JPH05186604A - Inorganic particle-containing epoxy resin granule powder - Google Patents

Abstract

PURPOSE:To provide composite granule powder, comprised of inorganic particles and an epoxy resin, with its granular size controllable over a wide range, adequately high in inorganic powder content, also controlled in electrical conductivity. CONSTITUTION:The objective granule powder with the granule surface coated with metal. The granules, comprised of (A) surface-lipophilized inorganic particles and (B) a cured epoxy resin, have the following characteristics: (1) number-average particle diameter: 1-1000mum and (2) the content of the inorganic particles: 80-99wt.%.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to an inorganic material in which the particle size can be controlled over a wide range, the content of the inorganic particles is high, and the surface properties of the granular material are coated with a metal. The present invention relates to an epoxy resin granule powder containing inorganic particles, which comprises an epoxy resin granule containing particles.

[0002]

2. Description of the Related Art The main uses of the epoxy resin granular powder containing inorganic particles according to the present invention are material powders for electrostatic latent image developers such as magnetic carriers, magnetic toners and conductive magnetic particles, electromagnetic wave absorbers, and Electromagnetic wave shield material powder, rubber, plastic coloring material, filler and reinforcing material, paint,
It is a coloring material for paints and adhesives, a matting material, a filling material and a reinforcing material.

In recent years, composite materials between different materials have been vigorously used as materials having high performance and novel functions. One of them is a composite granular material composed of inorganic particles and organic polymer (hereinafter, Various researches and developments have been carried out on the composite granular material, and they have been put to practical use.

These composite particles are mainly composed of a magnetic carrier when magnetic particles are used as the inorganic particles.
When colored pigment particles are used as the inorganic particles as the material powder for the electrostatic latent image developer such as magnetic toner and conductive magnetic powder, the coloring agent mainly for rubber, plastic, paint, paint and adhesive, Used as a matting agent.

In all of the above-mentioned fields, the properties commonly required for the composite granules are such that the composite granules having a desired size can be selected in a wide range of particle sizes depending on the application. In particular, it can be controlled over a range of 1 to 1000 μm, the content of the inorganic particles is as high as possible so that various properties and functions of the inorganic particles can be sufficiently exerted, and a composite depending on the application. That is, the conductivity of the granular material can be controlled.

First, regarding the average particle diameter of the composite granular material, as a conventional carrier material powder, Japanese Patent Laid-Open No.
No. 282563, “... The particle size of carrier particles is appropriate to be an average particle size of 20 to 400 μm in view of the balance between the developer life and the adhesion of the photoreceptor carrier and image quality.” As described below, the composite granular material of about 20 to 400 μm is used as the magnetic toner material powder.
JP-A No. 1-172972 describes that "when the average particle diameter of the toner exceeds 25 μm, the replenishment property is poor and the image becomes rough. When it is less than 5 μm, the cleaning property and the transfer property are deteriorated.” As described above, a composite granular material having a particle size of about 5 to 25 μm is used as a conductive magnetic powder.
The volume average particle diameter of the conductive magnetic particles is ⅕ of that of magnetic toner (about 5 to 25 μm).
It is preferable that the particle size is about 4/5, and the like.

Regarding the content of the inorganic particles contained in the composite granular material, Japanese Patent Laid-Open No. 60-188419 is used.
Another drawback of the emulsion polymerization method and the suspension polymerization method of the publication is that particles cannot generally be mixed with a large amount of inorganic or organic particles. In particular, it is difficult to mix a large amount of inorganic particles having a high specific gravity. , "The realization of such particles has been desired." As high as possible is required.

Next, it is strongly required that the composite particles have conductivity in various fields. In recent years, the use of clean rooms has increased in terms of safety, hygiene, and accuracy, and in order to minimize dust and dirt in clean rooms, antistatic materials have begun to be used in clean rooms. In addition, it is necessary to prevent static electricity in order to prevent discharge damage of ICs and LSIs. In general, an antistatic material is manufactured by dispersing conductive composite particles in a paint, rubber, plastic or the like to impart conductivity.

