JPH06211961A - Fine epoxy resin particle and its production - Google Patents

Abstract

PURPOSE:To provide easily the subject particles being adaptable for extensive uses and having a controlled particle diameter and any desired composition. CONSTITUTION:A process for producing an epoxy resin emulsion by emulsifying and curing fine spherical epoxy resin particles having a particle diameter of 0.1-300mum, a polyepoxy compound and a curing agent in an inert liquid, wherein hydrophobic silica in used as the emulsifier. Fine epoxy resin particles are separated from this emulsion in the form of a powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spherical epoxy resin fine particles and a method for producing the same, and more particularly, to a matting agent for plastics, a filler and a reinforcing agent for plastics and rubber, paint, It is useful as a matting agent for inks, paints and adhesives, fillers and reinforcing agents, powder coatings, polishing materials and additives for coatings, etc., and these fine particles are colored with pigments or dyes. Is suitably used as a coloring compounding agent or coating compounding agent for molding resins, chemically synthetic fibers, paper, films, non-woven fabrics and the like.

[0002]

2. Description of the Related Art Conventionally, a method for obtaining spherical fine particles of epoxy resin by curing a polyfunctional epoxy compound in an emulsion system is known, and as a specific example, the polyfunctional epoxy compound is dispersed in water as a dispersion medium. A method of emulsifying and curing with a water-soluble amine curing agent or piperazine derivative is disclosed in JP-B-62-48972 and JP-A-61-87721.

Further, there is a method of obtaining spherical particles by curing a polyfunctional epoxy compound in water in the presence of a water-soluble protective colloid as a suspension stabilizer.
It is disclosed in Japanese Patent No. 10320. Each of the above methods uses water as a medium, and uses a water-soluble protective colloid and a general organic surfactant.

[0004]

Since all of the above methods use water as a medium, it is not possible to use a substance such as an acid anhydride that reacts or decomposes with water, and the fine particles produced and obtained. There are various restrictions. Therefore, there is a drawback that it is difficult to obtain fine particles of epoxy resin having sufficient physical properties. Also, the presence of water is not always useful depending on the application, and the selection of water-soluble protective colloids and water-soluble stabilizers such as organic surfactants should be carefully and properly performed in order to obtain a stable emulsion. It is very complicated to choose. Further, it is unavoidable that these surfactants and the like are mixed in the obtained epoxy resin particles, which may adversely affect the physical properties of the epoxy resin.

In emulsion polymerization in an aqueous system, it is very difficult to control the particle size, and the polyfunctional epoxy compounds used in the aqueous system are also limited to some extent. Therefore, the object of the present invention is to solve the above-mentioned drawbacks of the prior art and to control the particle size, which is adaptable to a wide range of applications.
It is an object to easily provide epoxy resin fine particles having various compositions.

[0006]

The above object can be achieved by the present invention described below. That is, the present invention has a particle size of 0.1.
-300 μm and spherical epoxy resin fine particles, a polyfunctional epoxy compound and a curing agent, when emulsifying and curing in an inert liquid, a hydrophobic silica is used as an emulsifier. And a method for producing epoxy resin fine particles, characterized in that the epoxy resin fine particles are taken out from the emulsion as powder.

[0007]

The present inventors have found that hydrophobic silica dispersed in an inert liquid, particularly a fluorine-based inert liquid, can easily and stably emulsify a polyfunctional epoxy compound and a curing agent into fine particles. It was Further, as a feature of the hydrophobic silica used in the present invention, it is adsorbed in a particulate form on the interface of the fine particles of the epoxy resin to stabilize the emulsion, and the emulsifying ability is reduced due to the viscosity and heat generated during the synthesis process of the epoxy resin. Without this, it has a function of preventing the emulsified fine particles of the epoxy resin from coagulating into a large lump.

Further, the agglomeration of the epoxy resin generated when the epoxy resin fine particles are separated from the fluorine-based inert liquid to produce the powdery epoxy resin is prevented, and the fine particle powdery epoxy resin is produced. Work beneficially. This is a fundamentally different action from known organic emulsifiers and dispersion stabilizers.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. In the present invention, the epoxy resin is obtained by reacting a polyfunctional epoxy compound having two or more epoxy groups in one molecule with a polycarboxylic acid or an anhydride thereof (hereinafter referred to as a curing agent). It means a cured (crosslinked) resin.

