JP3389611B2 - Resin composite spherical powder containing inorganic particles - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Can be controlled over a long period, the content of inorganic particles is high, and
Shape and excellent environmental stability.
Inorganic particle-containing resin composite sphere with controllable electrical properties
It relates to powder. [0002] Resin composite sphere containing inorganic particles according to the present invention
The main use of powder is for magnetic carriers and magnetic toners.
Electrostatic latent image developer material, electromagnetic wave absorbing material and electromagnetic wave seal
Material, brake shoe and polishing material, lubrication material
Material, magnetic separation material, magnet material, ion exchange resin material
Material, immobilized enzyme carrier, display material for display, vibration control
Materials, paint materials, rubber and plastic coloring materials,
Filling materials, reinforcing materials and coloring for paints, paints and adhesives
Materials, matting materials, etc. [0003] In recent years, it has advanced performance and new functions.
Composites between dissimilar materials are being actively developed.
One of which is the use of inorganic particles and organic polymers.
Research and development of composites (hereinafter referred to as composites)
It has been carried out and put into practical use. [0004] These composites are composed of magnetic particles as inorganic particles.
When a magnetic element is used, the magnetic carrier and magnetic
As material powder for electrostatic latent image developer such as toner, inorganic particles
When color pigment particles are used as
Coloring for rubber and plastics, paints, paints and adhesives
Used as an agent and matting agent. In any of the above fields, there is a demand for composites.
The desired properties depend on the application and the desired size of the composite
The particle size is wide, so that the choice of
Can be controlled over a range of more than 0 μm and less than 1000 μm
To fully demonstrate the properties and functions of inorganic particles
Make the content of the above inorganic particles as high as possible.
In order to improve powder characteristics such as flow characteristics and filling properties,
The ring has a complex shape, such as a spherical shape and moisture resistance.
Excellent in environmental stability and depending on the application, conductive
Can be controlled. [0006] The content of inorganic particles contained in the composite
In other words, Japanese Patent Application Laid-Open No. Sho 60-188419
In the case of the emulsion polymerization method and the suspension polymerization method
Another disadvantage is that inorganic or organic particles
In general, it cannot be blended in large quantities. Especially heavy
It is difficult to mix large quantities of
The realization of was desired. As high as possible
Is required. With respect to the average particle size of the composite,
As the carrier material powder, JP-A-1-282563
In the publication, “‥‥ The particle size of the carrier particles is
From the balance between life and photoreceptor carrier adhesion and image quality,
It is appropriate that the average particle size is 20 to 400 μm.
As described in “‥”, a composite of about 20 to 400 μm
However, the material powder for magnetic toner is disclosed in
No. 972, “‥‥ Average particle diameter of toner exceeds 25 μm
When it is obtained, the supply is poor and the image is blurred. ‥
As described in “な る”, a composite of 25 μm or less is required.
ing. Regarding the environmental stability of the composite,
Japanese Unexamined Patent Publication No. Hei 3-203745 discloses that "the amount of triboelectric
Use a toner containing a charge control agent that fluctuates significantly
Image quality changes due to changes in temperature and humidity.
Providing high quality images becomes extremely difficult. "
As described, the amount of triboelectric charge due to fluctuations in temperature, humidity, etc.
Is not changed. Compatibility in vehicle
Speaking of, the surface of the composite becomes compatible with the vehicle etc.
Sufficient, uniform and strong coating with excellent resin
Is required. Next, composite granules are used in various fields.
It is strongly required to have electrical conductivity. In recent years,
Many clean rooms are used from the whole surface, hygiene and accuracy.
To reduce dust and debris in the clean room as much as possible
For this reason, antistatic materials are used in clean rooms.
I'm worried. Also, to prevent discharge breakdown of IC and LSI
Antistatic is required. Generally, antistatic
The material is made of conductive composites such as paint, rubber and plastic.
