JP3499881B2 - Resin composite spherical powder containing inorganic particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention has a wide range of particle sizes.
Can be controlled over a long period, the content of inorganic particles is high, and
Shape, and with environmental stability and vehicle, etc.
Resin spheres containing inorganic particles with excellent compatibility
It relates to a powdery substance. [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] 2. Description of the Related Art In recent years, it has advanced performance and new functions.
Composites between different types of materials are being actively developed.
One of them 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
Inorganic particles as material powder for electrostatic latent image developer such as toner
When colored 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
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 must have a spherical shape and moisture resistance.
Excellent environmental stability and compatibility with vehicles, etc.
Is to be excellent. [0006] The content of inorganic particles contained in the composite
In other words, Japanese Patent Application Laid-Open No.
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 a large amount. 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, “号 The particle size of the carrier particles is
From the balance between life and photoconductor 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 size of toner exceeds 25 μm
If it does, the supply will be poor and the image will be blurred. ‥
As described in “な る”, a composite of 25 μm or less is required.
ing. With respect to the environmental stability of the composite,
Japanese Unexamined Patent Publication No. Hei 3-203745 discloses that "the amount of triboelectricity varies depending on humidity.
Use toner containing 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. Conventionally, as organic polymers, 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 producing composites
Thermoplastic resin is used, and the thermosetting resin is granular
However, there is a practical problem because it is difficult to form the particles, particularly, to make the particles spherical. [0010] On the other hand, thermosetting resins are less than thermoplastic resins.
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
Method of cooling and pulverizing after kneading resin and curing agent, inorganic substances
Protects phenol and formaldehyde in the presence of particles
Polymerization with the aid of colloid (Japanese Patent Laid-Open No. 54-8 / 1979)
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. 22068) is known. [0012] SUMMARY OF THE INVENTION Inorganic particles and thermosetting
It is made 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 compatibility with vehicles, etc.
Composites are currently the most demanding
However, in the case of the above-mentioned known method, such duplication still exists.
No compound 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 as compared to the irregular shape, but it is hard to say that it is spherical
won. Further, Japanese Patent Application Laid-Open No. 62-27455, cited above.
And a 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,
The environmental stability of compound spheres is poor, and the surface of composite spheres
It is difficult to coat the resin uniformly and firmly
Compatibility with vehicles, etc.
Was. And these water-insoluble inorganic salts and water-soluble polymers
Suspension stabilizers such as washing with water or acid.
However, it was difficult to completely remove it. Therefore, the present invention provides a method for preparing a particle
Size can be controlled over a wide range, the content of inorganic particles is high, and
, Spherical and water-insoluble inorganic salts
Or suspension stabilizers such as water-soluble polymers
Environmental stability and compatibility with vehicles, etc.
Technology to obtain resin composite spherical powder containing inorganic particles
It is a technical task. [0017] Means for Solving the Problems The technical problems are as follows.
Can be achieved by the present invention. That is, the present invention
Is treated with a coupling agent having an amino group or an epoxy group.
Such as treated inorganic particles and cured phenolic resin
A composite having a spherical shape, wherein the number average of the composite is
The particle size 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 surface of the object0.05 to 10% by weight based on the weight of the composite sphere
ofResin composite sphere containing inorganic particles coated with resin
It is a powder. 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
With a coupling agent having an amino group or an epoxy groupprocessing
It is important to dosurfaceNot processed
When inorganic particles are used, a spherical composite is obtained.
It becomes difficult. [0020]surfaceTreatment is performed using a silane coupling agent or
Treat with a coupling agent such as a tanate coupling agent
There are methods. As the silane coupling agent, hydrophobic
Group, amino group, epoxy group
As a silane coupling agent having a group, vinyl tri
Chlorosilane, vinyltriethoxysilane, vinyl
S (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
Γ-aminopropyltriethoxysilane, N
-Β (aminoethyl) -γ-aminopropyltrimethoxy
Sisilane, N-β (aminoethyl) -γ aminopropyl
Metal dimethoxysilane, N-phenyl-γ-aminop
And propyltrimethoxysilane. A silane coupling having an epoxy group
As the agent, γ-glycidoxypropylmethyldiethoxy
Sisilane, γ-glycidoxypropyltrimethoxysila
, Β- (3,4-ethoxycyclohexyl) trimeth
Xysilane and the like. [0024] According to any of the above processing methods,
Can achieve the target, but adhesion with phenolic resin
Has amino group or epoxy group in consideration of 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 size.