In the field of electrostatic latent image developers, generally known as magnetic toner is a conductive magnetic toner obtained by adding a conductive material such as carbon in addition to ferromagnetic fine particles and resin. In addition, recently, an image developed using a conductive magnetic toner has a drawback that it is difficult to electrostatically transfer it onto another recording medium. Instead, the volume electric resistance is 10 ¹² Ωc
There is a method of developing using a magnetic toner having a high electric resistance of m or more. In order to improve the developability, which is a drawback of using the magnetic toner of high electric resistance, use of a conductive composite granular material having a smaller average particle diameter of the toner together with the magnetic toner of high electric resistance. Is proposed.

By the way, conventionally, organic polymers are roughly classified into thermoplastic resins such as vinyl-based, styrene-based, and acrylic acid-based resins and phenol-based resins, melamine-based resins,
Although thermosetting resins such as epoxy resins are known,
As the resin for producing the composite granules, a thermoplastic resin that is easily granulated is generally used, and it is difficult to granulate, and in particular, a thermosetting resin that is difficult to obtain spherical particles was not used. ..

On the other hand, the thermosetting resin is superior to the thermoplastic resin in durability, impact resistance and heat resistance. Therefore, a composite consisting of inorganic particles and the thermosetting resin, which takes advantage of these advantages, is used. Granular material is strongly demanded.

Conventionally, as a method for obtaining a composite composed of inorganic particles and a thermosetting resin, a method of pulverizing a composite composed of inorganic particles, an epoxy resin and a phenol resin acting as a curing agent (Japanese Patent Laid-Open No. 58-58). JP-A-122705), and as a method of granulating an epoxy resin, a method of preparing an uncured epoxy emulsion with the aid of an emulsifier and curing the uncured epoxy emulsion with a curing agent (Japanese Patent Laid-Open No. 2005-120605) JP-A-53-73249) is known. Furthermore, as a method for producing a composite particle comprising inorganic or organic particles and an epoxy resin, in the presence of inorganic or organic particles, an uncured epoxy emulsion is prepared with the aid of an emulsifier, and a water-soluble amine compound A method of curing with a curing agent (JP-A-60-188419) is known.

[0013]

A composite comprising inorganic particles and an epoxy resin, the particle size of which can be controlled over a wide range, the content of the inorganic particles is as high as possible, and the conductivity of which is controlled. Granular materials are currently most demanded, but in the case of the above-mentioned conventional method,
Such composite granules have not been obtained.

That is, according to the method described in JP-A-58-122705, the content of inorganic particles is high, but granulation is difficult.

Further, in the case of the method described in the above-mentioned JP-A-60-188419, the particle size of the composite granules is about 0.5 to 100 μm, and composite granules exceeding 100 μm are obtained. However, the content of the inorganic or organic particles is about 75% by weight at most, and the content is limited.

Further, since the cured epoxy resin particles are produced in the presence of 5% by weight, preferably 10% by weight or more of an emulsifier with respect to the resin, it is highly possible that the emulsifier is contained. It is high, and as a result, the charge amount of the composite granules tends to fluctuate, causing a problem in terms of product quality.

Therefore, the present invention comprises inorganic particles and an epoxy resin, the particle size can be controlled over a wide range, the content of the inorganic particles is as high as possible, and the conductivity is controlled. A technical problem is to obtain a composite granular material without using an emulsifier or the like.

[0018]

The above technical problems can be achieved by the present invention as follows.

That is, the present invention is composed of inorganic particles whose surface is made lipophilic and hardened epoxy resin, has a number average particle diameter of 1 to 1000 μm and a content of the inorganic particles of 80 to It is an inorganic resin particle-containing epoxy resin granular material powder in which the surface of the granular material of 99% by weight of the composite granular material is coated with a metal.