It is manufactured by dispersing
Have been. In the field of electrostatic latent image developers, magnetic toners
Generally, in addition to ferromagnetic fine particles and resin,
Conductive magnetic toner to which conductive materials such as
Have been. Recently, the use of conductive magnetic toner
The transferred image can be transferred electrostatically onto another recording medium.
There is a disadvantage that it is difficult, and a method to improve this disadvantage
The volume electric resistance is 10 in place of the conductive toner. ¹² Ωc
for developing using magnetic toner having high electric resistance of at least m
There is. Then, use the magnetic toner having a high electric resistance.
In order to improve the developability which is a drawback in the case,
Conductivity smaller than the average particle size of the toner together with the magnetic toner
It has been proposed to use complex composite particles. By the way, conventionally, as an organic polymer, large
Separately, vinyl, styrene, acrylic acid resins, etc.
Thermoplastic resin and phenolic resin, melamine resin,
Although thermosetting resins such as epoxy resins are known,
Generally easy to granulate as a resin for manufacturing composites
Thermoplastic resin is used, and thermosetting resin is granular
However, there is a practical problem because it is difficult to form the particles, particularly, to make the particles spherical. On the other hand, the thermosetting resin is compared with the thermoplastic resin.
It has excellent durability, impact resistance, and heat resistance.
It consists of inorganic particles and thermosetting resin that take advantage of these advantages.
There is a strong demand for composites. Conventionally, inorganic particles and thermosetting resin
As a method of obtaining a composite, inorganic particles and phenol
Cooling and pulverizing after kneading resin and hardener, inorganic material
Protects phenol and formaldehyde in the presence of particles
Method of polymerizing with the aid of colloid (JP-A-54-8)
No. 8995) and phenol in the presence of inorganic particles
Water-insoluble in the polymerization of
The presence of suspension stabilizers such as inorganic salts and water-soluble polymers
(Japanese Patent Application Laid-Open No. 62-27455,
No. 220068) is known. [0014] Inorganic particles and thermosetting
It is composed of phenol resin, which is a resin.
Particle size can be controlled over a wide range, and the content of inorganic particles is possible.
As high as possible and the particle shape is spherical,
Also has excellent environmental stability such as moisture resistance and conductivity control
Are the most demanding composites at present
However, in the case of the known method,
No complex has been obtained. That is, the inorganic particles and the phenol resin and the hard
In the case of cooling and pulverizing after kneading the
Although the content of equipment particles can be somewhat high,
The shape of the composite is irregular. Also, the above-mentioned Japanese Patent Application Laid-Open No. 54-88995.
In the case of the method described in the above, the content of inorganic particles is high
Each is about 75% by weight and its content is limited.
The shape of the surface increases on the curved surface compared to the irregular shape, but it is hard to say that it is spherical
won. Further, the above-mentioned Japanese Patent Application Laid-Open No. 62-27455.
And the method described in JP-A-2-220068.
In some cases, the particle size can be controlled over a wide range depending on the application.
, Which have a high content of inorganic particles and a spherical shape
Compound is obtained, but added to produce the composite sphere.
Suspension stabilizers such as water-insoluble inorganic salts and water-soluble polymers
Inevitably, a large amount remains on the surface of the composite sphere, and as a result,
The environmental stability of compound spheres is poor and the surface of composite spheres
Is difficult to coat uniformly and strongly with metal.
Therefore, it was difficult to control the conductivity. Soshi
To suspend these water-insoluble inorganic salts and water-soluble polymers.
Stabilizers can also be completed by washing with water or acid.
It was difficult to completely remove it. Therefore, the present invention provides a particle size
Size can be controlled over a wide range, the content of inorganic particles is high, and
And spherical, water-insoluble inorganic salts
Or suspension stabilizers such as water-soluble polymers
Environmental stability and control of conductivity.
Technology to obtain resin composite spherical powder containing inorganic particles
Subject. Means for Solving the Problems The technical problems are as follows:
This can be achieved by the present invention as follows. That is, the present invention
Inorganic particles with lipophilic surface and hardened pheno
And resin Spheres without suspension stabilizer Take shape
A composite having a number average particle diameter of 10 μm
Exceeding 1000 μm and containing the inorganic particles.