Examples of the polyfunctional epoxy compounds used in the present invention include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A diβ-methylglycidyl ether, and bisphenol hexafluoroacetone diglycidyl. Ether, tetraphenyl diglycidyl ether ethane, triphenyl diglycidyl ether methane, trimethylolpropane triglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether,

Diglycidyl ether of bisphenol A alkylene oxide adduct, polymerized fatty acid additive of bisphenol A diglycidyl ether glycerin triglycidyl ether, pentaerythritol diglycidyl ether, brominated bisphenol A
Glycidyl ether type epoxy resin such as diglycidyl ether, chlorinated bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, epoxy urethane resin, glycidyl ether such as p-oxybenzoic acid glycidyl ether ester Glycidyl ester type epoxy resin such as ester type epoxy type resin, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.,

Glycidyl amine type epoxy systems such as diglycidyl aniline, tetraglycidyl metaxylene diamine, triglycidyl-p-aminophenol, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, etc. Resin, epoxidized polybutadiene, linear aliphatic epoxy resin such as epoxidized soybean oil, 3,4-epoxy-6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate, 3,4- Epoxy cyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, vinylcyclohexene diepoxide, dicyclopep Data diene oxide, bis (2,
Alicyclic epoxy resins such as 3-epoxycyclopentyl) ether and limonendioxide,

Polyglycidyl ether of polyphenol, butadiene oxide diglycidyl ether, 2,
6-glycidyl phenyl glycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, divinylbenzene oxide, bis (2,3-epoxycyclopentene) ether, resorcin diglycidyl ether, 2-glycidylphenyl glycidyl ether, 3,4-epoxy -6-methylcyclohexylmethyl (3,4-epoxy-6-methylcyclohexane) carboxylate,

Octylene oxide, styrene oxide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether,
Cresol glycidyl ether, p-sec-butylphenyl glycidyl ether, cyclohexene vinyl monooxide, allyl glycidyl ether, glycidyl methacrylate, alkyl-substituted phenyl glycidyl ether, dipentene monooxide, acrylic acid glycidyl ester, epoxidized cadanol diester, tertiary Examples thereof include carboxylic acid glycidyl ester and α-pinene oxide alone or in a mixture.

Examples of the curing agent used in the present invention include aliphatic acids such as dodecylsuccinic acid, adipic acid, dichloromaleic acid and polyazelaic acid, and acid anhydrides thereof, tetrahydrophthalic acid, methylhexahydrophthalic acid and methyl. Alicyclic acids such as tetrahydrophthalic acid, hexahexahydrophthalic acid, tetrachlorophthalic acid, methyl nadic acid, chlorendic acid, tetrabromophthalic acid, methylcyclohexene tetracarboxylic acid, ethylene glycol bis (anhydrotrimate) and the like Acid anhydride,

Aromatic acids such as phthalic acid, pyromellitic acid, trimellitic acid, 3,3 '-, 4,4'-benzophenonetetracarboxylic acid and acid anhydrides thereof, acrylic acid,
Methacrylic acid, maleic acid, polymers such as fumaric acid esters, styrene-maleic acid copolymers, styrene-butadiene-acrylic acid copolymers and other carboxyl group-containing homopolymers and copolymers, maleic anhydride and acrylic Homopolymers and copolymers such as acid esters, ethylene-maleic anhydride copolymer, styrene-functional groups that can be converted to a carboxyl group by hydrolysis or alkali saponification of ethyl acrylate copolymer etc. Compounds with

Polymers in which a carboxyl group is introduced later by the reaction of carboxymethyl cellulose, carboxyl group-introduced polybutadiene, etc., natural polymers having a carboxyl group such as alginic acid, polymers containing a carboxyl group are caustic alkali, alkali carbonate, ammonia. , A salt of an organic amine or the like with an alkaline substance, or a mixture thereof. The types of polyfunctional epoxy compounds and curing agents used in the present invention, the amount used, the compounding ratio,
It is determined according to the purpose of use of the obtained powdery epoxy resin cured product, and is not particularly limited. It is desirable to use a curing accelerator, if necessary, in the case of slow reaction in the synthesis of epoxy resin.

