactured by Bakerite AG).

  Commercially available products of bisphenol F type epoxy resins include “jER” (registered trademark) 806, “jER” (registered trademark) 807, “jER” (registered trademark) 1750 (above, manufactured by Japan Epoxy Resin Co., Ltd.), “Epiclon” (Registered trademark) 830 (manufactured by Dainippon Ink & Chemicals, Inc.), “Epototo” (registered trademark) YD-170, “Epototo” (registered trademark) YD-175 (manufactured by Toto Kasei), “Bakelite” (registered trademark) EPR169 (manufactured by Bakerite AG), GY281, GY282, and GY285 (manufactured by Huntsman Advanced Material) are listed.

  Examples of commercially available resorcinol type epoxy resins include “Denacol” (registered trademark) EX-201 (manufactured by Nagase ChemteX Corporation).

  Commercial products of phenol novolac type epoxy resins include “jER” (registered trademark) 152, “jER” (registered trademark) 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and “Epicron” (registered trademark) 740 (Dainippon Ink). Chemical Industry Co., Ltd.), and EPN 179, EPN 180 (manufactured by Huntsman Advanced Materials), and the like.

  Specific examples of the glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethanes, glycidyl compounds of aminophenol, glycidylanilines, and glycidyl compounds of xylenediamine.

  Commercially available tetraglycidyldiaminodiphenylmethanes include “Sumiepoxy” (registered trademark) ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite” (registered trademark) MY720, “Araldite” (registered trademark) MY721, and “Araldite” (registered trademark). ) MY9512, “Araldite” (registered trademark) MY9612, “Araldite” (registered trademark) MY9634, “Araldite” (registered trademark) MY9663 (manufactured by Huntsman Advanced Materials), “jER” (registered trademark) 604 (Japan) Epoxy Resin Co., Ltd.), “Bakelite” (registered trademark) EPR494, “Bakelite” (registered trademark) EPR495, “Bakelite” (registered trademark) EPR496, and “Bakelite” (registered trademark) EPR497 , Made of Bakelite AG Corporation), and the like.

  Commercially available glycidyl compounds of aminophenol include “jER” (registered trademark) 630 (manufactured by Japan Epoxy Resin Co., Ltd.), “Araldite” (registered trademark) MY0500, “Araldite” (registered trademark) MY0510 (above Huntsman Advanced) -“Sumiepoxy” (registered trademark) ELM120, “Sumiepoxy” (registered trademark) ELM100 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of commercially available glycidyl anilines include GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.) and “Bakelite” (registered trademark) EPR493 (manufactured by Bakelite AG).

  Examples of the glycidyl compound of xylenediamine include TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).

  Specific examples of the glycidyl ester type epoxy resin include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, dimer acid diglycidyl ester and various isomers thereof.

  Examples of commercially available products of diglycidyl phthalate include “Epomic” (registered trademark) R508 (manufactured by Mitsui Chemicals) and “Denacol” (registered trademark) EX-721 (manufactured by Nagase ChemteX).

  Examples of commercially available hexahydrophthalic acid diglycidyl ester include “Epomic” R540 (manufactured by Mitsui Chemicals) and AK-601 (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of commercially available dimer acid diglycidyl ester include “jER” (registered trademark) 871 (manufactured by Japan Epoxy Resin Co., Ltd.) and “Epototo” (registered trademark) YD-171 (manufactured by Toto Kasei Co., Ltd.).

  Commercially available alicyclic epoxy resins include “Celoxide” (registered trademark) 2021P (manufactured by Daicel Chemical Industries), CY179 (manufactured by Huntsman Advanced Materials), “Celoxide” (registered trademark) 2081 (Daicel Chemical Industries). And “Celoxide” (registered trademark) 3000 (manufactured by Daicel Chemical Industries, Ltd.).

Usually, examples of the curing agent include aromatic amines, aliphatic amines, polyamide amines, carboxylic acid anhydrides and Lewis acid complexes, acid-based curing catalysts, and base-based curing catalysts. Specific examples of the aromatic amine include diaminodiphenyl sulfone and diaminodiphenylmethane. Specific examples of aliphatic amines include piperazine, hydrazine, hexane diacid dihydrazide, 4,4'-diaminodicyclohexylmethane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, piperidine, N, N -Dimethylpiperazine, triethylenediamine, polyamidoamine, octylamine, laurylamine, myristylamine, stearylamine, cocoalkylamine, beef tallow alkylamine, oleylamine, cured beef tallow alkylamine, N, N-dimethyllaurylamine, N, N-dimethyl Examples include myristylamine.

The curing agent in the present invention is at least one selected from the group consisting of piperazine, hydrazine, hexanedioic acid dihydrazide, diethylenetriamine, triethylenetetramine, 4,4'-diaminodicyclohexylmethane, diaminodiphenylsulfone and diaminodiphenylmethane. Preferred are piperazine and hydrazine.

  In addition, these curing agents can be used in combination with an appropriate curing aid in order to increase the curing activity. Preferred examples of the case where a curing aid is combined with an epoxy resin include an example of combining dicyandiamide with a urea derivative such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU) as a curing aid, Examples include a combination of a group 3 amine and a boron trifluoride ethylamine complex as a curing aid, and a combination of a carboxylic acid anhydride or a novolak resin with a tertiary amine as a curing aid.

  The fine particles of cured epoxy resin referred to in the present invention are fine particles of a cured epoxy resin obtained by reacting the epoxy resin and the curing agent, and have an average particle size of 50 to 400 nm, preferably 100 to 350 nm. It is. If the particle diameter of the cured epoxy resin particles is less than 50 nm, it is difficult to produce efficiently. Moreover, when the particle diameter of hardened | cured epoxy resin fine particle exceeds 400 nm, when it makes it a dispersion liquid, there exists a tendency for precipitation to arise easily. In the present invention, the average particle diameter of the cured epoxy resin particles is the volume average particle diameter measured with a laser diffraction / light scattering particle size distribution meter.

  The cured epoxy resin fine particles of the present invention may have any shape such as a true sphere, an oval sphere, a flat shape, a rock shape, a confetti shape, and an amorphous shape. In addition, the average particle diameter of the fine particles described above is set to a corresponding spherical average particle diameter when the shape of the fine particles is other than a spherical shape.

  The dispersion of fine particles of cured epoxy resin refers to a dispersion in which the cured fine particles of epoxy resin are dispersed in a dispersion medium. The solvent as the dispersion medium is composed of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ester solvent, a halogenated hydrocarbon solvent, a ketone solvent, an alcohol solvent, a polar solvent, an ether solvent and water. It may be at least one selected from the group. Preferable solvents include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, polar solvents, and water. The most preferred dispersion medium is water.

  Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane, cyclopentane and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. Examples of ester solvents include ethyl acetate and methyl acetate. Examples of the halogenated hydrocarbon solvent include chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl butyl ketone. Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol and the like. Examples of ether solvents include diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, dimethoxyethane and the like. In the present invention, the polar solvent is at least one solvent selected from dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, trimethylphosphoric acid, and N-methylpyrrolidone.

  The dispersion of fine particles of cured epoxy resin of the present invention contains a surfactant as an essential component. Examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. Examples of the anionic surfactant include fatty acid sodium, fatty acid potassium, and alkylbenzene. Sodium sulfonate, sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkyl ether sulfate, monoalkyl phosphate, sodium polyoxyethylene alkyl ether phosphate, sodium fatty acid ester sulfonate, sodium fatty acid ester sulfate, fatty acid alkyl Examples include sodium rosamide sulfate and sodium fatty acid amide sulfonate.

  Examples of the cationic surfactant include alkyl methyl ammonium chloride, alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, and alkyl pyridinium chloride.

  Examples of zwitterionic surfactants include alkylaminocarboxylates, carboxybetaines, alkylbetaines, sulfobetaines, phosphobetaines, and the like.

  Nonionic surfactants include sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene lanolin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol monofatty acid ester, fatty acid alkanolamide, fatty acid monoethanolamide. , Fatty acid diethanolamide, fatty acid triethanolamide, polyoxyethylene fatty acid amide, isopropanolamide, alkylamine oxide, polyoxyethyleneamine, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and derivatives thereof.

  The alkyl referred to here includes, for example, straight-chain saturated hydrocarbon groups or branched saturated hydrocarbon groups having 1 to 30 carbon atoms. The alkyl moiety may be a hydrogen atom, a linear unsaturated hydrocarbon group, or a branched unsaturated hydrocarbon group.

  In particular, the surfactant used in the present invention is preferably polyoxyethylene alkylphenyl ether (for example, nonylphenol ethylene oxide adduct), polyoxyethylene alkyl ether and derivatives thereof included in the above. A preferable range of the alkyl group includes a straight-chain saturated hydrocarbon group or a branched saturated hydrocarbon group having 1 to 20 carbon atoms. The alkyl moiety may be a hydrogen atom, a linear unsaturated hydrocarbon group, or a branched unsaturated hydrocarbon group.

  Particularly preferred surfactants include those having the following structure.

式中、Ｒは水素またはアルキル基であり、アルキル基の炭素数は１〜２０、好ましくは５〜１５である。また、ｎは５〜１００、好ましくは２０〜４０の整数である。

In formula, R is hydrogen or an alkyl group, and carbon number of an alkyl group is 1-20, Preferably it is 5-15. N is an integer of 5 to 100, preferably 20 to 40.

  Since polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and derivatives thereof have an appropriate HLB value for fine particles of cured epoxy resin, the dispersibility of the fine particles of cured epoxy resin in a dispersion medium is improved. While improving, the obtained dispersion liquid can maintain a long-term stable dispersibility.

  The cured epoxy resin particles and the dispersion thereof of the present invention can be prepared as follows.

  First, an epoxy resin and a surfactant are added to a reaction vessel, and stirred and mixed. In this case, the weight ratio of the epoxy resin to the surfactant is preferably 2 to 100 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. More preferably, it is 5 to 50 parts by weight. By setting the blending amount of the surfactant in such a range, fine particles having a fine particle diameter can be obtained.

  As a stirring temperature at the time of mixing an epoxy resin and surfactant, it is 20 to 80 degreeC, Preferably it is 30 to 70 degreeC, More preferably, it is 35 to 50 degreeC. By stirring under this temperature condition, foaming can be suppressed and stirring can be performed efficiently and uniformly. Further, the stirring speed is preferably 300 to 350 rpm, more preferably 310 to 330 rpm.

  By adding a dispersion medium to the thus obtained mixture of epoxy resin and surfactant, phase-emulsification is carried out to make an emulsion. Any dispersion medium may be used as long as it has a saturated solubility in the epoxy resin. For example, pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane, cyclopentane. Aliphatic hydrocarbon solvents such as benzene, toluene, xylene, etc., ester solvents such as ethyl acetate, methyl acetate, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1 1,1-trichloroethane, chlorobenzene, halogenated hydrocarbon solvents such as 2,6-dichlorotoluene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, methanol, ethanol, 1-propanol, 2-propanol Alcohol solvents such as Polar solvents such as sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, trimethylphosphoric acid, N-methylpyrrolidone, ether solvents such as diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglyme, dimethoxyethane, It may be at least one solvent selected from water. Preferably, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane, cyclopentane, and aromatic hydrocarbons such as benzene, toluene, xylene Solvent and water, particularly preferably water.

  The amount of the dispersion medium used at this time is 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the curing agent. Good.

  At this time, as a method of adding the dispersion medium to the mixture of the epoxy resin and the surfactant, any of a continuous dropping method, a divided addition method, and a batch addition method may be used, but preferably a continuous dropping method and a divided dropping method, The continuous dropping method is the most preferable for industrially efficient implementation. The time for dropping the dispersion medium is not particularly limited, but is in the range of 1 minute to 100 hours, preferably 30 minutes to 10 hours, and more preferably 1 hour to 5 hours.

  At this time, the temperature at which the dispersion medium is added is preferably -20 ° C to 200 ° C, more preferably 10 ° C to 100 ° C, and particularly preferably 20 ° C to 60 ° C.

  Moreover, as a stirring speed when a dispersion medium is dripped at the mixture of an epoxy resin and surfactant, Preferably it is 100-1600 rpm, More preferably, it is 200-900 rpm, More preferably, it is 400-700 rpm.

  The atmosphere in which the emulsion of the epoxy resin and the surfactant is prepared may be any of air, an inert gas atmosphere such as nitrogen, argon, carbon dioxide, or the like, but is preferably a nitrogen atmosphere.

  If prepared under the above-described conditions, an epoxy resin emulsion can be obtained in which the epoxy resin is dispersed very finely and uniformly without agglomeration and fusion of the epoxy resin during phase inversion emulsification. By curing the epoxy resin emulsion thus obtained, it is possible to obtain fine particles of a cured epoxy resin having a very fine particle size and a narrow particle size distribution.

  In the curing reaction step, a curing agent is added to the epoxy resin emulsion and mixed and stirred under predetermined conditions. The blending amount of the curing agent is preferably 1 to 100 parts by weight, more preferably 1 to 80 parts by weight, and further preferably 1 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin. The curing agent may be added as it is, but is preferably added in a solution state. Any solvent may be used as long as it can dissolve the curing agent, and a particularly preferable solvent is the same as the dispersion medium of the epoxy resin, and water is extremely preferable.

  The resulting emulsion containing an epoxy resin and a curing agent is heated and mixed to perform a curing reaction, whereby a dispersion in which fine particles of a cured epoxy resin are dispersed can be obtained. The heating temperature for curing the epoxy resin is preferably 20 ° C to 200 ° C, more preferably 20 ° C to 100 ° C, and even more preferably 40 ° C to 80 ° C. The time for performing the curing reaction is preferably in the range of 10 minutes to 100 hours, more preferably 30 minutes to 10 hours, and even more preferably 1 hour to 5 hours. In addition, the reaction atmosphere may be any of air, an inert gas atmosphere such as nitrogen, argon, carbon dioxide, or the like, but is preferably a nitrogen atmosphere.

  The stirring speed when the epoxy resin is cured to form fine particles is preferably 100 to 1600 rpm, more preferably 200 to 900 rpm, and still more preferably 300 to 350 rpm.

  By operating at these temperature, time, and stirring conditions, a dispersion of the desired cured epoxy resin particles can be obtained without agglomeration and fusion.

  The cured epoxy resin particles can be obtained by separating the cured epoxy resin particles from the dispersion obtained by the above-described method for producing a dispersion of cured epoxy resin particles. The method for separating fine particles of cured epoxy resin is not particularly limited, and a commonly performed method such as a centrifugal separation method, a filtration separation method, spray drying, or centrifugal precipitation can be used.

  The epoxy resin fine particles obtained in the present invention have a small average particle size and a narrow particle size distribution, so the specific surface area of the particles is large, the adsorptive power is strong, the activity of reaction with other substances is strong, the contact area is large, etc. Has the advantage of.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

<Analysis method>
Particle Size Measurement / Particle Size Distribution Measurement A particle size distribution and an average particle size were measured using a laser diffraction / light scattering type particle size distribution meter (Microtrac S3500 manufactured by Nikkiso Co., Ltd.).

Example 1
100 parts by weight of bisphenol A type epoxy resin (jER (registered trademark) 828 manufactured by Japan Epoxy Resin Co., Ltd., hereinafter referred to as “EP828”) and 10 parts by weight of nonylphenol ethylene oxide adduct (Emulgit 9 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , Hereinafter referred to as “emulsifier”) was placed in a reaction vessel and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 600 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion of the product was obtained. The average particle diameter of the obtained fine particles was 350 nm.

Example 2
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 10 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 700 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion of the product was obtained. The average particle diameter of the obtained fine particles was 300 nm.

  The photograph which observed the microparticles | fine-particles of the obtained epoxy resin hardened | cured material with the scanning electron microscope was shown in FIG. Further, after the obtained dispersion of fine particles of the cured epoxy resin was stored for 6 months, the particle size distribution of the fine particles of cured epoxy resin in the dispersion was measured. The results of the obtained particle size distribution are shown in FIG. Even after storage for 6 months, changes in the particle size distribution and average particle size of the cured epoxy resin particles were hardly observed.

Example 3
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 16 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 500 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion was obtained. The average particle size of the obtained fine particles was 200 nm.

  The photograph which observed the microparticles | fine-particles of the obtained epoxy resin hardened | cured material with the scanning electron microscope was shown in FIG. Further, the particle size distribution of the fine particles of the obtained cured epoxy resin was measured, and the result of the obtained particle size distribution is shown in FIG.

Example 4
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 16 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 550 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion was obtained. The average particle diameter of the obtained fine particles was 190 nm.

Example 5
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 25 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 400 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion was obtained. The average particle size of the obtained fine particles was 230 nm.

Example 6
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 25 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 450 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion was obtained. The average particle size of the obtained fine particles was 210 nm.

Example 7
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 40 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 550 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution composed of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, and the reaction was performed at 40 ° C. and a stirring speed of 320 rpm for 24 hours, followed by stirring and curing to cure the epoxy resin. A fine particle dispersion was obtained. The average particle diameter of the obtained fine particles was 190 nm.

Example 8
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 40 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes. Next, after adjusting the stirring speed to 550 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Thereafter, 20 parts by weight of deionized water was added, and after stirring for 10 minutes, 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous solution of a curing agent composed of 6 parts by weight of hydrazine and 120 parts by weight of deionized water is added, and the mixture is reacted at 40 ° C. and a stirring speed of 320 rpm for 24 hours. A dispersion was obtained. The average particle size of the obtained fine particles was 200 nm.

Comparative Example 1
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 16 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 100 rpm for 20 minutes. At this point, when visual observation was performed, it was in a non-uniform state. After adjusting the stirring speed to 500 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. At this point, phase separation had occurred. Subsequently, 20 parts by weight of deionized water was added and stirred for 10 minutes, and then 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous hardener solution consisting of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, followed by stirring and curing at 20 ° C. and a stirring speed of 320 rpm for 24 hours. did.