The surface of the composite sphere having a weight of 80-99% by weight is metal
Inorganic particle-containing resin composite spherical powder coated with
is there. Next, various conditions for implementing the present invention will be described.
I will describe. As the inorganic particles in the present invention, water
Insoluble iron oxide, ferrite, titanium oxide, zinc oxide, etc.
Metal oxides, hydroxides, metals such as aluminum hydroxide
Selected from hydroxides and other sulfides, carbides, etc.
Species or two or more can be used. In the present invention, the inorganic particles are
It is important to carry out lipophilic treatment.
In the case of using inorganic particles that have not been
It is difficult to obtain a composite having a good quality. In the lipophilic treatment, a silane coupling agent or
Treat with a coupling agent such as a titanate coupling agent.
Method or inorganic particles in an aqueous medium containing a surfactant.
A method of dispersing and adsorbing a surfactant on the particle surface
is there. As the silane coupling agent, hydrophobic
Group, amino group, epoxy group, hydrophobic
As a silane coupling agent having a group, vinyl tri
Chlorosilane, vinyltriethoxysilane, vinyl
Ris (β-methoxy) silane, etc.
As a coupling agent, isopropyl triisostearo
Il titanate, isopropyl tridodecyl benzene
Ruphonyl titanate, isopropyl tris (dioctyl
Pyrophosphate) titanate, and the like. A silane coupling agent having an amino group
Are γ-aminopropyltriethoxysilane, N
-Β (aminoethyl) -γ-aminopropyltrimethoxy
Sisilane, N-β (aminoethyl) -γ aminopropyl
Metal dimethoxysilane, N-phenyl-γ-aminop
Propyl trimethoxysilane, and the like. Silane-based coupling having an epoxy group
As the agent, γ-glycidoxypropylmethyldiethoxy
Sisilane, γ-glycidoxypropyltrimethoxysila
, Β- (3,4-ethoxycyclohexyl) trimeth
Xysilane and the like. As the surfactant, a commercially available surfactant is used.
Can be used, having inorganic particles or on the particle surface
Those having a functional group capable of binding to a hydroxyl group are desirable,
Speaking of ionic, cationic or anionic
Is preferred. The present invention can be applied to any of the above-described processing methods.
Can achieve the target, but adhesion with phenolic resin
It has an amino group or an epoxy group in consideration of its properties
Treatment with a silane coupling agent is preferred. The composite spherical material according to the present invention has a number average particle diameter.
Has a spherical shape exceeding 10 μm and 1000 μm or less.
And the content of the inorganic particles is 80 to 99% by weight.
is there. The particle size of the composite sphere is determined by the number average particle diameter.
Is freely controlled in the range of more than 10 μm and 1000 μm
be able to. When the content of the inorganic particles is less than 80% by weight,
In this case, the properties and functions of the inorganic particles can be fully demonstrated.
It is not possible to obtain a complex spherical product. Over 99% by weight
Phenolic resin to bind inorganic particles
Becomes weaker. In the present invention, the surface of the composite sphere is coated.
Metals are known Ni, Co, Cu and Ag,
Control conductivity by changing the type and amount of metal
can do. The amount of metal coating is 0.0
When the content is 5% by weight or more and less than 0.05% by weight,
Insufficient and non-uniform coatings are easily formed,
This makes it difficult to freely control the conductivity. Also,
If the coating amount is too large, the content of inorganic particles in the composite spherical
Degrades and fully develops the properties and functions of inorganic particles.
You will not be able to perform. Preferably 0.1 to 10% by weight.
You. Resin composite sphere containing inorganic particles according to the present invention
Powder is prepared in the presence of inorganic particles and a basic catalyst.
Phenols and phenols and aldehydes in aqueous medium
React and cure while stirring in the body, and harden with inorganic particles.
To form a composite consisting of phenolic resin
The surface is subjected to lipophilic treatment as the inorganic particles
And the stirring is performed at 1 m / sec.
