JPS6262828A - Coated spherical fine particle of epoxy resin - Google Patents

Abstract

PURPOSE:To obtain the titled fine particle capable of imparting electrical conductivity, varying the electrification tendency, changing the color hue, etc., by adsorbing and coating a spherical epoxy fine particle hardened with an amine harder with solid fine particles having specific relationship between the average particle diameters. CONSTITUTION:The objective fine particle is produced by adsorbing and coating a spherical epoxy fine particle hardened with an amine harder with solid fine particles having an average particle diameter relationship of formula 5d<=D (d is average particle diameter of the solid fine particle and D is average particle diameter of the spherical epoxy fine particle). The spherical epoxy fine particle is produced preferably by suspending fine particles of an epoxy compound in an aqueous liquid and hardening the suspending fine particles with a water-soluble amine harder. EFFECT:The particle enables the change of the hydrophilic property of surface, impartment of opacity, impartment of magnetism and improvement in fluidity. USE:Toner for electrostatic copying machine and its assistant.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to epoxy-based spherical fine particles whose surfaces are coated with solid fine particles.

According to the present invention, conductive attachment, charging, [(change of 1,
Change the hydrophilicity of the surface, prevent blocking, change the hue,
It has effects such as improving opacity (q supply, magnetism 1 and 1 supply, and fluidity), and can be used as an auxiliary agent for electrostatic projectors, as well as chemical compounds, pharmaceuticals, and coatings. 1'j1, Adhesives, coating agents, inks, paper, films, plastic compositions, etc. are suitably used as compounding agents for the body, etc.

[Prior art] TiO2'F1 molecules, talc particles, PMM are added to nylon 12 microspheres, polyethylene microspheres, polystyrene microspheres, etc.
An example of coating △particles etc. in 1980-12
Published in Publication No. 7313 and the lecture (print of the lecture abstract) given at the Masumi Koishi Exhibition of Masumi Koishi, a professor at Tono Rijin, 84). However, there are no known examples of shield coating on epoxy-based spherical particles.

[Problems to be Solved by the Invention] It is generally known that solid particles may be adsorbed on the surface of airframe-like particles.In many cases, organic spherical particles and solid particles established between
n) A method of electrostatic adsorption and avoidance has been used that takes advantage of the overlapping relationship, that is, the difference in the direction of charge. For this reason, not only are the adsorption properties of objects that are close to each other in the electrification series inferior, but
It was often observed that no stratification occurred at all, and the practical significance was low.

For this reason, examples of conventional industrial use include:
Coated particles in which titanium oxide particles are adsorbed onto nylon 12 spherical fine particles are used in just one sip as a cosmetic formulation.

If many types of solid particles could be easily adsorbed onto organic spherical particles, the practicality would be greatly improved and many applications would be expected to be developed.

The present invention provides novel coated fine particles in which many types of solid fine particles are adsorbed onto epoxy-based spherical fine particles.

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.

Epoxy-based spherical fine particles hardened with an amine-based curing agent,
A coated epoxy spherical fine particle characterized in that it is adsorbed and coated with solid fine particles whose average particle diameter has the following relationship.

5d≦D d: Average particle diameter of solid fine particles D: Average particle diameter of epoxy spherical fine particles The details of the present invention will be sequentially explained below.

The epoxy spherical fine particles constituting the present invention are generally prepared as follows.

Mechanically pulverized particles of an uncured epoxy compound that is solid at around room temperature, or an epoxy compound that has been partially or fully cured with an amine-based curing agent, are spheroidized by a method such as gravity falling through a heating cylinder, and then spheroidized with an amine-based curing agent. There is a method of avoiding completion of curing by contacting with a system curing agent (referred to as the first method).

Another method is to suspend an uncured epoxy compound in an aqueous liquid and then cure it (this is the second method).
.

There are various methods for suspending uncured epoxy compounds in aqueous liquids. A method of discharging an epoxy compound or its solution into water from a nozzle that vibrates in the air or in a liquid, a method of discharging an epoxy compound or its solution into water in a pulse form from a nozzle in the air or in a liquid, and a method of discharging an epoxy compound or its solution into water from a nozzle that vibrates in the air or in a liquid. There are various methods such as emulsification.