As the curing accelerator, known compounds used for acid curing of polyfunctional epoxy compounds can be used, and specific examples thereof include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, and 2 ，
Tertiary amines such as 4,6-tris (dimethylaminomethyl) phenol, some secondary amines, quaternary ammonium salts such as benzyltrimethylammonium chloride, 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-
Examples thereof include imidazole such as 2-methylimidazole and metal salts of carboxylic acid. The amount of the curing accelerator used is 0.1 to 20 phr, preferably 0.1 to 1 phr. Further, BF ₃ complex, imidazole derivative, diaminomaleonitrile and its derivative, melamine and its derivative, polyamine salt, carboxylic acid ester, methylhydrazine, amine imide compound, aromatic diazonium salt, diaryl iodonium salt, triallyl sulfonium salt, triallyl. Known latent hardeners such as selenium salts can also be used.

When the polyfunctional epoxy compound and the curing agent are mixed or used alone, when the polyfunctional epoxy compound and the curing agent are solid at room temperature or viscosity adjustment is required to make them easy to handle, they are heated. Low viscosity and melting above the melting point, mixing with other polyfunctional epoxy compounds and curing agents or forming a eutectic mixture, adjustment of viscosity with organic solvents and diluents, etc. You can do it.
In addition, additives such as viscosity modifiers, viscosity modifiers, fillers, anticorrosives, flame retardants, colorants, and flexibility imparters can be used as necessary, but the type and optimum The blending amount is
It must be decided each time according to the purpose.

The inert liquid in which the polyfunctional epoxy compound and the curing agent are emulsified and dispersed may be any organic solvent which is incompatible with the polyfunctional epoxy compound and the curing agent, and is not particularly limited, but is preferred. Such a solvent is a fluorine-based organic solvent. Examples thereof include, for example, perfluoropentane, perfluorohexane, perfluoroheptane,
Perfluorooctane, perfluorocyclohexane,
Perfluorotetrahydrofuran, perfluorodecalin, perfluoromethyldecalin, perfluorotri-
n- butylamine, _{3-hydro-1,3-chloro-perfluorobutane, CF 3 - {[O-} CF (CF 3) -CF 2] n - (O-CF 2) m} -OC
Specific examples thereof include perfluoropolyether represented by F ₃ and mixtures thereof.

These inert liquids, particularly fluorine-based inert liquids, are nonflammable and are excellent in insolubility, thermal stability and chemical resistance. Further, since the surface tension is extremely small, it has the property of wetting the surface of all substances, but in the low boiling point type, attention must be paid to volatilization loss from the viewpoint of manufacturing cost. In the present invention, hydrophobic silica is used as an emulsifier in order to emulsify the raw material of the epoxy resin in the inert liquid. This hydrophobic silica is obtained by chemically changing the surface of hydrophilic silica with a hydrophobic compound to make it hydrophobic. As the hydrophilic silica used for producing the hydrophobic silica, a wet-process silica synthesized by reaction of sodium silicate and acid, hydrolysis of alkoxysilane or reaction of calcium silicate and acid, or oxyhydrogen of silicon halide. Preference is given to dry process silica which is hydrolyzed in the flame at high temperature or is synthesized from quartz by the arc method.
Further, such silica powder has a surface area of 30 to 400 m ² / g, and has a certain amount of silanol groups (≡SiOH) on the particle surface depending on its type and surface area.

The method of making the surface of the hydrophilic silica hydrophobic is described by the silanol group (≡SiO) existing on the surface of the silica.
H) is a method of reacting a hydrophobic compound with the surface of the compound to make it hydrophobic, and the compound used for hydrophobization includes a functional group capable of reacting with a silanol group (≡SiOH) and a hydrophobic group. It is not particularly limited as long as it is a compound having a group as a group, but examples thereof include halogenated alkylsilane, alkoxysilane, alkylsilazane, halogenated fluoroalkylsilane, fluoroalkylalkoxysilane and perfluoroalcohol (thioalcohol).
Etc.