By performing at the above-mentioned peripheral speed of the stirring blade, the surface becomes lipophilic.
Such as treated inorganic particles and cured phenolic resin
A composite having a spherical shape, the number average of the composite being
The particle diameter is more than 10 μm and not more than 1000 μm, and
Composite sphere having a content of the inorganic particles of 80 to 99% by weight
The composite sphere is covered with a metal by chemical plating or the like.
Obtained by overturning. [0034] In the above reaction, the
Occasionally, the curing reaction proceeds to make the surface lipophilic.
Such as treated inorganic particles and cured phenolic resin
After forming a composite spherical product consisting of
Then, an aqueous dispersion containing the composite sphere is obtained. Next, this aqueous dispersion is filtered, centrifuged, etc.
After separating solid and liquid according to the usual method,
More, the surface hardens with the lipophilic inorganic particles
A composite sphere made of the phenol resin is obtained. In the above reaction, the amount of the inorganic particles is
0.5 to 200 times the weight of enols is preferred
No. Considering the strength of the composite spherical powder that is generated,
Preferably it is 4 to 100 times. The phenols include, in addition to phenol,
m-cresol, p-tert-butylphenol, o
-Propylphenol, resorcinol, bisphenol
Alkyl phenols such as
Part or all of the alkyl group is substituted with a chlorine or bromine atom
Phenolic hydroxyl groups such as halogenated phenols
There is a compound having the formula
Phenol is preferred. As the phenol resin, Novola is generally used.
In the plastic type, resole type and natural resin modified molding
Although water-soluble solvents such as alcohol and acetone are acceptable,
Those which dissolve in the agent are desirable. As the aldehydes, formalin or
Formaldehyde in any form of laformaldehyde
And furfural, but formaldehyde is preferred.
Good. Moles of aldehydes to phenols
The ratio is preferably from 1 to 4, more preferably from 1.2 to 3.
is there. When the molar ratio is less than 1, a composite sphere is difficult to form.
And the strength of the resin tends to be weak even if it is formed
There is. On the other hand, if the molar ratio exceeds 4, after the reaction
Unreacted aldehydes remaining in aqueous media increase
Tend. As the basic catalyst, a conventional resole resin
The basic catalyst used in the production can be used,
Water, hexamethylenetetramine, diethyltrim
Alkylamines such as amines and polyethyleneimine.
You. The amount of these basic catalysts based on phenols is
The ratio is preferably 0.02 to 0.7. The reaction is carried out in an aqueous medium.
The total amount of solid content is 30 to 95% by weight.
Preferably, the content should be 60 to 90% by weight.
No. The spheroidization and heavierization of the composite sphere are performed as described above.
Due to shearing and consolidation due to rotation speed during stirring
The stirring speed is an important factor because it is affected by
It is important to carry out at a high stirring blade peripheral speed of not less than seconds. 1
In the case of m / sec or more, the composite obtained as the speed increases
The average particle size of the spherical particles tends to gradually decrease,
At a high stirring speed of about m / s, the average
Particle size less than 10 μm or composite spherical
The phenomenon that the destruction occurs may appear. Furthermore, composite
Duplication affecting the adhesiveness of resin coating on spherical surfaces
The porosity of the spheres will be lost. Stirring speed
Granulation under mild stirring conditions of less than 1 m / sec
Stabilization or control particle size
Or the strength of the composite sphere is weak
Or become. In the reaction, the type of inorganic particles and
Appropriate shearing and consolidation depending on the amount of water used for the reaction.
By changing and adjusting the peripheral speed of the stirring blade in this way,
Control of the average particle size of the composite spheres obtained in the desired range
it can. Here, the stirring blade peripheral speed is the tip of the stirring blade.
It refers to the peripheral speed. Composite spherical material used for coating with metal
Are pre-vacuum dried and dried under normal pressure
Any of the wet condition immediately after filtration
Can also be used. The composite particles are subjected to a well-known chemical plating.