In the present invention, 1-3 regarding the above-mentioned first method and second method.
Although not limited to this, the second method is particularly preferred in terms of particle uniformity, nacreousness, and the like. Among these, the method of emulsification using a surfactant is a preferred method from the viewpoint of productivity, and the present inventor has already disclosed the method in JP-A No. 59-170114,
Japanese Patent Application No. 1987-10296 and Japanese Patent Application No. 1987-175
It has been proposed in issues such as No. 37.

The epoxy compound used in the present invention preferably contains two or more epoxy groups in the molecule.

Examples include glycidyl ether of bisphenol A type, diglycidyl ether of polyethylene glycol, polyglycidyl ether of phenol novolak type compound, N, N, N'', N'-tetraglycidyl m-xylene diamine, etc. Compounds with one epoxy group in the molecule, such as glycidyl methacrylate, may be used as needed.
It is possible to add a small amount of 1 to etc. Also used in the present invention is a modified epoxy compound in which a part of the epoxy group is bonded to a compound having an amino group or the like.

In the first method, among the above-mentioned epoxy compounds, those that are solid at around room temperature are mechanically pulverized, or they are partially or completely cured with an amine-based curing agent such as piperazine or metaxylylene diamine. It is prepared by mechanically crushing a solid resinous material. Subsequently, these particles are charged from the top of a heating cylinder whose internal temperature is about 60 to 400'C, and spheroidized by a method such as avoiding falling under the force of a car. After spheroidization, the particles are immersed in an aqueous solution containing an amine curing agent such as piperazine, ethylene diamine or metaxylylene diamine or an organic solvent solution such as dioxane, or directly combined with a curing agent), and processed as needed. By heating roughly, the particles of the amine curing agent are cured.

In these curing reactions, curing agents other than amine curing agents such as phthalic anhydride may coexist.

In a second method, particles of an epoxy compound suspended in an aqueous liquid are cured with an amine-based curing agent. In this method, the curing agent and curing method are not particularly limited; A method of curing by adding a water-soluble amine curing agent to the suspension.

For the former method, ethylenediamine, diethylene 1-lyamine, N(2-aminoethyl>piperazine, etc.), which are liquid at room temperature, are suitable as curing agents.
．． A maximum of 2 to 1.2 parts is added to the epoxy compound and then made into an aqueous suspension.

Examples of the method of curing an aqueous suspension of an epoxy compound by adding a water-soluble amine curing agent to it (the latter method) include the following.

(A> When adding a water-soluble curing agent to an epoxy compound emulsion and curing it into fine particles, piperazine or a piperazine derivative represented by the following general formula is stoichiometrically calculated from the epoxy equivalent of the epoxy compound emulsion. A method using a water-soluble curing agent containing 0.15 equivalents or more.

(R, R' are hydrogen atoms or hydrocarbon residues having 1 to 4 carbon atoms) (B) When adding a water-soluble curing agent to an emulsion of an epoxy compound and curing it into fine particles, hydrazine or hydrazine represented by the following general formula A method using a water-soluble curing agent containing a derivative in an amount of 0.2 equivalents or more calculated stoichiometrically from the epoxy equivalent [d] of an emulsion of an epoxy compound.

(R represents hydrogen, an alkyl group having 5 or less carbon atoms, a phenyl group, or a 2-hydroxyethyl group).

(C) A water-soluble curing agent is added to the emulsion of the epoxy compound and the mixture is hardened into particles with an average particle size of 0.5 to 50.
When manufacturing μm spherical epoxy particles, (I> epoxy compound emulsion has HLB12
10% by weight of the above surfactant based on the epoxy compound
(n) The water-soluble curing agent is an amine compound which is obtained by mixing an equivalent amount of the above epoxy compound at room temperature and having a Shore A6ffi of 70 or more after being left for 8 hours. , a method in which the amine compound is added in an amount of 0.5 equivalent or more relative to the epoxy compound.

In order to achieve the present invention, any of the above-mentioned methods may be used, and although the method is not particularly specific, the above (A>, (
B) and (C) are 1:1 preferred.

The following compounds are generally mentioned as the amine curing agent used in the present invention, but are not particularly limited to them: polyethylene polyamines such as piperazine, hydrazine, ethylenediamine, diethylene monoamine, triethylenetetramine, etc. alcohol amines such as monoethanolamine, N(2-aminoethyl>piperazine, etc.).

In the second method, an aqueous suspension of the epoxy compound is prepared, and an example of this method is given below.

■ In the air or in a liquid (a method in which the epoxy compound or its solution is continuously discharged from a moving nozzle to cut it into droplets and collect it in the liquid.

■ A method in which an epoxy compound or its solution is ejected in pulses from a nozzle in the air or in a liquid, and then collected in the liquid.

■ A method of emulsifying using a combination U of an epoxy compound containing a surfactant and water.

■ A method of emulsifying using a combination of a powder emulsifier, an epoxy compound, and water.

■ A method of emulsifying using a combination U of water and an epoxy compound containing a protective colloidal substance.

Among the above methods, methods 1 to 2 are preferably used in the present invention from the viewpoint of productivity, but a combination of methods 1 to 2 is also preferably used in the present invention.

The surfactant is not limited to 4j7 in the method 1 (△) and (B) for increasing the epoxy spherical fine particles by 1%, and is not limited to 4j7.
Any commonly known emulsifier for uncured epoxy resins can be used without any problem. The surfactant to be used in method 1 (C) is a surfactant with a IILB value of 12 or more, based on the epoxy compound in an amount of 10 times ♀? Use 6 or more. When the HLB value does not satisfy this range, there is a tendency that the hardening does not occur in the form of particles even if the above-mentioned 1h constant amine curing agent is used.

In general, types of surfactants suitably used in the present invention include polyoxyethylene/phenol-substituted ether type, polyoxyethylene/polyoxyb [1-pyrene block,
Ether-based nonionic surfactants such as polyethers, ester-type nonionic surfactants such as polyethylene glycol with high handling fatty acid sprue, and polyhydric alcohol fatty acid esters are required.

When using a powder emulsifier such as ITI t1 hirulose or Bali sulfate, this method is suitable for producing relatively large particles with an average particle size of 10 to 1000 μm.

In place of the surfactant, it is also possible in the present invention to emulsify with a substance exhibiting a protective colloid effect, such as polyvinyl alcohol, hydroxymedyllerulose, or algin KJ-thorium.

When emulsifying an epoxy compound using a surfactant, powder emulsifier, or protective colloid, use an epoxy compound containing them or water and gradually add water to the epoxy compound being stirred at high speed. is common. The concentration of the produced emulsion is usually 10 to 80%.

The general method for adding an amine curing agent to a suspension of an epoxy compound is to add the curing agent directly or in the form of an aqueous solution. The curing agent may be a mixed system with other amine-based curing agents or other types of curing agents, but it is preferable that the specific curing agent described above satisfies the specific usage conditions.

In the second method, ■ Add the curing agent to the epoxy compound in advance.
If you want to make it into a suspension in water, after suspending it in water for 14 minutes,
(2) When adding a curing agent after making an epoxy compound into an aqueous suspension, if the curing agent is added in small amounts, the curing reaction will occur if the suspension is left standing or gently stirred. To achieve a sufficiently cured state, there is a method of heating the entire product.

In both the first method and the second method, additives such as pigments may be added to the epoxy compound as a raw material if necessary, and additives such as pigments may be added to the epoxy compound to reduce the viscosity. It may contain diluents, etc.

After curing, the particles can be made quaternized by quaternizing the amines contained therein with a quaternizing agent.

Further, the particles after curing may adsorb ions of compounds having 11 groups of anions such as sulfone groups, carboxyl groups, and phenol 11-hydroxyl groups to the extent that the invention is not impaired.

The epoxy spherical fine particles used in the present invention can be prepared by the method described above. The present invention has an average particle diameter of 0.5 to 1
Particles of 000 μm, preferably 1 to 500 μm are always suitably used. If the average particle diameter is larger than this, it tends to become difficult to uniformly adsorb and coat the solid fine particles onto the epoxy spherical fine particles. Moreover, if the average particle diameter is smaller than this, excessive aggregation occurs during wicking and embedding, and a good coating treatment tends to be impossible.

Next, the solid fine particles used in the present invention will be explained.

Examples of the types of solid fine particles used in the present invention are as follows:
Fine metal powders and colloidal particles such as copper, silver, gold, brassica, palladium, nickel, and chromium; fine powders and colloidal particles such as antimony-doped or undoped tin oxide, indium oxide, conductive titanium oxide, and carbon black; Silicon dioxide, fine silica, titanium oxide,
Fine particle titanium oxide, alumino, boehmite, lead sulfide,
Triiron tetroxide, chromium oxide, cadmium sulfide, paris sulfate
Inorganic fine powders, colloidal particles, inorganic pigments such as oxides such as rum, sulfides, sulfates and hydroxides, viscosity 11, talc,
Fine powder such as zeolite, organic chain 1" class 1 such as Fuclocyanine Blue and Red No. 202, fine powder of organic polymer,
A fine powder of an organic compound, which can be used alone or in combination.

In the present invention, it is preferable that the average particle diameter of the epoxy spherical fine particles and the average particle diameter d of the solid fine particles satisfy the following relationship.

5d≦D When the average particle diameter d of the solid fine particles becomes relatively larger than the average particle diameter of the epoxy spherical fine particles, the adsorption coverage of the epoxy spherical fine particles decreases, and they tend to fall off easily. There is.

The following method is suitable for feeding solid particles to epoxy spherical particles.

■ A slurry of spherical particles and solid particles are mixed and stirred. This method often results in only a small amount of solid particles being deposited.

(2) Heat and stir the above mixture at 50°C or higher, preferably 80°C or higher. By this method, most solid fine particles can be deposited.

■ Add salting-out compounds such as sulfuric acid, phosphoric acid, acetic acid, hydrochloric acid, sodium chloride, aluminum chloride, and caustic soda to the mixture described in step 1 and prepare by stirring.

Additionally, warm the stomach if necessary.

■ A mixture of epoxy spherical particles and solid particles is stirred in a mortar, ball mill, etc.

The amount of coverage of epoxy spherical particles by solid particles is “
Although it cannot be absolutely limited because it varies depending on the purpose of coating and the type of solid fine particles, it is preferable from the viewpoint of effectiveness that the amount is 0.5% by weight or more based on the weight of the epoxy spherical fine particles. . Although it is difficult to unconditionally define the upper limit of coverage, it is preferable that it be 1000% by weight or less in terms of reducing the shedding of adsorbed particles.

[Example] Example 1 A commercially available bisphenol A diglycidyl ether type epoxy resin (Epicote 828, oil-based epoxy resin) was placed in a 100CC polytube, and a commercially available bisphenol A diglycidyl ether type epoxy resin (Epicote 828, oil-based epoxy resin) was placed in a 100CC polytube. Noigun EA, a polyoxyethylene/phenol-substituted ether surfactant
0.8 g of -137 (manufactured by Dai-Kogyo Seiyaku) was added. 80 Orpm, 1 with a stirring rod with a Teflon plate blade attached to the tip.
Kneaded for a minute. Next, add 6cc of water in 4 bowls.
．． 5 CC was added in sequence at 1 minute intervals while stirring at 800 rt) m. A milky white emulsion was obtained in the polycup.

To this uncured epoxy emulsion was added a hardening solution prepared by dissolving 0.6 grams of piperazine in 3 cc of water, and the mixture was homogenized by gentle stirring.

This solution was left standing at 25°C for 5 days, and the average particle size was 6.
It was cured to a spherical shape of 41 μm.

Suction the hardened particles using filter paper; separate them by filtration, re-disperse them into washed particles in water, and create a dispersion containing 10% of the particles by mass/! -1 point.

Equal amounts of rutile-type titanium oxide J[-600A (Teikoku Kako Co., Ltd., average particle size 0.2 μm) and nonionic surfactant Noigun FA-137 are thoroughly kneaded in advance to uniformly disperse titanium oxide. In the previous step, 50% by weight of this slurry was added to the spherical fine particle dispersion liquid based on the solid content (4j is 50 parts titanium oxide to 100 parts of the spherical fine particles), and the mixture was gently mixed with a Teflon-coated magnetic rotor. The temperature was raised to 95°C while stirring. Just like this 1 n
As a result of the treatment, the titanium oxide solution became transparent and the titanium oxide was absorbed into the spherical fine particles. ; After filtration and drying,
When the particles were observed under a SEM electron microscope, it was found that the surface of the spherical fine particles on the right was coated with titanium oxide.

Example 2 A 10 volume % dispersion of fireball-shaped fine particles (right) with an average particle diameter of 6 μm prepared in the same manner as in Example 1 was added to the solid content.
(' 40 "Ji ij'r % (Q"J ')t
';Iko> (J) S 11 S'j Den I'IM
Chemical 7-tan IE CT'T-1 (Titan Kogyo Co., Ltd., τ
[・Uniform particle size: 0.25 μm) slurry was added. This slurry was prepared by thoroughly kneading equal amounts of ECTTl and Noigun [Δ-137]. Phosphoric acid was added to the Teflon-coated magnet 1 while stirring gently with a rotor, so that l-1=3. Next is 7i! 7Q,
When treated at 95°C for 11 hours, the supernatant liquid became transparent and ECT-1 was adsorbed onto the spherical fine particles. S.E.
In the M electron microscope dormitory as well, it was found that ECTT-1 coated the organic spherical particles as in Example 1.

Example 3 In the same manner as in Example 1, 15I was added to a 10% dispersion of organic spherical particles with an average particle diameter of 6 μm, based on the solid content.
A slurry of conductive tin oxide ECPT-1 (manufactured by Mitsubishi Metal Industry Co., Ltd., average particle diameter of 0.1 μm or less) was added in an amount of % (based on particles). This slurry was prepared by thoroughly kneading equal amounts of ECPT-1 and Noigun EAi37 in advance.

Transfer this mixture to a 300CC glass ripple tube with a diameter of 2mm.
Place it in a shaker (Nippon Rikagaku Kikai Co., Ltd., MRK Shaker JMS-1 type) with the glass beads.
300 rl) m for 5 minutes.

Subsequently, a small amount of phosphoric acid was added to make the mixture acidic, and the mixture was shaken again for 30 minutes.

When the particles and glass beads were separated using a 200 m wire mesh and left to stand, the supernatant liquid became transparent, and ECPT-1 was adsorbed to the organic spherical particles. The coating state was confirmed by SEM electron microscopy.

Example 4 10g of Epicoat 828 used in Example 1 was added to 100c
c For polycups, surfactant Noigun EA-137
0.8 g and 0.30 g of crystalline cellulose (Avicel RC-591, manufactured by Fukai Kasei Co., Ltd.) as a powder emulsifier were added. Emulsification was performed in the same manner as in Example 1 to obtain an uncured epoxy emulsion.

Add 10 cc of 0.8 equivalent piperazine to this emulsion.
The hardening liquid dissolved in water was added and homogenized by gentle stirring. Spherical particles with an average particle diameter of 50 μm were obtained by standing at 25° C. for 10 days to avoid curing reaction.

The cured particles were temporarily washed and then redispersed in water to form an approximately 10% dispersion.

Carbon black MΔ-8 (Mitsubishi Kasei Corporation, average particle size 0.1 μm or less) and Neugen EΔ-137 in equal proportions)
The mixture was thoroughly kneaded and added to the above dispersion in an amount of 40% by weight (based on particles) based on the solid content, and the mixture was thoroughly stirred. After adding phosphoric acid to make P l-1 about 3, heat to 98° with stirring.
The temperature was raised to C and the treatment was continued for 11 hours.

After cooling, it was neutralized to PI-1=6.5 with a 1N aqueous sodium hydroxide solution. The upper liquid was transparent, and the carbon black was absorbed by the organic spherical particles. The particles after drying were electrically conductive.

Example 5 Epicor 1-828 4C) q was placed in a 300 cc polycup, and the surfactant Neugun EΔ-137 was added to it for 6 hours.
Then, in the same manner as in Example 1, an uncured epoxy emulsion was prepared by adding 24 cc of water in four parts using a bob. 3
Add 1,5 equivalent h1 of hydrated hydrazine dissolved in 0Q water and let it stand to cure for ○ days at 25°C.U, average particle size 1.
There were 17 spherical particles with a diameter of 5 μm.

The hardened particles were filtered, washed, and then redispersed in 40Qq of water.

After thoroughly kneading magnetic iron oxide BL-120 (manufactured by Jitan Kogyo Co., Ltd., average particle size 0.3 μm) with an equal amount of Noigun E△-137, 90% by weight (based on solid content) was added to the above dispersion. Particles) and phosphoric acid was added up to 12 parts while stirring with a Teflon-coated blade stirrer. Subsequently, the temperature was raised to 60'C. After cooling, pH = 6.5 with 1N caustic soda aqueous solution.
neutralized to.

The supernatant liquid was transparent, and BL-120 was adsorbed to the organic spherical particles.

The particles after filtering and drying exhibited magnetism, and even when suctioned with a V11 stone, the particles behaved as one, and no separation of BL-120 and organic spherical particles was observed.