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 composite sphere that can be cut. Over 99% by weight
Phenolic resin to bind inorganic particles
Becomes weaker. In the present invention, the surface of the composite sphere is coated.
Well-known resins include epoxy resin and polyester resin.
Fat, styrene resin, melamine resin, acrylonitrile
Polymer, polyamide resin, silicon resin and fluororesin
There is one or more kinds of resins selected from
Phase with the vehicle or resin composition
Solubility can be improved. The coating amount of the resin is0.
05-10% by weightAnd less than 0.05% by weight
Is likely to result in an insufficient and uneven coating,
Improve compatibility with the target vehicle and freely adjust the charge amount
It becomes difficult to control. Also, if the coating amount is too large
The content of inorganic particles in the composite sphere is reduced,
The various properties and functions possessed cannot be exhibited sufficiently. Good
Preferably, it is 0.1 to 10% by weight. The 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 or phenols and aldehydes in aqueous medium
React and cure while stirring in the body, and harden with inorganic particles.
The formation of a composite consisting of phenolic resin
Per, as the inorganic particlessurface treatmentBeing inorganic
While stirring the particles at a rate of 1 m / sec or more.
By performing at the peripheral speed of the stirring blade, the inorganic
Of spherical particles composed of particles and cured phenolic resin
A composite having a number average particle size of 10 μm
Exceeding 1000 μm and containing the inorganic particles.
Obtaining a composite spherical material having a weight of 80 to 99% by weight;
Obtained by coating spherical objects with resin in the usual way
You. In the above reaction, the reaction is the same at 80 ° C. or higher.
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, the 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 a 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. As phenols, 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 a phenol resin, Novola is generally used.
In the plastic type, resole type, and modified natural resin
Water-soluble solvents such as alcohol and acetone may be used.
Those that 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, it is difficult to form a composite sphere.
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, ordinary resole resins
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 water 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 carried out by
Shearing and consolidation due to the rotation speed during stirring
The stirring speed is an important factor because it is affected by
It is important to perform at a high stirring blade peripheral speed of at least 2 seconds. 1
In the case of m / sec or more, the composite obtained as the speed increases
The average particle size of the spheres tends to gradually decrease,
At a high stirring speed of about m / sec, the average
Particle size less than 10 μm or composite spherical
The phenomenon that the destruction of the material occurs may appear. Furthermore, composite
Duplication affecting adhesion of resin coating on spherical surface
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 in the reaction.
By changing and adjusting the peripheral speed of the stirring blade in this way,
Control the average particle size of the composite spherical product obtained by
it can. Here, the peripheral speed of the stirring blade is the tip of the stirring blade.
It refers to the peripheral speed. Composite spherical material used for coating with resin
Are pre-vacuum dried and dried under normal pressure
Any of the wet state immediately after filtration
Can also be used. The coating of the composite sphere with a resin is well known in the art.
The method may be performed according to the following method. Me
Coating with lamin resin, composite spheres and melamines and
Aldehydes and neutralized or weakly basic aqueous media
The reaction is performed by stirring and reacting, followed by gelation.
U. Gelation may be performed in the presence of an acidic catalyst if necessary.
Is also good. Further heat treatment of the gelled product
Harden. The temperature at this time is preferably 130 to 150 ° C.
New The ultrafine melamine resin is a composite spherical material.
Surface can be uniformly and densely coated,
The electrical resistance of the composite sphere can be effectively improved
You. Moreover, it is coated with ultra-fine melamine resin.
Large specific surface area and high effective electrical resistance
Easy to be. Melamines include melamine and melamine
Adducts of formaldehyde, such as dimethylolmela
Min, trimethylol melamine, hexamethylol melamine
Precondensates of mine and melamine / formaldehyde
Of these, melamine is most preferred. An example of a coating reaction with a melamine resin is as follows.
Will be described. While stirring the aqueous medium vigorously, melamine
Aldehydes and complex spheres at room temperature
After adjusting H to 7 to 9.5, 0.5 to 1.5 with stirring.
° C / sec, preferably at a rate of 0.8 to 1.2 ° C / sec.
To 90 ° C., preferably 80 to 85 ° C.
React for 10-30 minutes, preferably 15-20 minutes
Let Next, the content is cooled to 30 ° C. or less.
After adding the acidic catalyst, the heating rate was gradually increased while stirring.
At a reaction temperature of 75 to 95 ° C, preferably 80 to 90 ° C.