Thus, it can be covered with a metal. That is, chemistry
The plating method is to use a strongly acidic stannous chloride
Immersion solution, then immersion in a strongly acidic palladium chloride solution
After immersion and activation, chemical plating
JP-A-56-25770, JP-B-59-5663
Report), use strongly acidic palladium-tin colloid solution
Catalysis for chemical plating
Method of applying chemical plating and then performing chemical plating (US Patent
No. 3011920), an aqueous suspension containing an object to be plated,
From cationic, anionic and nonionic surfactants
Palladium hydrosol containing one or more selected species
Is mixed and stirred to form a palladium coating on the surface of the object to be plated.
After adsorbing the roid, washing with water and filtering,
The substrate to be plated on which the colloidal
Method (Japanese Patent Publication No. 2-58353) and
The surface of the kimono should be changed to alkaline earth metal chloride or 4th cycle in advance.
After pretreatment with an aqueous solution of a transfer metal salt,
Water suspension containing anionic substances and anionic and / or nonionic
Mix and stir with palladium hydrosol containing surfactant
Adsorb palladium colloid on the surface of the object to be plated.
And then washed with water and filtered.
Method for chemical plating of the plating object on which
By any method such as Japanese Patent Publication No. 2-58354).
It may be. As a metal ion solution for chemical plating
Is one of commonly used nickel, cobalt, copper, silver, etc.
Species or two or more can be used. First, the most important point in the present invention is that the surface is
Lipophilic treated inorganic particles and hardened phenol
A spherical composite comprising a resin and the composite.
The number average particle diameter of more than 10 μm and 1000 μm or less,
And the content of the inorganic particles is 80 to 99% by weight.
Particles whose metal spheres are covered with metal
Resin composite spherical powder has a wide range of particle sizes.
The content of the inorganic particles in the composite is high, and
It has a spherical shape and water-insoluble inorganic salts and highly water-soluble
Due to the absence of suspension stabilizers such as molecules on the surface
Excellent environmental stability such as moisture resistance, controllable conductivity
It is the fact that it is capable. Particle Size of Composite Spherical Material in the Present Invention
Is the solid content in the raw material
Phenol resin component ratio with respect to form concentration and inorganic particles
Number average particle depending on the degree of lipophilicity of the inorganic particle surface
The diameter is controlled in the range of more than 10 μm and 1000 μm or less.
The composite sphere that can be generated as these values increase
The particle size of the articles tends to increase. Also,
As mentioned above, the stirring blade peripheral speed is faster than 1m / sec.
In this case, the particle size of the composite spherical
Noise tends to be smaller. In the present invention, the content of the inorganic particles is high.
The present inventor later explained the reason why a composite sphere was obtained.
As shown in the comparative example, the surface of the inorganic particles is lipophilic.
If not, the content of inorganic particles is controlled.
Lipophilic treatment on the surface of inorganic particles
I believe that it is due to being. In the present invention, water-insoluble inorganic salts and water
Even when no suspension stabilizer such as a soluble polymer is used,
The present inventor will explain later about the reason for obtaining the presented composite.
As shown in the examples and comparative examples described above,
When inorganic particles that do not have
Because no compound can be obtained, lipophilic inorganic particles
I think that it was due to the use of a child. In the present invention, the surface of the composite sphere is treated with water.
Suspension stabilizers such as soluble inorganic salts and water-soluble polymers
Due to excellent environmental stability such as moisture resistance
In both cases, sufficient and uniform coating of metal becomes possible
Therefore, the conductivity is effectively controlled with a small amount of metal coating.
Can also be freely conductive depending on the type of metal
Can be controlled. In the present invention, the composite spherical material
Surface of the composite sphere due to the high content of inorganic particles
Many irregularities are formed, and therefore, the composite spherical object
The metal coated on the surface is firmly coated, such as impact and friction
Is hardly peeled off by the mechanical stress of Next, the present invention will be described with reference to Examples and Comparative Examples.
explain. In the following Examples and Comparative Examples,
The average particle size is measured using a laser diffraction particle size distribution analyzer (Horiba, Ltd.)