Example 6 10 Cl of Epikote 828 was placed in a 100 cc polycup, and 0.6 g (as pure content) of Emuljit 49, a commercially available polyoxyethylene alkyl phenyl ether surfactant having an ILB of 20.5, was added thereto. Emulsification was performed in the same manner as in Example 1 to obtain uncured Evogashi emulsion.

To this emulsion was added 1 equivalent of N (
2-Aminoethyl)piperazine was added and homogenized by gentle stirring. After static curing at 25°C for 10 days, 1.7 spherical particles with an average particle diameter of 7.3 μm were obtained. Shifiltration,
After washing, it was redispersed in water to make a 10% slurry. After thoroughly kneading Regi Juno 1 Red No. 202 (average particle size 0.7 μm) with an equal amount of Neugen EA-137, 50% by weight (based on particles) on a solid content basis was added to the slurry above, and Zarani P)-
Phosphoric acid was added up to 14. The mixture was treated at 98° C. for 11 hours while stirring with a magnetic rotor. After cooling, it was neutralized to PI-1=6.5 with a 1N aqueous sodium hydroxide solution. Upper liquid (
was transparent, and the pigment was adsorbed on the spherical particles.

The state of the coating was confirmed by in-depth observation using a SEM electron microscope.

In addition, a stoichiometrically determined equivalent mixture of Epicor 1-828 and N(2-aminoethyl)piperazine was prepared at room temperature 8.
Shore A hardness after standing for a period of time is 80.

Example 7 10 g of commercially available phenol novolak type Epo 4 resin (Ebi = 1-to 152, manufactured by Yuka Shell Epoxy) was
The mixture was placed in a 0 cc polycup, and 0.8 g of surfactant ↑1 agent Noigun FA-137 was added thereto.

Emulsion was carried out in the same manner as in Example 1, followed by aCC.
Add 0.8 equivalents of piperazine dissolved in water and heat at 25°
C. for 6 days to form spherical particles with an average particle diameter of 6 μm.

The hardened particles were filtered and washed, and then redispersed in 190 g of water. Add alumina sol △S-520 (Ell) to this liquid.
Seikagaku Co., Ltd.) (average particle size 0.1 μn or less) was added to the particles at a rate of 30%, and while stirring, 0.1N caustic soda aqueous solution was added to P10 to adsorb the alumina sol to the organic spherical fine particles. .

Organic pigment phthalocyanine blue (average particle size 0°8μm
) was thoroughly kneaded with an equal amount of Nogun LA-137, and then 30% by weight of solid content r-30 (relative to 'D machine spherical fine particles) was added.
The mixture was treated at 98° C. for 10) while stirring with a magnetic rotor. After cooling, the mixture was neutralized to pH=7.5 with a 1N aqueous phosphoric acid solution. The supernatant liquid was transparent, and the pigment was adsorbed on the organic spherical particles.

It should be noted that it was almost impossible to directly adsorb phthalocyanine blue onto the organic particles using the methods of Examples 1 to 6 without first adsorbing the alumina sol onto the organic spherical particles as in this example.

[Effects of the Invention] According to the present invention, it was possible to provide novel coated epoxy-based spherical fine particles in which the surfaces of epoxy-based spherical fine particles are adsorbed and coated with various solid fine particles.

The effects of the present invention are listed below.

■ There are many types of solid particles that absorb into epoxy spherical particles, and many types of coated epoxy spherical particles can be produced.

(2) The amount of solid particles adsorbed to the epoxy spherical particles is large and uniform.

According to the present invention, it is possible to change the hue, chargeability, hydrophilicity, impart magnetism, and conductivity of epoxy spherical fine particles.
It can be used as a drain for electrostatic copying and its auxiliary, as well as chemical products, pharmaceuticals, paints, and adhesives. agent,
Suitable compounding agents for coating agents, inks, paper, films, plastic moldings, etc. have become available.

Special [Applicant] Toshi Co., Ltd.

Claims (2)

[Claims] (1) Coated epoxy spherical fine particles, characterized in that epoxy spherical fine particles cured with an amine curing agent are adsorbed and coated with solid fine particles whose average particle diameters have the following relationship. 5d≦D d: Average particle diameter of solid fine particles D: Average particle diameter of epoxy spherical fine particles (2) Claim 1, characterized in that the epoxy spherical fine particles are obtained by curing epoxy compound fine particles suspended in an aqueous liquid with a water-soluble amine curing agent. coated epoxy spherical particles.