The halogenated alkylsilane is (R ¹ ) _n -Si-
(X) _m , R ¹ is, for example, a C _1-20 linear or branched alkyl group or — [(R ² ) ₂ Si—O] _p —R ² , and p is 1 to 1 Two
0, R ² is a methyl group or a phenyl group, X is a halogen atom, n and m are integers of 1 to 3, and n + m is 4
Is. Alkoxysilane is represented by _{^{(R 1) n -Si- (OR}} 3) m, R 1, n and m are as defined above, R ³ is methyl or ethyl. Alkylsilazanes are [(CH ₃ ) ₃ Si] ₂ NH
Alternatively, it is [(CH ₃ ) ₃ Si] ₃ N or the like.

The halogenated fluoroalkylsilane is (R
⁴ -R ⁵ ) _n (CH ₃ ) _q -Si- (X) _m , R ⁴ is a C _3-12 linear or branched perfluoroalkyl group, and R ⁵ is CH ₂ , C ₂ H
₄ , CONHC ₃ H ₆ or SO ₂ N (C ₃ H ₇ ) C ₃ H ₆ , and q is 0 or 1
And n and m are integers of 1 to 3 and n + m + q is 4.
X is a halogen atom. The fluoroalkylalkoxysilane is represented by (R ⁴ -R ⁵ ) _n (CH ₃ ) _q -Si- (OR ³ ) _m , and R ³ ,
R ⁴ , R ⁵ , n, m and q are the same as above. Perfluoro alcohol (thio alcohol) is represented by ^{(R 4 -R 5) OH,} R 4 and R ⁵ are as defined above. These compounds
Silanol groups (≡ present on the surface of hydrophilic silica particles
Hydrophobic silica is produced by reacting with (SiOH).

Particularly preferred hydrophobic groups introduced by the above compounds are: = Si = (CH ₃ ) ₂ groups, -Si≡ (CH ₃ ) ₃ groups, ≡Si-C ₈
H ₁₇ group,-{[Si (CH ₃ ) ₂ -O] _q -Si (CH ₃ ) ₃ } group (1≤q≤1
5, preferably 3 ≦ q ≦ 10), ≡Si— (C ₂ H ₄ —C ₈ H ₁₇ ) group and ≡Si—O— (C ₂ H ₄ —C ₈ H ₁₇ ) group. The reaction between the silanol group on the surface of the hydrophilic silica and the compound reactive with the silanol group is easily achieved by bringing them into contact with each other. At this time, the treatment efficiency can be improved by heat treatment or addition of a catalyst, if necessary. The hydrophobic silica thus obtained has a concentration of a functional group reactive with a silanol group in the compound of 1 relative to hydrophilic silica having a surface area of 1000 m ² (for example, 10 g of silica having a surface area of 100 m ² / g). It is preferable to treat with a compound equivalent to millimolar to 6 millimolar.

The amount of the hydrophobic silica prepared as described above can be 0.5 part by weight or more per 100 parts by weight of the raw material of the epoxy resin, and preferably 1.
It is 0 to 20 parts by weight. If the amount is less than 0.5 parts by weight, the emulsifying ability of the raw material of the epoxy resin is insufficient, the emulsion particles are large and the stability of the emulsion is poor, and it is difficult to obtain a stable emulsion having fine emulsion particles. On the other hand, if the amount exceeds 20 parts by weight, the emulsifying ability of the raw material of the epoxy resin can be produced without any problem, but the effect of the emulsion stabilizer is excessive and there is no particular advantage. Further, the hydrophobic silica used in the present invention may be used alone, or two or more kinds may be mixed and used to prepare the intended emulsion and fine particles.

The amount of hydrophobic silica used can be determined by the water repellency and oil repellency of the silica surface after treatment (measured using a contact angle measuring instrument manufactured by Kyowa Interface Science). Hydrophobic silica used in the present invention, by using the above preferred ratio, it is possible to prevent the aggregation of the epoxy resin fine particles when producing an emulsion of the raw material of the epoxy resin in the inert liquid, It is possible to produce a uniform and stable emulsion of fine particles of epoxy resin. The preferred primary particles of the hydrophobized silica as described above are 7 nm to 50 nm, but the present invention is not limited to this and it is necessary to finely disperse the hydrophobized silica in an inert liquid during practical use.
As the disperser, known dispersers such as an ultrasonic disperser, a homogenizer, a sand mill, a ball mill, a high speed mixer and an attritor can be used.

The epoxy resin emulsion in the present invention is a solid at room temperature, which is obtained by mixing or independently mixing the polyfunctional epoxy compound and the curing agent in the fluorine-based inert liquid in which the hydrophobic silica is dispersed. When the raw material of the epoxy resin is used alone, it is melted by heating or by using a fluorine-based inert liquid in which hydrophobic silica preheated is dispersed.
Alternatively, it is made into a liquid by a method such as using a diluent and finely dispersed and emulsified. It is produced by reacting and hardening this emulsion.

The particle size of the fine particles in the emulsion thus produced can be controlled at 1.0 μm to 300 μm. The particle size of the emulsified epoxy resin is affected by the type and addition amount of the hydrophobic silica or the shearing force of the emulsifying machine. The shearing force for emulsifying the molten epoxy resin is determined in the initial stage of emulsification, and the stronger this is, the smaller the particle size of the epoxy resin becomes. An important factor in hydrophobic silica is the type and concentration of hydrophobic groups present on its surface,
Further, the dispersibility in a fluorine-based inert liquid and the dispersed particle size.

That is, the action of the hydrophobic silica as an emulsion stabilizer is an O / O emulsifier, which acts in correlation with the hydrophilic and hydrophobic strength of the epoxy resin and the fluorine-based inert liquid. . The dispersed particle size of the epoxy resin particles is determined by the primary particle size of the dispersed hydrophobic silica, the affinity with the fluorine-based inert liquid and the shearing force of the disperser. Generally, the larger the shearing force, the smaller the dispersed particle size. Become. The hydrophobic silica in the stable emulsion in the fluorine-based inert liquid exists in the form of fine particles at the interface of the epoxy resin particles, and is due to the action of preventing the aggregation of the epoxy resin particles.

The reason for this is not clear, but it is a comprehensive action such as the interfacial tension of the hydrophobic silica with the liquid, the balance of the hydrophobic group / hydrophilic group, and the affinity with the fluorine-based inert liquid. As a result of considering these conditions,
By adjusting the amount of hydrophobic silica added to the liquid, it is possible to control the particle size of the epoxy resin in the emulsion, and the larger the amount added, the smaller the particle size, and the smaller the amount, the larger the particle size. Become. Also, when the amount of hydrophobic silica added to the epoxy resin is the same and the particle size of the sufficiently dispersed hydrophobic silica dispersion is different, the larger the particle size of the hydrophobic silica, the larger the particle size of the epoxy resin. The diameter increases, and the smaller the particle size of the hydrophobic silica, the smaller the particle size of the epoxy resin.

The epoxy resin fine particles of the present invention can be obtained by simply separating the inert liquid from the above epoxy resin dispersion under normal pressure or reduced pressure. As the device for separating the inert liquid, any known device such as a spray dryer, a vacuum dryer with a filtering device, a vacuum dryer with a stirring device, a vacuum dryer with a vibrating device, and a tray dryer can be used. According to the method as described above, spherical fine particles of an epoxy resin having a uniform particle diameter can be obtained without any complicated and costly pulverization step or classification operation as in the prior art.

Further, in the present invention, in the production of the above-mentioned epoxy resin fine particles, as a raw material, a coloring agent such as a dye or a pigment, a plasticizer, a stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent,
Fine particles suitable for various uses of epoxy resin fine particles can be obtained by mixing various additives such as an abrasive and an extender pigment. The epoxy resin fine particles of the present invention obtained as described above are shown in FIG. 1 (magnification: 150 times) and FIG. 2 (magnification: 15 times).
(0 times), it is a spherical particle having a very narrow particle size distribution, and since hydrophobic silica remains on the surface to some extent, it has excellent fluidity and automatic metering is possible.

[0034]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, the contents or% are based on weight. Example 1 (Preparation of Hydrophobic Silica Dispersion) Hydrophobic silica was mixed at a concentration of 5% with a fluorine-based inert liquid and dispersed using an ultrasonic disperser until the dispersion became stable. A hydrophobic silica dispersion was obtained.

[0035]

[Table 1] M = CH ₃ contact angle: A dispersion liquid in which hydrophobic silica is dispersed in a liquid is uniformly applied on a polyethylene terephthalate film and dried to form a hydrophobic silica layer having a thickness of 80 μm, and a contact angle measuring device (Kyowa Interface Science) is used. (Manufactured by K.K.) at 20 ° C. and water droplets having a diameter of 2 mm or less are placed on the hydrophobic silica layer for measurement.

Example 2 A two-liter separable flask equipped with a homomixer for emulsification [TK Homomixer Mark II type manufactured by Tokushu Kika Kogyo Co., Ltd.] and 1000 parts of perfluoropolyether having a boiling point of 110 ° C. Hydrophobic silica dispersion 8 No. 1
2) Charge 500 parts with 40 while uniformly mixing and stirring
The temperature was raised to ° C.

While operating the emulsifying machine, bisphenol A diglycidyl ether (epoxy equivalent: 187 g / e
q) A homogeneous mixture of 267 parts and 233 parts of 4-methylhexahydrophthalic anhydride is gradually added to make the emulsion stable. Furthermore, after adding 1.0 part of 2-ethyl-4-methylimidazole as a curing accelerator, the curing reaction was carried out at 100 ° C. for 6 hours, and the dispersion of the epoxy resin fine particles was confirmed by microscopic observation. While collecting this dispersion liquid with a vacuum dryer equipped with a stirrer at a vacuum degree of 20 mmHg,
Dry for about 2 hours at a jacket temperature of 50 ° C, then
It was dried at mmHg and 70 ° C. for about 2 hours to obtain an epoxy resin fine powder of the present invention. This one has an average particle size of 51
The particles were spherical fine particles in which no agglomerates of μm were observed.

Example 3 A 2-littill separable flask in which an emulsifying ultra disperser (formerly LK-22, formerly manufactured by IKA, West Germany) was set, and perfluoropolyether 80 having a boiling point of 110 ° C.
0 part and the hydrophobic silica dispersion liquid (No. 1) 60 of Example 1
0 parts were charged, and the temperature was raised to 50 ° C. with uniform mixing and stirring. While operating the emulsifier, bisphenol A diglycidyl ether (epoxy equivalent 187 g / eq) 32
A homogeneous mixture of 1 part and 279 parts of 4-methylhexahydrophthalic anhydride is gradually added to make the emulsion stable.

After further adding 1.0 part of 2-ethyl-4-methylimidazole as a curing accelerator, the curing reaction was carried out at 100 ° C. for about 6 hours, and the dispersion of the epoxy resin fine particles was confirmed by microscopic observation. The dispersion was dried at a jacket temperature of 50 ° C. for about 2 hours, and further at 5 mmHg and 70 ° C. for about 2 hours, while the inert liquid was collected at a vacuum degree of 20 mmHg by a vacuum dryer equipped with a stirrer. , To obtain the epoxy resin fine powder of the present invention. The particles were spherical fine particles having an average particle size of 7 μm and no agglomerates.

Examples 4 to 15 Compositions of polyfunctional epoxy compounds and curing agents, emulsification temperatures, etc. are shown in Tables 2 to 4 below, and others are described in Tables 2 to 4 in the same manner as in Examples 2 and 3. Got the result.

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

Example 16 500 parts of perfluoro n-butylamine having a boiling point of 174 ° C. and that of Example 1 were placed in a 1-liter separable flask in which an ultradisperser for emulsification (formerly West Germany IKA, model LK-22) was set. Hydrophobic silica dispersion (No.8)
250 parts were charged, and the temperature was raised to 80 ° C. with uniform mixing and stirring. 189 parts of solid bisphenol A diglycidyl ether (epoxy equivalent 471 g / eq, melting point 69 ° C.) was preheated to about 80 ° C. at room temperature, and 61 parts of hexahydrophthalic anhydride was added and dissolved therein,
Make a homogeneous mixture.