(Manufactured by Co., Ltd.).
The child form is a scanning electron microscope S-800 (manufactured by Hitachi, Ltd.)
(Manufactured by Sakusho). The saturation magnetization is
Type magnetometer VSM-3S-15 (manufactured by Toei Kogyo Co., Ltd.)
And the value measured under an external magnetic field of 10 KOe.
Was. The content of inorganic particles in the composite depends on the true
Use a multi-volume density meter (Micromeritics, Inc.)
) And calculate from this specific gravity.
The calculated values are shown. The conductivity was measured using a TRG142 current generator (Bamboo
DA-RIKEN Co., Ltd.) and ME-540 voltmeter (SOAR
Measured by the four-terminal method using
You. The humidity resistance was measured at a temperature of 33 ° C. and a relative humidity of 90%.
Environment (hereinafter referred to as environment A), temperature 15 ° C, relative humidity
15% environment (hereinafter referred to as environment B)
And the toner charge amount measured in (1). That is, under both environments
The smaller the fluctuation of the toner charge, the better the environmental stability
Means that. The charge amount of the toner is determined according to the composite sphere 9
5 parts by weight and commercially available toner CLC-200 black (product
200m mixture with 5 parts by weight (manufactured by Canon Inc.)
g is blow-off charge amount measuring machine Model TB-200
(A) (μ) measured using a Toshiba Chemical Co., Ltd.
From c), the formula [A × 1 / 0.2 × 0.05 (μc / g)]
Indicated by the value calculated as the converted value per g obtained according to
Was. <Production of Composites> Examples 1 to 10 Comparative Examples 1 to 3; Example 1 A spherical particle having an average particle diameter of 0.24 μm in a Henschel mixer.
After mixing 400 g of magnetite particles and stirring well,
Tanate-based coupling agent (Preneact TTS: Ajino
2.0 g) and heated to about 100 ° C.
By mixing and stirring well for 30 minutes,
Spherical magnetite particles coated with TTS were obtained.
Separately, in a 1 l four-necked flask, 40 g of phenol, 3
7% formalin 60g, lipophilic magnetite
400 g, 10 g of 28% ammonia water, 60 g of water 2 m
Rises to 85 ° C in 40 minutes while stirring at a blade peripheral speed of /
And reacted and cured at the same temperature for 180 minutes.
Magnetite particles covered and hardened phenolic tree
A composite consisting of fat was produced. Next, in the flask
Was cooled to 30 ° C. and 0.5 l of water was added.
Thereafter, the supernatant was removed, and the lower layer precipitate was washed with water.
Air dried. Then, this is put under reduced pressure (5 mmHg or less)
After drying at 50 to 60 ° C., the composite sphere (hereinafter, composite sphere)
A). The obtained composite sphere A has a number average particle size.
70 μm, and a scanning electron microscope photograph (× 10
00), it has a spherical shape close to a true sphere.
As shown in the scanning electron micrograph (× 10000) of
The surface of the composite sphere was uneven. Also, the magneta
The content of the particles was 86.3% by weight,
Conversion was 74 emu / g. Examples 2 to 10, Comparative Examples 1 and 2 Types and amounts of inorganic particles, types and amounts of lipophilic treatment agents,
Type and amount of phenols, amount of 37% formalin, salt
Various types and amounts of basic catalyst, amount of water and stirring blade speed
Except having changed, composites B through
L was obtained. Table 1 shows the main manufacturing conditions at this time,
Table 2 shows various characteristics. The composites obtained in Examples 2 to 10 were scanned
Observations by scanning electron microscope show that each of them has a spherical shape close to a true sphere
Was. Composite spherical product obtained in Example 3 and Example 4
Is a scanning electron micrograph (× 300) of FIG. 3, and FIG.
Each is shown in a scanning electron micrograph (× 3000).
The composite obtained in Comparative Example 1 is a scanning electron microscope shown in FIG.
As shown in the photograph (× 300), it had an irregular shape. Ma
The composite obtained in Comparative Example 2 was observed with a scanning electron microscope.