Reacted for 60-150 minutes, preferably 80-110 minutes
Let In such a reaction, a gelation reaction occurs simultaneously with the reaction.
Then, the surface of the particles is coated with the melamine resin. This
After the reaction and coating, the reaction product is cooled to 30 ° C or less.
In other words, the particle surface is coated with ultra-fine melamine resin
The obtained aqueous dispersion of the composite sphere is obtained. Next, this dispersion is subjected to filtration, centrifugation and the like.
After solid-liquid separation according to the method, washing is performed,
Ultra-fine melamine by heat treatment at a temperature of 0 to 150 ° C
When the resin is cured, the surface is evenly hardened into ultrafine particles.
A composite sphere coated with the melamine resin is obtained. Next, coating with an acrylonitrile polymer
Is a simple substance composed mainly of composite spheres and acrylonitrile
Stir in a weakly acidic aqueous medium under an inert gas atmosphere
And then polymerize. Acrylonitrile
The main monomer is insoluble in water as the polymerization proceeds
Precipitates on the surface of composite spheres as ultrafine particles or film-like substances
You. Composite sphere because it can be uniformly and densely coated
The electric resistance of the object can be effectively improved. As the monomer, acrylonitrile or
Uses a mixture of acrylonitrile and other vinyl monomers.
Can be used. Use in addition to acrylonitrile
There is no restriction on the vinyl monomer.
Len, divinylbenzene, vinyltoluene 4-bromos
Styrene compounds such as styrene, methyl methacrylate,
Methyl acrylate, acrylic acid, ethylene glycol dye
Tacrylate, 2-hydroxyethyl methacrylate, etc.
Can be used. The acidic catalyst optionally used includes:
Mineral acids such as sulfuric acid and hydrochloric acid, formic acid, phosphoric acid, oxalic acid, etc.
Can be The amount of these acidic catalysts used depends on the pH of the reaction initiation system.
Is preferably maintained so as to be 5 to 6. A composite spherical material and acrylonitrile as main components
Reacts with inert gas such as nitrogen, argon, etc.
It is carried out in an atmosphere and proceeds at a temperature in the range of room temperature to 70 ° C.
Let go. Inert gas is oxygen that prevents the progress of the polymerization reaction.
It is necessary for the purpose of removing
Reaction speed is low and efficiency is poor. At temperatures above 70 ° C
The polymerization reaction rate is too high, and a uniform film cannot be obtained. Ma
The amount of water charged is not particularly limited, but the amount of the composite
It is desirable that the content be about 60% by weight. A composite spherical material and acrylonitrile as main components
An example of a coating reaction with a monomer to be formed will be described below. nitrogen
Under air flow, disperse the composite spheres in an aqueous medium,
A nitrile monomer and an acid catalyst were added, and the temperature was raised to 35 ° C.
Stir for ~ 15 minutes. Here potassium persulfate and sulfurous acid
Slowly add aqueous sodium solution and react at the same temperature for 1-3 hours.
Respond. In such a reaction, the particle surface is
Is coated with an acrylonitrile-based polymer. in this way
After reacting and reacting, the reactant is cooled to 20 ° C.
Particle surface is coated with acrylonitrile polymer
An aqueous dispersion of the composite sphere is obtained. Next, the dispersion is filtered or centrifuged.
After solidification and separation according to a conventional method, washing is performed.
Acrylonitrile polymer after heat treatment at 20 ° C
Acrylonitrile-based polymerization
A composite sphere covered with a body coat is obtained. Coating with a polyamide can be carried out by using the well-known anion.
A polymerization method can be used. In other words,
Lactams, their solvents and anionic polymerization catalysts
Of the composite particles in a polyamide polymerization solution
Activate the lactam by adding an activator under stirring
Nion polymerization is initiated and ring opening polymerization of lactams
This is done by producing lamide. Polyamide formed by the progress of the polymerization reaction
Makes the entire surface of the composite spherical object uniformly and densely coated
Can effectively increase the electrical resistance of the composite sphere.
High mechanical strength.
Can be. As lactams, polyamides are produced.
All lactams such as caprolactam, enane
Lactam, capryllactam, lauryl lactam, etc.
Of these, caprolactam is the most preferred.
New The proportion of lactams used is
And preferably 0.5 to 40% by weight, particularly preferably 5 to 40% by weight.
30% by weight. If less than 0.5% by weight, coating
The amount may be insufficient, while exceeding 40% by weight
In some cases, the polyamide resin forms
Separation from objects may be difficult. The solvent used is in the range of 80 to 200 ° C.
Halogenated or unhalogenated with a boiling point of
Aliphatic hydrocarbons, such as paraffinic or cycloaliphatic or
Is an aromatic (eg, xylene or toluene) solvent
is there. This solvent dissolves the lactam,
Catalyst that does not dissolve and is used in the method of the present invention.
That do not react with any of the chemicals, lactams, and composite spheres
Must. The catalyst is sodium or a compound thereof, for example,
For example, sodium hydride or sodium methylate
And preferably sodium hydride. The activator is lactam N-carboxyani
Lido, isocyanate, carbodiimide, cyanimid
, Acyllactam, triazine, urea, N-substituted imine
And esters. The coating reaction with the polyamide resin is carried out using an organic solvent.
In this case, the amount of solvent charged in this case is not particularly limited.
No, so that the concentration of the composite sphere is 10 to 50% by weight.
Is desirable. An example of a polyamide coating reaction is described below.
I do. Nitrogen atmosphere in the order of solvent, composite sphere, and lactam
At room temperature, add at room temperature and heat up slowly with gentle stirring
Degree: 0.5 to 10 ° C./min, preferably 2 to 6 ° C./mi
90 to 150 ° C, preferably 100 to 120 ° C at n
The temperature is raised and at this temperature for 30 to 120 minutes, preferably 4
Maintain for 5 to 75 minutes to dissolve all lactams,
5 to 30% of the solvent used is distilled off, and it may be present
Water which has potential is distilled off by azeotropic distillation. Then in the atmosphere
, Add the catalyst and stir at 90-150 ° C, preferably
Or heated to 100-130 ° C and dissolved in a solvent beforehand.
Activated activator at a constant rate for 1-4 hours, preferably
After the addition in 1.5 to 3 hours, the reaction temperature is 90-150.
C., preferably at 100 to 130 ° C. for 10 to 90 minutes.
Preferably, the reaction is carried out for 20 to 60 minutes. By such a reaction,
Polyamide is uniformly coated on the particle surface. in this way
After reacting and coating, cool the reaction to below 30 ° C
And a composite sphere with a spherical surface coated with polyamide
A solvent dispersion of the product is obtained. Next, this dispersion is usually subjected to filtration, centrifugation, etc.
After solid-liquid separation by the method,
The spheres are dried at a temperature of 80-100 ° C. further,
Neutralize the alkaline catalyst residue with a weak acid aqueous solution such as phosphoric acid and solidify.
After liquid separation, it is dried again at a temperature of 80 to 100 ° C.
And a composite spherical object whose surface is uniformly coated with a polyamide layer
Is obtained. Epoxy resin, polyester resin, polystyrene
For example, coating with resin, silicon resin and fluorine resin
For example, using a spray dryer to apply resin to the composite spherical
How to spray, Henschel mixer, high speed mi
Dry mixing of composite spheres and resin using xer etc.
Method, a method of impregnating a composite spherical material into a solvent containing a resin, etc.
Either method may be used. As the epoxy resin, bisphenol A
Epoxy resin and novolak epoxy resin
Ester resins such as ethylene glycol and triethyl
Polyols such as len glycol and dicarboxylic acids, for example
For example, it is obtained by condensation polymerization of maleic acid, itaconic acid, etc.
Polyester resins, etc.
Polystyrene such as polystyrene and styrene-butyl acrylate
-Acrylic copolymer, styrene-butadiene copolymer
Styrene-maleic anhydride copolymer, etc.
Heat-curable silicone resin or cold-curable silicone resin
Silicone resin such as silicone resin or silicone oil
Or a silane coupling agent, etc.
Is polytetrafluoroethylene, polyvinylidene fluoride
And tetrafluoroethylene-ethylene copolymers.
A nitrogen-containing resin or the like can be used. [0067] First, the most important point in the present invention is that the surface is
Treated with coupling agent having amino group or epoxy group
Inorganic particles and cured phenolic resin
A composite having a spherical shape comprising:
The diameter is more than 10 μm and not more than 1000 μm, and
Composite sphere with content of inorganic particles of 80-99% by weight
The surface of an object0.05 to 10% by weight based on the composite sphere
Resin composite spherical powder containing inorganic particles coated with resin
The body has a wide range of control over particle size,
High in the content of inorganic particles
Suspension stabilizers such as water-insoluble inorganic salts and water-soluble polymers
Environmental stability such as moisture resistance due to absence of surface
Excellent compatibility with both vehicle and vehicle
It is real. Particle Size of Composite Spherical Material in the Present Invention
Is the solid content in the raw materials
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 within 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 particle surface of the inorganic particles issurface
If not treated, the content of inorganic particles is limited
The surface of the inorganic particles is not treated.
I think that it is due to. In the present invention, water-insoluble inorganic salts and water
Even when a suspension stabilizer such as a soluble polymer is not used,
The present inventor will explain later about the reason why the presented composite is obtained.
As shown in Examples and Comparative Examples described below,surfaceBeing processed
When inorganic particles are not used, spherical composite
Because you can not get things,surfaceTreated inorganic particles
I think it is due to the use. 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 resin becomes possible
Therefore, the compatibility with the vehicle and the resin in the resin composition is excellent.
In particular, the type of resin coated on the surface of the composite sphere is
When the same type of vehicle or resin in the resin composition
Means that the surface compatibility of the composite sphere is more improved
Become. And the amount of charge can be effectively controlled with a small amount of resin coating.
Can be controlled, and the amount of charge can be
It can be controlled freely. In the present invention, the composite sphere is contained in
Surface of the composite sphere due to the high content of inorganic particles
Many irregularities are formed, and therefore, the composite spherical
The resin that is coated on the surface is firmly coated, and it is possible to
Is hardly peeled off by the mechanical stress of [0073] Next, the present invention will be described based on 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
Multi-volume density meter (Micromeritics
) And calculate from the magnitude of this specific gravity.
The calculated value was shown. The moisture 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)
It is shown by the toner charge amount measured in. In other words, 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 Composite> Example 19 Comparative Examples 1-3 Example 1 A spherical particle with an average particle size of 0.24 μm in a Henschel mixer
After mixing 400 g of magnetite particles and stirring well,Shi
runCoupling agent"KBM-602 (trade name: Shin-Etsu
Chemical Co., Ltd.) "Add 2.0 g and heat up to about 100 ° C
And then mix and stir well for 30 minutes.KBM-6
02To obtain spherical magnetite particles. Another
In a 1 l four-necked flask, 40 g of phenol, 37
% Formalin 60g,surfaceTreated magnetite 40
0g, 28% ammonia water12g, water40g1.8m
Rises to 85 ° C in 40 minutes while stirring at a blade peripheral speed of / s
And react and cure at the same temperature for 180 minutes,KBM-6
02Magnetite particles coated with
A composite comprising a phenolic resin and a phenolic resin was produced. Next,
Cool the contents of Lasco to 30 ° C and remove 0.5 l of water.
After the addition, the supernatant is removed and the lower precipitate is removed.
Washed and air dried. Then, this was removed under reduced pressure (5 mmHg
Dried at 50 to 60 ° C. to form a composite sphere (hereinafter, composite
(Referred to as sphere A). The obtained composite sphere A has a number average particle diameter.
30μm, scanning electron microscope (× 1000)Observation
Result, A spherical shape close to a true sphere, and a scanning electron microscope
Mirror (× 10000)Observation results, The surface of the composite sphere is concave
It was convex. In addition, the content of magnetite particles,
81.3Weight percent, and the saturation magnetization is70emu / g
there were. Example 29, Comparative Examples 1-2 The type and amount of inorganic particles,surfaceType and amount of treatment agent
Type and amount of enols, amount of 37% formalin, base
The type and amount of the reactive catalyst, the amount of water, and the stirring blade speed
Except that the compound B was changed to the composite BK
Got. Table 1 shows the main manufacturing conditions at this time.
Table 2 shows the characteristics. Example 29The composite obtained in the above is a scanning type
As a result of observation with an electron microscope, each of them showed a spherical shape close to a true sphere.
I was Example2And examples3Composite sphere obtained in
The figure1Scanning electron micrograph (× 300) of FIG.2of
Each is shown in a scanning electron micrograph (× 3000).
The composite obtained in Comparative Example 1 is shown in FIG.3Scanning electron microscope
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 as small as 10 μm or less.
Was. Incidentally,surfaceExamples as treatment agents1,2,
4,7"KBM-602 (trade name:
Shin-Etsu Chemical Co., Ltd.) is a silane cup with an amino group.
Example of a ring agent3,5,6,8,9Examples of each
"KBE-403" (trade name: Shin-Etsu Chemical Co., Ltd.)
Is a silane coupling agent having an epoxy group.
You. Also, the embodiment8Is a commercially available phenolic resin
Novolac resin "Barcam TD-213 (product
Name: Dainippon Ink and Chemicals, Inc.) at the beginning of the reaction
Use 20 g of methanol in addition to water to dissolve in water
Was. Example9Is a commercially available water-soluble phenolic resin
Plyofen 5023 (a commercial resin)
Product name: manufactured by Dainippon Ink and Chemicals, Inc.). Comparative Example 3 In a 1 l three-necked flask, 50 g of phenol, 37%
6.5 g of formalin, spherical particles having an average particle diameter 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 with stirring
And 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.
After adding 0.5 l of water, the supernatant was 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.
Composite spherical object (hereinafter, composite spherical object)L). Get
Composite sphereLAre shown in Table 2. <Coating with Resin> Example10~14 Comparative Example 4; [0083] [0084] [0085] [0086] [0087] Example10 Compound spheres in a Henschel mixer under a stream of nitrogenB1
Kg andPolyester resin FC-023 (Mitsubishi Rayon
(Made by Corporation)Add 15 g and heat to 120 ° C with stirring
Then, the mixture was stirred at the same temperature for 1 hour.polyesterBy resin
The coating is a scanning electrophotographic microscopeObservation results, Enough and even
Was one. GotpolyesterCovered by resin
Table 4 shows various properties of the composite spherical material. Example11, Comparative Example 4 Various types of composite spheres, resin types and mixing amounts
Example except for10Covered with resin in the same way as
The obtained composite sphere was obtained. Main conditions and various conditions at this time
Show characteristics3Shown in The resin obtained in Comparative Example 4
The overlaid composite spheroids are exposed to the presence of calcium fluoride.
Due to insufficient moisture resistance, the charge
Insufficient, sufficient and uniform resin coating
Not admitted. [0090] [Table 1][0091] [Table 2][0092] [0093] [Table 3][0094] The resin composite sphere containing inorganic particles according to the present invention
The surface of the objectCups with amino or epoxy groups
With a ring agentTreated inorganic particles and phenolic resin
And a spherical composite comprising:
The average particle diameter is more than 10 μm and not more than 1000 μm, and
In addition, the content of the inorganic particles is 80 to 99% by weight.
Because the surface of the composite sphere is covered with resin,
Particle size can be controlled over a wide range, including inorganic particles.
High weight, spherical, and water-insoluble
Suspension stabilizers such as water-soluble inorganic salts and water-soluble polymers
Environmental stability, such as moisture resistance, and
Both have excellent compatibility with vehicles and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron micrograph (× 300) showing the particle structure of the composite sphere obtained in Example 2 . FIG. 2 is a scanning electron micrograph (× 3000) showing the particle structure of the composite sphere obtained in Example 3 . FIG. 3 is a scanning electron micrograph (× 300) showing the particle structure of the composite sphere obtained in Comparative Example 1.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08K 9/06 C08L 61/06 C08L 61/06 C09D 7/12 C09D 7/12 C09J 11/04 C09J 11/04 C09K 3/14 520L C09K 3/14 520 C10M 171/06 C10M 171/06 C12M 1/40 Z C12M 1/40 C10N 20:06 A G03G 9/083 B01J 13/02 L 9/107 G03G 9/08 101 C10N 20:06 9 / 10 311 321 (72) Inventor: Shigeru Horai, Otake Plant, Meiji Shinkai 1-4, Otake City, Hiroshima Pref. (72) Inventor Hiroshi Akai Otake, Inc. 1-4, Meiji Shinkai, Otake City, Hiroshima Prefecture In the factory (56) References JP-A-4-34441 (JP, A) JP-A-3-152553 (JP, A) JP-A-4-11624 (JP, A) JP-A-2-2200 68 (JP, A) JP-A-2-68138 (JP, A) Patent 3001239 (JP, B2) Patent 3389611 (JP, B2) Patent 3175743 (JP, B2)

Claims (1)

(57) [Claim 1] A composite having a spherical shape composed of inorganic particles whose surface is treated with a coupling agent having an amino group or an epoxy group and a cured phenol resin. The number average particle size of the composite exceeds 10 μm and is 1000
μm or less, and the content of the inorganic particles is 80 to 9
9% by weight of the surface of the composite spherical object is
A resin composite spherical powder containing inorganic particles, which is coated with 0.05 to 10% by weight of a resin.