Comparative Example 2
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 16 parts by weight of an emulsifier were placed in a reaction vessel, and stirred at 40 ° C. and a stirring speed of 320 rpm for 20 minutes to be uniform. While maintaining the stirring speed, 20 parts by weight of deionized water was added and stirred for 10 minutes. Subsequently, 20 parts by weight of deionized water was added and stirred for 10 minutes, and then 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, an aqueous curing agent solution consisting of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water was added, followed by stirring and curing at 20 ° C. and a stirring speed of 320 rpm for 24 hours. However, only a block-shaped cured epoxy resin was obtained, and the desired fine particles could not be obtained.

Comparative Example 3
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 16 parts by weight of an emulsifier were placed in a reaction vessel and set at 40 ° C. and a stirring speed of 700 rpm. At this time, the viscosity was high and stirring was not possible. .

Comparative Example 4
100 parts by weight of a bisphenol A type epoxy resin (EP828) and 1.1 parts by weight of an emulsifier were placed in a reaction vessel, and the mixture was stirred for 20 minutes at 40 ° C. and a stirring speed of 320 rpm to be uniform. After adjusting the stirring speed to 500 rpm, 20 parts by weight of deionized water was added and stirred for 10 minutes. Subsequently, 20 parts by weight of deionized water was added and stirred for 10 minutes, and then 20 parts by weight of deionized water was further added and stirred for 10 minutes. Subsequently, a curing agent aqueous solution consisting of 14 parts by weight of piperazine and 111.6 parts by weight of deionized water is added, and stirring and curing is performed at 20 ° C. and a stirring speed of 320 rpm for 24 hours. Got. The average particle diameter of the obtained fine particles was 8.5 μm.

  Since the resin fine particles of the present invention have a small average particle size and a narrow particle size distribution, they have advantages such as a large specific surface area of the particles, strong adsorptive power, strong activity of reaction with other substances, and a large contact area. Therefore, it is extremely useful in the fields of paints, electronic information materials, fine chemicals and the like.

It is the figure which copied the photograph which observed the epoxy resin hardened material microparticles | fine-particles obtained by Example 2 with the scanning electron microscope. It is a graph showing the particle size distribution measured after preserve | saving the epoxy resin hardened material fine particle dispersion obtained by Example 2 for 6 months. It is the figure which copied the photograph which observed the epoxy resin hardened material microparticles | fine-particles obtained by Example 3 with the scanning electron microscope. 6 is a graph showing the particle size distribution of fine particles of cured epoxy resin obtained in Example 3. FIG.

Claims (9)

Fine particles of a cured epoxy resin obtained by curing an epoxy resin and a curing agent, the average particle diameter of which is 50 to 400 nm and the curing agent is piperazine, hydrazine, hexanedioic acid dihydrazide, diethylenetriamine, triethylenetetramine, Epoxy resin cured fine particles , which are at least one selected from the group consisting of 4,4'-diaminodicyclohexylmethane, diaminodiphenylsulfone and diaminodiphenylmethane . A dispersion of cured epoxy resin particles, wherein the cured epoxy resin particles according to claim 1 and a surfactant are dispersed in a dispersion medium. The dispersion of fine particles of cured epoxy resin according to claim 2 , wherein the surfactant is polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or a derivative thereof. The dispersion of fine particles of cured epoxy resin according to claim 2 or 3, wherein the surfactant is polyoxyethylene alkylphenyl ether. Mix the epoxy resin and surfactant, mix by heating and stirring, then change the stirring speed, stir and mix with deionized water to produce an epoxy resin emulsion, and cure to this epoxy resin emulsion The method for producing a dispersion of fine particles of an epoxy resin cured product according to claim 2 , wherein a curing reaction is carried out by adding an agent. 6. The method for producing a fine particle dispersion of cured epoxy resin according to claim 5 , wherein 2 to 100 parts by weight of the surfactant is blended with 100 parts by weight of the epoxy resin. The temperature of the said hardening reaction is 35-50 degreeC, The manufacturing method of the epoxy resin hardened material fine particle dispersion of Claim 5 or 6 characterized by the above-mentioned. The stirring speed when mixing the epoxy resin and the surfactant is 300 to 350 rpm, the stirring speed when adding deionized water to the obtained mixture is 400 to 700 rpm, and the stirring speed when performing the curing reaction. The method for producing a dispersion of fine particles of an epoxy resin cured product according to claim 5, 6 or 7, wherein the viscosity is 300 to 350 rpm. The cured epoxy resin particles according to claim 1, wherein the cured epoxy resin particles are separated from the dispersion of the cured epoxy resin particles obtained by the production method according to any one of claims 5 to 8 . A method for producing fine particles.

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