As a result of the observation, it was found that the average particle diameter was 10 μm or less.
Was. Examples 2 and 3,
"KBM-602 (trade name: used in each of Examples 5 and 8)
Shin-Etsu Chemical Co., Ltd.) is a silane cup with an amino group.
It is a ring agent and each of Examples 4, 6, 7, 9, 10
"KBM-403" (trade name: Shin-Etsu Chemical Co., Ltd.)
Is a silane coupling agent having an epoxy group.
You. In Example 9, commercially available phenolic resin was used.
Novolac resin "Barcam TD-213 (product
Name: Dainippon Ink and Chemicals, Inc.) "
Use 20g of methanol in addition to water to dissolve in water
Was. In Example 10, commercially available water was used as the phenol resin.
"Plyofen 5023" which is a soluble resol resin
(Trade name: manufactured by Dainippon Ink and Chemicals, Inc.). Comparative Example 3 50 g of phenol, 37%
6.5 g of formalin, spherical particles having an average particle size of 0.24 μm
400 g of gnetite, 7.8 g of 28% ammonia water,
1 g of calcium iodide and 100 g of water are added with stirring
While stirring at a blade peripheral speed of 2 m / sec.
° C, react at the same temperature for 180 minutes, cure,
A composite consisting of gnetite and cured phenolic resin
Generated. Next, cool the contents in the flask to 30 ° C.
And after adding 0.5 l of water, the supernatant is removed,
The lower composite was washed with water and air-dried. Then this
Is dried under reduced pressure (5 mmHg or less) at 50 to 60 ° C.
A composite sphere (hereinafter, referred to as composite sphere M) was obtained. Get
Table 2 shows various properties of the obtained composite sphere M. <Coating with Metal> Examples 11 to 17 Comparative Example 4 Preparation of Palladium Hydrosol Samples A to C; Sample: A
Dissolve in 2.5 ml of an aqueous solution containing 250 μmol,
To 94 ml with pure water. This solution is stirred vigorously
While stearyl trimethyl ammonium chloride
1 ml of an aqueous solution containing 10 mg is added, followed by hydrogenation
5 ml of an aqueous solution containing 200 μmol of sodium iodide is dropped
When lowered, the color of the solution changes suddenly, and the color is black-brown and transparent at pH 9.0.
Palladium hydrosol was obtained. Sample: B Polyethylene glycol-p-nonyl as a surfactant
Phenyl ether (Polyethylene glycol polymerization degree 1
PH 8.5 in the same manner as in Sample A except that 0) was used.
Of palladium hydrosol was obtained. Sample: C sodium dodecylbenzenesulfonate as a surfactant
PH 8.7 in the same manner as Sample A, except that
A palladium hydrosol was obtained. Preparation of Metal Plating Solution Samples I to III; Sample: I (Preparation of Nickel Plating Solution) 0.1 mol of anhydrous nickel (II) chloride at 4 mol / l
Dissolved in an aqueous ammonia solution at a concentration of 0.2 mol /
l of sodium hypophosphite 500 ml and add a total volume of 1
and then adjust the pH of the solution to 8.9 with concentrated hydrochloric acid.
Was. Sample: II (Preparation of Cobalt Plating Solution) 0.05 mol of cobalt (II) sulfate heptahydrate, 0.05 mol.
2 mol sodium hypophosphite, 0.2 mol que
Sodium phosphate dihydrate and 0.5 mol of sulfuric acid
Dissolve monium in pure water to make a total volume of 1 liter.
A pH of 1 was added by adding a 7.4 mol / l aqueous ammonia solution.
Adjusted to zero. Sample: III (Preparation of copper plating solution) 0.8 mol / l of Rossell salt and 0.8 mol / l of
Sodium hydroxide and 0.5 mol / l copper sulfate (I
I) Dissolve pentahydrate in pure water to make 100 ml, and add 3 ml
100 ml of a 5% formaldehyde solution was mixed. Example 11 A composite particle A having an average particle diameter of 70 μm (conductivity 6.3 ×
10 ^-8 S / cm) of 10 g of palladium hydro
Immersed in 300 ml of water at room temperature for 60 minutes, washed with water and filtered
did. Composite granules adsorbed with the above palladium colloid
The product A was immersed in the nickel chemical plating solution of Sample I at room temperature.