This homogeneous mixture is gradually added to the above dispersion liquid while the emulsifier is functioning to make the emulsion stable.
Further, 1.0 part of benzyldimethylamine was added as a curing accelerator, followed by curing reaction at 100 ° C. for 2 hours and at 150 ° C. for 4 hours, and the dispersion of the epoxy resin fine particles was confirmed by microscopic observation. This dispersion was dried by a vacuum dryer equipped with a stirrer at a vacuum degree of 5 mmHg while collecting an inert liquid. The jacket temperature was set to 100 ° C., and the particles were taken out after about 3 hours to obtain spherical fine particles having an average particle diameter of 26 μm and having no agglomerates.

Example 17 In a 1-liter separable flask equipped with an emulsifying ultra disperser (formerly LK-22 manufactured by West Germany IKA), 500 parts of perfluoro n-butylamine having a boiling point of 174 ° C. and Example 1 were added. Hydrophobic silica dispersion (No. 6)
250 parts and 100 ° C with uniform mixing and stirring
The temperature was raised to. Tetrabromobisphenol A diglycidyl ether (epoxy equivalent of 400
128 parts (g / eq, softening point: 76 ° C.) is preheated to about 100 ° C., and 122 parts of chlorendic acid anhydride is added thereto to form a mixture.

This mixture was gradually added to the above dispersion while operating an emulsifying machine to make the emulsion stable, then 0.5 part of 1-benzyl-2-methylimidazole as a curing accelerator was added, and the mixture was heated to 150 ° C. Cure for about 3 hours,
Dispersion of the epoxy resin fine particles was confirmed by microscopic observation. The degree of vacuum of this dispersion liquid is 5 m with a vacuum dryer equipped with a stirring device.
It was dried while collecting the inert liquid with mHg. Adjust the jacket temperature to 100 ° C and take out after about 3 hours to obtain an average particle size of 2
Spherical fine particles with no aggregate of 0 μm were obtained.

Example 18 500 parts of perfluoro n-butylamine having a boiling point of 174 ° C. and that of Example 1 were placed in a 1-liter separable flask in which an ultra disperser for emulsification (formerly LK-22 manufactured by IKA, West Germany) was set. Hydrophobic silica dispersion (No.8)
250 parts and 100 ° C with uniform mixing and stirring
The temperature was raised to. Bisphenol A diglycidyl ether (epoxy equivalent 471 g / eq, melting point 69)
189 parts by weight) and melted in the dispersion to make the emulsion stable while operating the emulsifier.

Next, 61 parts of hexahydrophthalic anhydride was finely pulverized in advance, this was gradually added, and the mixture was emulsified while melting. Further, 1.0 part of benzyldimethylamine was added as a curing accelerator, 2 hours at 100 ° C, 150
A curing reaction was carried out at 4 ° C. for 4 hours, and dispersion of the epoxy resin fine particles was confirmed by microscopic observation. This dispersion was dried by a vacuum dryer equipped with a stirrer at a vacuum degree of 5 mmHg while collecting an inert liquid. The jacket temperature was set to 100 ° C., and the particles were taken out after about 3 hours to obtain spherical fine particles having an average particle diameter of 30 μm and in which no agglomerates were observed.

[0050]

[Effects] According to the present invention as described above, it is possible to provide, with a simple method, fine particles of epoxy resin having a narrow particle size distribution, a spherical shape and good fluidity with high productivity.

[0051]

[Brief description of drawings]

FIG. 1 is a micrograph of the fine particles obtained in Example 7 (magnification: 150 times).

FIG. 2 is a micrograph of the microparticles obtained in Example 1 (magnification 150 times).

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[Procedure amendment]

[Submission date] December 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Epoxy resin fine particles and method for producing the same

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

The particle size of the fine particles in the emulsion thus produced can be controlled at 1.0 μm to 300 μm. The particle size of the emulsified epoxy resin is affected by the type and addition amount of the hydrophobic silica or the shearing force of the emulsifying machine. The shearing force for emulsifying the liquid epoxy resin is determined in the initial stage of emulsification, and the stronger this is, the smaller the particle size of the epoxy resin becomes. An important factor in hydrophobic silica is the type and concentration of hydrophobic groups present on its surface,
Further, the dispersibility in a fluorine-based inert liquid and the dispersed particle size.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Example 2 In a 2 liter separable flask in which a homomixer for emulsification [TK Homomixer Mark II type manufactured by Tokushu Kika Kogyo] was set, 1,000 parts of perfluoropolyether having a boiling point of 110 ° C. and Example 1 were used. Hydrophobic silica dispersion (No.
2) Charge 500 parts with 40 while uniformly mixing and stirring
The temperature was raised to ° C.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Example 3 In a 2 liter separable flask in which an emulsifying ultra disperser (formerly LK-22, manufactured by IKA, West Germany) was set, perfluoropolyether 800 having a boiling point of 110 ° C.
Part and hydrophobic silica dispersion liquid (No. 1) 600 of Example 1
And parts were charged, and the temperature was raised to 50 ° C. with uniform mixing and stirring. Bisphenol A diglycidyl ether (epoxy equivalent 187 g / eq) 321 while operating the emulsifier
Parts and 279 parts of 4-methylhexahydrophthalic anhydride are gradually added to make the emulsion stable.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

[0041]

[Table 2]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

Example 16 500 parts of perfluorotri-n-butylamine having a boiling point of 174 ° C. and Example 1 were placed in a 1-liter separable flask having an emulsifying ultra disperser (formerly LK-22, manufactured by IKA, West Germany) set therein. Hydrophobic silica dispersion (No.
8) Charge 250 parts with 80 parts while uniformly mixing and stirring
The temperature was raised to ° C. Bisphenol A solid at room temperature
Diglycidyl ether (epoxy equivalent 471 g / eq,
(Melting point 69 ° C.) 189 parts are preheated to about 80 ° C.,
To this, 61 parts of hexahydrophthalic anhydride is added and dissolved to obtain a uniform mixture.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Example 17 In a 1-liter separable flask in which an emulsifying ultra disperser (formerly LK-22, manufactured by IKA, West Germany) was set, 500 parts of perfluorotri-n-butylamine having a boiling point of 174 ° C. and Example 1 were used. Hydrophobic silica dispersion (No.
6) Charge 250 parts and mix uniformly while stirring 10
The temperature was raised to 0 ° C. Tetrabromobisphenol A diglycidyl ether (epoxy equivalent 4
00g / eq, softening point 76 ° C) 128 parts in advance about 100
Heat to ℃, and add chlorendic acid anhydride 12 to it.
Add 2 parts to make a mixture.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

Example 18 500 parts of perfluorotri-n-butylamine having a boiling point of 174 ° C. and that of Example 1 were placed in a 1-liter separable flask in which an ultradisperser for emulsification (formerly LK-22, manufactured by IKA, Germany) was set. Hydrophobic silica dispersion (No.
8) Charge 250 parts with 10 while mixing and stirring uniformly.
The temperature was raised to 0 ° C. To this dispersion, 189 parts of bisphenol A diglycidyl ether (epoxy equivalent 471 g / eq, melting point 69 ° C.) was added and melted in the dispersion to make the emulsion stable while operating the emulsifier.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiharu Sasaki 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Dainichi Seika Kogyo Co., Ltd.

Claims (8)

[Claims] 1. Epoxy resin fine particles having a particle diameter of 0.1 to 300 μm and a spherical shape. 2. The epoxy resin fine particles according to claim 1, wherein hydrophobic silica is attached to the surface of the fine particles. 3. The epoxy resin fine particles according to claim 2, wherein the hydrophobic silica is a hydrophobic silica obtained by chemically modifying the surface of hydrophilic silica with a hydrophobic compound. 4. A method for producing an emulsion of an epoxy resin, which comprises using hydrophobic silica as an emulsifier when emulsifying and curing a polyfunctional epoxy compound and a curing agent in an inert liquid. 5. The method for producing an epoxy resin emulsion according to claim 4, wherein the curing agent is a polycarboxylic acid or an anhydride thereof. 6. The method for producing an emulsion of an epoxy resin according to claim 4, wherein the hydrophobic silica is a hydrophobic silica obtained by chemically changing the surface of hydrophilic silica with a hydrophobic compound. 7. The method for producing an emulsion of an epoxy resin according to claim 4, wherein the inert liquid is a fluorine-based inert liquid. 8. A method for producing epoxy resin fine particles, which comprises extracting the epoxy resin fine particles in the form of powder from the emulsion of the epoxy resin according to any one of claims 4 to 7.