Next, various conditions for carrying out the present invention will be described.

The composite granules according to the present invention are obtained by reacting bisphenols and epihalohydrin in an alkaline aqueous medium in the presence of inorganic particles, or by curing an uncured epoxy resin in an aqueous medium. In producing a composite granular material composed of inorganic particles and a cured epoxy resin, it is obtained by using, as the inorganic particles, inorganic particles whose surface is subjected to lipophilic treatment.

The inorganic particles in the present invention may be those which are not dissolved in water or are not altered or modified by water. For example, magnetite particles ( FeO _x.
Fe ₂ O ₃ (0 <x ≦ 1)), maghemite particles, particles obtained by depositing or containing cobalt on these, hematite particles, ferric hydroxide particles, ferrite particles containing barium or strontium, and manganese. Oxide particles such as spinel type ferrite particles containing one or more kinds of metals selected from nickel, zinc and zinc, titanium oxide particles, silica particles, talc particles, alumina particles, barium sulfate particles, barium carbonate particles. , Cadmium yellow particles, calcium carbonate particles, zinc white particles and the like can be used.

As for the particle morphology of these inorganic particles, any shape such as cubic, polyhedral, spherical, acicular and plate-like can be used, and the average particle diameter is the desired composite particle. It can be used as long as it is smaller than the average particle diameter of the product, but is 0.01 to 5.0 μm, and particularly 0.1 to 5.0 μm.
It is preferably in the range of 2.0 μm.

The inorganic particles whose surface is subjected to lipophilicity treatment according to the present invention can be prepared by simply mixing the inorganic particles and the lipophilicity treating agent or by mixing the inorganic particles and the lipophilicity treating agent in an aqueous solvent. Then, it can be obtained by any method such as a method of adsorbing the lipophilic treatment agent on the particle surface.

As the lipophilic treatment agent, a titanate-based or silane-based coupling agent having a lipophilic group, a silylating agent, and silicone oil can be used.
In particular, those having a functional group reactive with the epoxy resin (-NH _2, Formula 1, etc.) are preferable because an effect of such increase the strength of the composite granules themselves.

[0026]

[Chemical 1]

Examples of titanate coupling agents having a lipophilic group include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis ( Dioctylpyrophosphate) ethylene titanate and the like are silane coupling agents having a lipophilic group, such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
-Phenyl-γ-aminopropyltrimethoxysilane,
γ-glycidoxypropylmethyldiethoxysilane, β
-(3,4 epoxycyclohexyl) ethyltrimethoxysilane (the above are silane coupling agents having a functional group capable of reacting with an epoxy resin), vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy). Ethoxy) silane and the like, silylating agents such as hexamethyldisilazane, trialkylalkoxysilane and trimethylethoxysilane, and silicone oils such as dimethyl silicone oil and methyl hydrogen silicone oil.

The amount of treatment with the lipophilic treatment agent is 0.1 to 5.0% by weight based on the inorganic particles. If the amount is less than 0.1% by weight, the lipophilic treatment is insufficient, and thus the composite particulate material having a high content of inorganic particles, which is the object of the present invention, cannot be obtained. If it exceeds 5.0% by weight, the degree of lipophilicity is too large, and the adhesiveness of the produced composite granules increases, causing aggregation of the composite granules, resulting in one large lump. Therefore, it becomes difficult to control the particle size of the composite granular material.

As the bisphenols in the present invention, compounds having two or more phenolic hydrogen groups such as bisphenol A, bisphenol F, bisphenol S and resorcin can be used. Bisphenol A is preferable from the economical point of view.

The amount of bisphenols used is 0.5 to 25% by weight based on the inorganic particles. If the amount is less than 0.5% by weight, the amount of the epoxy resin produced becomes insufficient with respect to the inorganic particles, so that it becomes difficult to obtain a composite granular material. When it exceeds 25% by weight, the amount of the epoxy resin produced becomes excessive with respect to the inorganic particles, and it is impossible to obtain a composite granular material having a high content of the inorganic particles, which is the object of the present invention. In addition, agglomeration of the composite granules easily occurs, and it becomes difficult to control the particle size of the composite granules.

As the epihalohydrin in the present invention, epichlorohydrin, epibromhydrin, epiiodohydrin and the like can be used, and epichlorohydrin is preferable.

The amount of epihalohydrin used is 0.3 to 20% by weight based on the inorganic particles. If the amount is less than 0.3% by weight, the amount of the epoxy resin produced becomes insufficient with respect to the inorganic particles, so that it becomes difficult to obtain composite particles. If it exceeds 20% by weight, the amount of the produced epoxy resin will be excessive with respect to the inorganic particles, and it is impossible to obtain a composite granular material having a high content of the inorganic particles, which is the object of the present invention. In addition, agglomeration of the composite granules easily occurs, and it becomes difficult to control the particle size of the composite granules.

The bisphenols and epihalohydrin used in the present invention are used in a molar ratio of 0.5 to 1.0:
It is 1.0. When it is less than 0.5, the granulation becomes difficult due to the influence of reaction by-products and the like caused by the excess epihalohydrin. If it exceeds 1.0, the curing rate will be high, and it will be difficult to obtain composite granules, and even if obtained, the spread of the particle size distribution will be large.

The alkaline aqueous medium in the present invention is obtained by adding an alkali such as sodium hydroxide or potassium hydroxide to water.

The reaction in the present invention is carried out by stirring an alkaline aqueous medium containing inorganic particles, bisphenols and epihalohydrin in the presence of a curing agent at 60 to 90 ° C.
The temperature is raised to a temperature in the range of 1 to allow the polymerization reaction to proceed for about 1 to 5 hours, or while stirring in an aqueous medium containing inorganic particles and an uncured epoxy resin in the presence of a curing agent, 60
It is carried out by elevating the temperature to a temperature in the range of to 90 ° C. and allowing the curing reaction to proceed for about 1 to 8 hours.

The curing agent is widely known as a curing agent for epoxy resins. For example, acid anhydrides and amines can be used.

As the uncured epoxy resin, epoxy compounds having two or more epoxy groups in the molecule such as glycidyl ether at both ends of bisphenol A and glycidyl ether at both ends of polyethylene glycol can be used.

In the present invention, the composite particles formed in the alkaline aqueous medium or in the aqueous medium may be subjected to solid-liquid separation by a usual method such as filtration and centrifugation, and then washed with water and dried by heating.

As the composite particles used for coating with the metal, any of those which have been previously vacuum-dried, those which have been dried under normal pressure, and those which have been wet immediately after filtration can be used.

The composite granules can be coated with metal by well known chemical plating. That is, as a method for chemical plating, a material to be plated is immersed in a strongly acidic stannous chloride solution, then immersed in a strongly acidic palladium chloride solution for activation treatment, and then chemically plated. 56-25770, Japanese Examined Patent Publication No. 59-5663), a method of contacting an object to be plated with a strongly acidic palladium-tin colloidal solution to impart palladium that acts as a catalyst for chemical plating, and then performing chemical plating. (U.S. Pat. No. 3,011,920), an aqueous suspension containing an object to be plated and a palladium hydrosol containing one or more selected from cationic, anionic and nonionic surfactants are mixed and stirred. Then, the palladium colloid is adsorbed on the surface of the object to be plated, washed with water, filtered, and then the object to be plated on which the palladium colloid is adsorbed is chemically plated. Method (Japanese Patent Publication No. 2-58353) and the surface of an object to be plated are pre-treated with an aqueous solution of an alkaline earth metal chloride or a fourth period transition metal salt in advance, and then a water suspension containing the pre-treated object to be plated The liquid and a palladium hydrosol containing an anionic and / or nonionic surfactant are mixed and stirred to adsorb the palladium colloid on the surface of the object to be plated, then washed with water and filtered, and then the palladium colloid Any method such as a method of chemically plating the object to be adsorbed (Japanese Patent Publication No. 2-58354) may be used.

As the metal ion solution for chemical plating, one or more kinds of nickel, cobalt, copper, silver and the like which are commonly used can be used.

The metal coating amount was 0.
When it is at least 05% by weight and less than 0.05% by weight, an insufficient and nonuniform coating is likely to be formed, and it becomes difficult to freely control the conductivity which is the object of the present invention. On the other hand, if the coating amount is too large, the content of the ferromagnetic fine particles in the composite granular material decreases, and a large magnetization value cannot be obtained. It is preferably 0.1 to 10% by weight.

[0043]

First, the most important point in the present invention is that the surface is composed of inorganic particles having a lipophilic treatment and a cured epoxy resin, and the number average particle diameter is 1 to 1000 μm. The inorganic particle-containing epoxy resin particles in which the surface of the composite particles having a content of 80 to 99% by weight is coated with a metal can control the particle size over a wide range, and the content of the inorganic particles is It is high and its conductivity is controlled.

The particle size of the composite granules in the present invention is the solid concentration in the raw material charged in producing the composite granules, the ratio of the epoxy resin component to the inorganic particles, the degree of lipophilicity of the surface of the inorganic particles, and the like. The particle size of the composite granules produced tends to increase as these values increase.

With respect to the reason why a composite granular material having a high content of inorganic particles can be obtained in the present invention, the present inventor has
As shown in Comparative Examples below, when the particle surface of the inorganic particles is not subjected to lipophilic treatment, since the content of the inorganic particles is limited, the particle surface of the inorganic particles have been subjected to lipophilic treatment. I believe that this is due to

In the present invention, the reason why the emulsifier does not have to be used is that the inventor uses the uncured epoxy resin, which is the initial reaction product, and the inorganic particles by making the surface of the inorganic particles lipophilic. This is probably because the properties of the composite are very easy to emulsify.

In the present invention, the conductivity can be freely controlled by controlling the type and amount of the metal coated on the surface of the granular material of the composite granular material.

In the present invention, since the content of the inorganic particles contained in the composite granules is high, many irregularities are formed on the surface of the composite granules. The metal that is coated on the surface of the granular material is strongly adhered,
It is difficult to peel off due to mechanical stress such as impact or friction.

[0049]

The present invention will be described below with reference to Examples and Comparative Examples. In addition, the number average particle diameter in the following examples and comparative examples is shown by a value measured by a laser diffraction type particle size distribution meter (manufactured by Horiba Ltd.), and the particle morphology of the composite particles is a scanning type. Electron microscope S-800 (Co., Ltd.)
It was observed by Hitachi). Saturation magnetization is a vibrating sample magnetometer VSM-3S-15 (Toei Industry Co., Ltd.)
Manufactured by K.K.) and the value was measured under an external magnetic field of 10 KOe. The content of the inorganic particles in the composite granules is shown by a value calculated by measuring the true specific gravity of the composite granules using a multi-volume densitometer (manufactured by Micrometics Co., Ltd.) and calculating from the magnitude of this specific gravity. It was Conductivity is T
RG142 current generator (manufactured by Takeda Riken Co., Ltd.) and ME
It was measured by a four-terminal method using a -540 voltmeter (manufactured by SOAR Co., Ltd.).

<Production of Composite Granules> Examples 1 to 17 Comparative Examples 1 to 2; Example 1 In a 500 ml four-necked flask, 50 ml of water, 5.50 g of sodium hydroxide, 20 g of bisphenol A, 10 g of epichlorohydrin, anhydrous. Silane coupling agent KBM602 having 2.0 g of phthalic acid and 0.5% by weight of particle surface
200 g of magnetite particles (average particle diameter 0.24 μm) coated with (manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred. After the temperature was raised to 80 ° C. at a rate of 1.0 to 1.5 ° C./min, the mixture was continuously stirred for 1.5 hours at the normal temperature to form a composite granular material. Next, the content in the flask was filtered off, washed with water and dried to obtain a composite granular material. The obtained composite granular material had a number average particle diameter of 36.6 μm, and
As shown in the scanning electron micrograph (× 1500), the shape was close to a true sphere. Further, as shown in the scanning electron micrograph (× 12000) of FIG. 2, it was confirmed that the surface of the composite granular material was formed with a large number of irregularities of the inorganic particle units contained therein. The content of magnetite particles was 86.6% by weight, and the saturation magnetization was 73.6 emu / g.

Examples 2-17, Comparative Examples 1-2 Except that the types of inorganic particles, the amount of bisphenol, the amount of epichlorohydrin, the amount of sodium hydroxide, the type and amount of the curing agent, and the amount of water were variously changed. A composite granular material was produced in the same manner as in Example 1. Examples 2 to 1
Composite granules B to Q were obtained by the respective examples of No. 7. As a result of observing each of the obtained composite granular materials B to Q with a scanning electron microscope, many irregularities were formed on the surface. The composite particles obtained in Example 2 and Example 5 are the scanning electron micrographs (× 150) of FIGS. 3 and 4, respectively.
As shown in 0), it had a spherical shape.

Table 1 shows the main production conditions at this time, and Table 2 shows various characteristics of the composite granular material. As a result of electron microscopic observation, the products obtained in Comparative Examples 1 and 2 were a mixture in which inorganic particles and resin were separated. Incidentally, "KBE403" and "KBE903" used as lipophilic agents are both silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd.
"Planeact TTS" is a titanate coupling agent manufactured by Ajinomoto Co., Inc.

<Coating with Metal> Examples 18 to 24; Preparation of Palladium Hydrosol Samples A to C; Sample: A Palladium (II) chloride (50 μmol) was dissolved in an aqueous solution (2.5 ml) containing sodium chloride (250 μmol), and then purified water. Diluted to 94 ml. While vigorously stirring this solution, 1 ml of an aqueous solution containing 10 mg of stearyltrimethylammonium chloride was added, and then 5 ml of an aqueous solution containing 200 μmol of sodium borohydride was added dropwise, the color of the solution suddenly changed, and a blackish brown transparent palladium having a pH of 9.0 was obtained. A hydrosol was obtained.

Sample: B Polyethylene glycol-p-nonylphenyl ether as a surfactant (Polyethylene glycol polymerization degree 1
0) was used in the same manner as Sample A except that pH was 8.5.
To obtain a palladium hydrosol.

Sample: C A palladium hydrosol having a pH of 8.7 was obtained in the same manner as in Sample A except that sodium dodecylbenzenesulfonate was used as the surfactant.

Preparation of metal plating solution Samples I to III; Sample: I (preparation of nickel plating solution) 0.1 mol of anhydrous nickel (II) chloride 4 mol / l
Dissolved in an aqueous ammonia solution of 0.2 mol / mol
1 volume of sodium hypophosphite (500 ml)
After adjusting to 1, the pH of the solution was adjusted to 8.9 with concentrated hydrochloric acid.

Sample: II (Preparation of cobalt plating solution) 0.05 mol of cobalt (II) sulfate heptahydrate, 0.
2 mol of sodium hypophosphite, 0.2 mol of sodium citrate dihydrate and 0.5 mol of ammonium sulfate were dissolved in pure water to a total volume of 1 l, and a 7.4 mol / l aqueous ammonia solution was added to the solution. PH to 1
Adjusted to 0.

Sample: III (preparation of copper plating solution) 0.8 mol / l of Rochelle salt, 0.8 mol / l of sodium hydroxide and 0.5 mol / l of copper sulfate (I
I) Dissolve pentahydrate in pure water to make 100 ml, and further add 3
100 ml of 5% formaldehyde solution was mixed.

Example 18 Composite granular material A having an average particle diameter of 86.6 μm (conductivity: 5.
10 g of (9 × 10 ⁻⁸ S / cm) was immersed in 38 ml of the palladium hydrosol of Sample A at room temperature for 60 minutes, then washed with water and separated by filtration. The composite granular material A having the palladium colloid adsorbed thereon was immersed in the nickel chemical plating solution of Sample I at room temperature, washed with water and dried. Table 3 shows the main production conditions and various properties of the nickel-plated composite particles at this time.
As a result of electron microscopic observation, it was confirmed that the obtained composite granular material was uniformly and strongly nickel-plated on the particle surface.

Examples 19 to 23 Metal-plated composites were carried out in the same manner as in Example 18 except that the kind of the composite granular material as the object to be plated, the kind of palladium hydrosol and the kind of the chemical plating solution were changed. Granules were obtained. Table 3 shows the main production conditions and various characteristics of the metal-plated composite particles at this time. In addition, Example 19
As a result of electron microscopic observation, it was confirmed that the surface of each of the metal-plated composite particles obtained in each of Examples to No. 23 was uniformly and strongly plated.

The electric conductivity of the composite particles B and C before the metal plating treatment was 6.7 × 10 ^-8 S / cm and 8.
It was 3 × 10 ⁻⁸ S / cm.

Example 24 10 g of the composite granular material A was dispersed and mixed in a solution of 1.7 g of stannous chloride, 3.0 ml of concentrated hydrochloric acid and 150 ml of water, left for 60 minutes, and then filtered. The obtained particle powder was dispersed and mixed in a solution consisting of 0.13 g of palladium chloride, 3.0 ml of concentrated hydrochloric acid and 150 ml of water, left for 60 minutes, and then filtered and activated. The activated composite granules were nickel-plated using the nickel plating solution of Sample I in the same procedure as in Example 18.
Table 3 shows the main production conditions and various properties of the nickel-plated composite particles at this time. As a result of electron microscopic observation, it was confirmed that the obtained composite granular material was uniformly and strongly nickel-plated on the particle surface.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

EFFECTS OF THE INVENTION The inorganic particle-containing epoxy resin granular material powder according to the present invention is composed of inorganic particles whose surface has been subjected to lipophilic treatment and epoxy resin, and the particle size can be controlled over a wide range. Content is high and the conductivity is controlled. In addition, since the inorganic particle-containing epoxy resin particulate powder according to the present invention does not contain an emulsifier, there is no fluctuation in the charge amount, so that no problem in terms of product quality occurs, and durability and resistance It is also excellent in impact resistance and heat resistance.

[0067]

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph (× 1500) showing a particle structure of a composite granular material obtained in Example 1.

2 is a scanning electron micrograph (× 15000) showing the surface state of the composite granular material obtained in Example 1. FIG.

FIG. 3 is a scanning electron micrograph (× 1500) showing the particle structure of the composite granular material obtained in Example 2.

FIG. 4 is a scanning electron micrograph (× 1500) showing the particle structure of the composite granular material obtained in Example 5.

5 is a scanning electron micrograph (× 2000) showing the particle structure of the composite granular material obtained in Example 18. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiki Matsui 1-4 Shinkai, Meiji Shinkai, Otake City, Hiroshima Prefecture Toda Kogyo Co., Ltd. Otake Plant

Claims (1)

[Claims] 1. A surface comprising inorganic particles having a lipophilic treatment and a cured epoxy resin, and having a number average particle diameter of 1
To 1000 μm, and the content of the inorganic particles is 8
Epoxy resin granule powder containing inorganic particles, characterized in that the surface of the granules of the composite granules is 0 to 99% by weight.