Thereafter, it was washed with water and dried. The conductivity of the obtained composite granule is
1.3 S / cm. As a result of observation with an electron microscope, a particle table was obtained.
It was confirmed that the surface was uniformly and firmly plated.
Was. Examples 12 to 16 and Comparative Example 4 Composite granules to be plated, palladium hydrosol
Implemented except for various types of plating and chemical plating solution
Obtain composite spheres plated with metal in the same manner as in Example 11.
Was. Main manufacturing conditions and metal-plated composite spheres
Table 3 shows the properties of the article. Further, in Examples 11 to 16
The metal-plated composite sphere obtained in each example was
As a result of electron microscope observation, the particle surface is uniform and strong.
It was confirmed that plating was performed. Obtained in Comparative Example 4
Metal-plated composite spheres are made of calcium fluoride
Because the control of conductivity is not enough due to the presence of
Metal coating was found to be insufficient and uneven
You. Example 17 10 g of the composite granules A was 1.7 g of stannous chloride, concentrated hydrochloric acid
Disperse and mix in a solution consisting of 3.0 ml and 150 ml of water
After leaving for 60 minutes, the mixture was filtered off. The resulting particle powder
To 0.13 g of palladium chloride, 3.0 ml of concentrated hydrochloric acid and water
Disperse and mix in a 150 ml solution and leave for 60 minutes
After that, the mixture was separated by filtration and activated. Activation process
The composite granules were recovered using the nickel plating solution of Sample I.
Nickel plating was performed in the same procedure as in Example 11. [Table 1] [Table 2] [Table 3] The resin composite sphere containing inorganic particles according to the present invention
The particles are made up of inorganic particles whose surface is
And a spherical composite comprising a phenolic resin and a phenolic resin.
The number average particle diameter of the composite is more than 10 μm and not more than 1000 μm
Below, and the content of the inorganic particles is 80 to 99 weight
% Of the composite sphere is coated with metal.
Particle size can be controlled over a wide range,
High in particle content and spherical
Also, suspension stabilizers such as water-insoluble inorganic salts and water-soluble polymers
Environment such as moisture resistance due to the absence of surface
Excellent stability and sufficient and uniform metal coating
The presence allows control of conductivity.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron micrograph (× 1000) showing the particle structure of the composite sphere obtained in Example 1. FIG. 2 is a scanning electron micrograph (× 10000) showing the particle structure of the surface of the composite sphere obtained in Example 1. FIG. 3 is a scanning electron micrograph (× 300) showing the particle structure of the composite sphere obtained in Example 3. FIG. 4 is a scanning electron micrograph (× 3000) showing the particle structure of the composite sphere obtained in Example 4. FIG. 5 is a scanning electron micrograph (× 300) showing the particle structure of the composite sphere obtained in Comparative Example 1. FIG. 6 is a scanning electron micrograph (× 100) showing the particle structure of a composite spherical object coated with metal obtained in Example 11.
0).

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiki Matsui 1-4, Meiji Shinkai, Otake City, Hiroshima Prefecture Inside the Otake Plant of Toda Kogyo Co., Ltd. (56) References JP-A-3-263801 (JP, A) JP-A 3-152553 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08J 3/12-3/16 B01J 2/00, 13/02

Claims (1)

(57) [Claims] [Claim 1] The surface is composed of lipophilic inorganic particles and a hardened phenol resin, and contains a suspension stabilizer.
A composite exhibited Manai sphere shape, the composite number average particle diameter of 10μm or less 1000μm beyond is, and, the surface of the composite spherical matter content is 80 to 99% by weight of the inorganic particles a metal A resin composite spherical powder containing inorganic particles, characterized by being coated with: