JP2003147089A - Composite particle of amino resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain amino resin composite particles in which an inorganic compound is fixed on the surface of the amino resin particles, e.g. the amino resin composite particles in which child particles comprising the inorganic compound are fixed on the surface of mother particles comprising the amino resin particles. SOLUTION: The amino resin composite particles are obtained by reacting an amino compound such as benzoguanamine or the like with formaldehyde to prepare a reactive solution containing an amino resin precursor to be the mother particles, subsequently mixing the reactive solution with an aqueous dispersion of the inorganic compound such as silica powder or the like to be child particles in the presence of an emulsifier by adding shearing force to obtain an emulsion and add a catalyst to the emulsion and cure the emulsion to obtain the amino resin composite particles. The obtained amino resin composite particles have >=10% fixing percentage of the inorganic compound measured by coming off test.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to, for example, a matting agent for paints, a light diffusing agent, a rheology control agent, a column filler, an IC filler, a film coating agent, a wax additive, or an antibody, a conductive agent. The present invention relates to an amino resin composite particle that can be suitably used as a hydrophilic particle, a cosmetic, a particle for toner, an additive for toner, an abrasive, and the like.

[0002]

2. Description of the Related Art Conventionally, as one method for producing composite particles, for example, as a method for coating particles, there are a hybrid method, a microencapsulation method, a spray coating method and the like. For example, the hybrid method is a mother particle particles such as polyamide resin or polyacrylic resin, as a child particle particles such as titanium oxide or silica, by mixing the mother particles and child particles by dry mixing, This is a method in which the collision energy (impact force or heat) is used to implant a plurality of child particles on the surface of the mother particles and the mother particles are coated with the child particles.

However, in the above hybrid method in which dry mixing is performed, when the mother particles become hard to a certain extent or more, it becomes impossible to drive the child particles onto the surface of the mother particles. Therefore, the hybrid method is unsuitable as a method for producing composite particles by fixing inorganic compound particles such as titanium oxide on the surface of particles such as amino resin particles having a crosslinked structure.

On the other hand, as a method for forming amino resin particles as composite particles, a method is known in which an inorganic resin particle is attached to the surface of the amino resin particle by curing the amino resin precursor in the presence of the inorganic compound. ing. For example, in JP-A-52-51493, a catalyst is used,
A method for producing amino resin composite particles having silica particles adhered on the surface thereof is disclosed by curing a benzoguanamine resin precursor together with a melamine resin precursor and silica particles in an emulsion state.

[0005]

However, in the method described in the above publication, the benzoguanamine resin precursor is cured with simple stirring to obtain the amino resin composite particles, so that the silica particles are fixed to the amino resin particles. Therefore, if an external force is applied to the amino resin composite particles, most of the silica particles will fall off from the amino resin particles.

Further, in the method described in the above publication, a homomixer is used in the emulsification step for obtaining the amino resin precursor, but in the subsequent steps such as the inorganic compound addition step and the curing step, the inorganic compound is added. It is not specifically shown that a shearing force is applied in order to fix the compound to the amino resin particles. Also, of course, in the above publication,
There is no suggestion or description of the amino resin composite particle itself in which the inorganic compound is fixed to the amino resin particle, of course, the amino resin composite particle in which the inorganic compound is fixed on the surface of the amino resin particle at a high fixation rate. Is not disclosed.

In the above publication, from the viewpoint of disintegration during pulverization,
The inorganic resin is merely attached to the amino resin particles in order to prevent aggregation of the amino resin particles in the curing step, and the amino resin particles obtained by these known methods are filtered, dried, pulverized, classified, etc. Inorganic compounds fall off after a normal purification step of amino resin particles. Therefore,
In the amino resin particles produced by the known technique, the inorganic compound is substantially not firmly fixed (fixed) to the surface of the amino resin particles, and the inorganic compound particles are more likely to fall off even when external force is applied. It was not possible to obtain a few amino resin composite particles.

Therefore, there is a demand for amino resin composite particles in which the inorganic compound particles are less likely to fall off even when an external force is applied, that is, amino resin composite particles in which the inorganic compound particles are fixed on the surface of the amino resin particles. .

The present invention has been made in view of the above conventional problems, and an object thereof is to provide amino resin composite particles in which an inorganic compound is fixed on the surface of amino resin particles, for example, mother particles composed of amino resin particles. An object is to provide amino resin composite particles in which child particles made of an inorganic compound are fixed on the surface.

[0010]

Means for Solving the Problems The inventors of the present invention set the production conditions for fixing an inorganic compound on the surface of amino resin particles, particularly the stirring conditions for mixing an amino resin precursor emulsion and an inorganic compound. Various studies were conducted. As a result, the inventors of the present application have found stirring conditions to be adopted in order to stably obtain the amino resin composite particles. Further, when the inventors of the present application pay attention to the sticking ratio of the inorganic compound that has fallen off from the amino resin composite particles as the physical properties of the finally obtained amino resin composite particles, they show the morphology of the amino resin composite particles accurately. I found that I could do it.

In order to solve the above problems, the amino resin composite particles of the present invention are amino resin composite particles in which an inorganic compound is fixed on the surface of the amino resin particles, and the amino resin composite particles are 10% by weight. Diameter of suspension containing 92m
In a container having a diameter of 40 mm, a stirring blade having a blade size of 40 mm in diameter was used, and the peripheral speed of the tip of the stirring blade was 5.2 m /
It is confirmed that the inorganic compound is dropped from the surface of the amino resin composite particles by stirring under the condition of s, and the sticking rate of the inorganic compound obtained by measuring the amount of the dropped inorganic compound is 10% or more. It has a feature.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention are characterized in that the amount of the inorganic compound dropped off from the surface of the amino resin composite particles is measured by a centrifugal separation method. There is.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention are characterized in that the amount of the inorganic compound dropped off from the surface of the amino resin composite particles is measured by a heat treatment method. .

Furthermore, the amino resin composite particles of the present invention are
In order to solve the above problems, the inorganic compound is fixed as child particles on the surface of the mother particles with the amino resin particles as mother particles, and the average particle diameter of the inorganic compound is amino that is mother particles. 0.0 of the average particle diameter of the resin particles
5 to 0.001 times, the average particle size of the amino resin particles is in the range of 1 to 30 μm, and the average particle size of the inorganic compound is in the range of 0.001 to 1.5 μm. The average particle size of the mother particles is larger than the average particle size of the child particles.

According to the above-mentioned constitution, the amino resin composite particles have an adhesion rate of the inorganic compound, for example, the child particles of the inorganic compound, of 10% or more. Therefore, for example, even when an external force is applied, the drop-off of the child particles, that is, the drop-off of the inorganic compound is smaller than that of the conventional amino resin composite particles. Therefore, an amino resin composite particle in which an inorganic compound is stably adhered to the surface of an amino resin particle, for example, an amino resin composite in which child particles made of an inorganic compound are stably adhered to the surface of a mother particle composed of amino resin particles Particles can be provided.

Therefore, the amino resin composite particles of the present invention are
It has properties as amino resin particles and properties derived from an inorganic compound fixed to the surface of the particles.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention contain the above-mentioned amino resin precursor,
Amino compound and formaldehyde at 95-98 ° C
The viscosity of the reaction solution is 2 × 10 ^{-2 to} 5.5 in the temperature range of
It is characterized in that it is obtained by reacting until a point within the range of × 10 ^-2 Pa · s.

According to the above constitution, by setting the viscosity of the reaction liquid within the above range, it is possible to obtain amino resin composite particles (mother particles) having substantially uniform particle diameters (narrow particle size distribution).

The amino resin particles of the present invention are milk obtained by reacting an amino compound with formaldehyde to obtain an amino resin precursor having a methylol group, and then mixing the amino resin precursor with an emulsifier. It is amino resin particles obtained by curing the amino resin precursor by adding a catalyst to the suspension. Therefore, specifically, amino resin crosslinked particles may be used. Therefore, the description of the mother particles in the amino resin composite particles may be the same as the mother particles composed of the amino resin crosslinked particles. Further, the obtained amino resin composite particles may also be amino resin crosslinked composite particles.

In order to solve the above problems, the amino resin composite particles of the present invention include an amino resin precursor which is to be amino resin particles and an amino resin which is being cured to be amino resin particles. Precursor, and at least one selected from amino resin particles, and an inorganic compound to be fixed, in a state of being dispersed in water, in the presence of an emulsifier, by being obtained by mixing while applying a shearing force It is characterized by being.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention have the above-mentioned shearing force as an amino resin precursor to be amino resin particles or an amino resin precursor in the middle of curing to be amino resin particles. , And at least one selected from amino resin particles and an inorganic compound to be fixed in water in the presence of an emulsifier, with a tip peripheral speed of 2 m / s or more and 30 m / s or less It is characterized by being imparted by shearing with a blade.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention have the above-mentioned shearing force as the amino resin precursor to be amino resin particles and the amino resin precursor in the process of curing to become amino resin particles. , And at least one selected from amino resin particles and an inorganic compound to be fixed, in a state of being dispersed in water, in the presence of an emulsifier, 3 MPa
As described above, it is characterized in that they are applied by colliding with each other at a discharge pressure of 49 MPa or less.

In order to solve the above-mentioned problems, the amino resin composite particles of the present invention have the above-mentioned shear force in the tank in a stirring device having a tank in which a baffle for changing the flow direction to a right angle is continuously installed. In addition, at least one selected from an amino resin precursor to be amino resin particles, an amino resin precursor in the course of curing to be amino resin particles, and an amino resin particle, and an inorganic compound to be fixed are dispersed in water. In the presence of an emulsifier, 0.1 MPa or more, 1.
It is characterized in that it is provided by being pressure-fed at a discharge pressure of 47 MPa or less and forced circulation or liquid feeding.

According to the above structure, at least one selected from the group consisting of amino resin precursors to be amino resin particles, amino resin precursors in the process of curing to become amino resin particles, and amino resin particles, and an inorganic substance to be fixed. Since the compound and the compound are dispersed in water and mixed in the presence of an emulsifier while applying a shearing force to emulsify or suspend while applying a shearing force, these amino resin precursor and / or amino resin The surface of the particles (that is, at least one selected from amino resin precursors to be amino resin particles, amino resin precursors in the process of curing to be amino resin particles, and amino resin particles) becomes soft due to emulsion or suspension. The surface of these amino resin precursors and / or amino resin particles in the state of It may be attached to (secured). Therefore, according to the above configuration, the inorganic compound can be firmly fixed (fixed) to the surface of the amino resin precursor and / or the amino resin particles, so that the inorganic compound is removed even when an external force is applied. It is possible to easily and inexpensively provide the amino resin composite particles having a smaller amount.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The following will describe one embodiment of the present invention. In the present specification, the particle state in the production process of the amino resin particles (amino resin crosslinked particles) according to the present invention is represented by two liquid states, “emulsion” and “suspension”. According to the usual definition, an "emulsion" is one in which liquid particles are dispersed as colloidal particles or coarser particles in a liquid to form an emulsion, and a "suspension" is a liquid. Refers to those in which solid particles are dispersed as colloidal particles or particles that can be seen with a microscope. Therefore, in the production process of the amino resin particles in the present invention, the state at the time of emulsification may be expressed as “emulsion” and the state at the time of curing may be expressed as “suspension”. In addition, although both forms may coexist during curing,
In the present specification, the state of curing is sometimes referred to as “suspension”. The dispersion liquid containing the finally cured amino resin composite particles is a suspension.

The amino resin composite particles according to the present invention are obtained by fixing (fixing) an inorganic compound on the surface of the amino resin particles, and the amino resin composite particles contain 10% by weight (that is, 10% by weight as a solid content). The suspension was placed in a container having a diameter of 92 mm and stirred at a tip peripheral speed of the stirring blade of 5.2 m / s using a stirring blade having a blade size of 40 mm to obtain the amino resin composite particles. The inorganic compound is dropped from the surface of the, and the sticking rate of the inorganic compound obtained by measuring the amount of the dropped inorganic compound is 10% or more. The inorganic compound is
It may be fixed (fixed) on the surface of the amino resin particles in any state as long as the fixing ratio is 10% or more and the film is firmly fixed on the surface of the amino resin particles. The fixing form of the inorganic compound may be, for example, a form in which amino resin particles are used as mother particles (core particles) and the amino resin particle surfaces are covered in a film shape, and the amino resin particle surfaces have child particles. It may be fixed as. Among them, the preferred form is the latter, and the amino resin composite particles according to the present invention are obtained by fixing (fixing) child particles made of an inorganic compound on the surface of mother particles made of amino resin, and the sticking rate of the child particles. Is preferably 10% or more. 1 and 2, the structure of the amino resin composite particles according to an embodiment of the present invention obtained in Example 6 described later, that is, the surface of the amino resin particles as mother particles (core particles) is made of an inorganic material. An example of a state in which the compound is fixed is shown by an electron micrograph (7500 times).

The amino resin composite particles of the present invention having the above-mentioned fixing rate of 10% or more are amino resin precursors to be amino resin particles, amino resin precursors in the middle of curing to be amino resin particles, and amino. At least one selected from the resin particles, and an inorganic compound to be fixed, in the state of being dispersed in water, in the presence of an emulsifier, by mixing while applying a shearing force, an amino resin precursor emulsion,
Alternatively, it is a preferred embodiment to suspend the amino resin precursor or amino resin particles in the middle of curing and fix the inorganic compound. Further, in the method for producing amino resin composite particles according to the present invention described below, the sticking rate is 1
This is a preferred production mode for obtaining the amino resin composite particles of the present invention of 0% or more.

The method for producing the amino resin composite particles according to the present invention is selected from amino resin precursors to be amino resin particles, amino resin precursors in the process of curing to be amino resin particles, and amino resin particles. At least one and an inorganic compound to be fixed are mixed (emulsified or suspended) in a state of being dispersed in water in the presence of an emulsifier while applying a shearing force to form the amino resin particles. The method comprises an inorganic compound fixing step of fixing an inorganic compound to at least one surface selected from a precursor, an amino resin precursor in the course of curing to be amino resin particles, and amino resin particles.

As described above, the amino resin precursor and / or the amino resin particles (that is, the amino resin precursor to be the amino resin particle) are obtained by mixing (emulsifying or suspending) while applying shearing force. To firmly adhere (fix) the inorganic compound to the soft layer formed on the surface of at least one selected from amino resin precursors and amino resin precursors that are being cured to become amino resin particles, by the above shearing force. You can Therefore, according to the present invention, the child particles made of an inorganic compound are firmly fixed (fixed) to the surface of the amino resin particles to be the core particles (mother particles).
Can be made.

In the present invention, the amino resin precursor to be the amino resin particles and the inorganic compound to be fixed are mixed in water in the presence of an emulsifier while applying a shearing force (emulsion). In the case of), a curing step is further performed in which a catalyst is added to cure the amino resin precursor to obtain amino resin particles. Further, the inorganic compound fixing step is an emulsion for preparing an amino resin precursor emulsion by mixing an aqueous dispersion of an amino resin precursor to be amino resin particles and an aqueous solution of an emulsifier and emulsifying the mixture. It is preferable to include a preparation step, and an inorganic compound mixing step of mixing the emulsion obtained in the emulsion preparation step and the inorganic compound while applying a shearing force. By adding a catalyst (curing catalyst) to the above emulsion to cure the amino resin precursor, mother particles made of the cured amino resin (amino resin crosslinked particles) are provided on the surface of the inorganic particles, and child particles made of an inorganic compound. However, it is possible to obtain the amino resin composite particles fixed at the above fixing rate. More specifically, a suspension containing the amino resin composite particles can be obtained. Also,
In the inorganic compound mixing step, the inorganic compound,
It is preferably mixed with the above emulsion in a state of being dispersed in water. More preferably, an emulsion comprising an aqueous dispersion of an amino resin precursor to be the mother particles and an aqueous solution of an emulsifier (hereinafter referred to as an emulsifier aqueous solution), and an aqueous dispersion of an inorganic compound to be the child particles. , After emulsifying while applying a shearing force, by adding a catalyst and curing, to the surface of the mother particles made of the amino resin, the child particles made of the inorganic compound added in the state of the aqueous dispersion, It is possible to more efficiently obtain the amino resin composite particles fixed at the fixing ratio.

The above mother particles (amino resin particles) are prepared by reacting an amino compound with formaldehyde to obtain an amino resin precursor having a methylol group, and then mixing the amino resin precursor with an aqueous emulsifier solution. By adding a catalyst to the emulsion thus obtained, the amino resin precursor can be cured to form amino resin particles.

Specific examples of the amino compound include benzoguanamine (2,4-diamino-6-phenyl-sy).
m.-triazine), cyclohexanecarboguanamine,
Examples thereof include cyclohexenecarboguanamine and melamine. These amino compounds may be used alone,
Further, two or more kinds may be used in combination, but it is particularly preferable to contain at least one compound selected from the above exemplified compound group in the range of 40% by weight or more and 100% by weight or less, and benzoguanamine is contained. Most preferably, it is contained within the above range.

Water is used as a solvent when the amino compound is reacted with formaldehyde. Therefore, as the form of addition of formaldehyde, specifically, it is added (prepared) in the state of an aqueous solution (formalin (trademark)).
And a method of generating formaldehyde in the reaction liquid by adding trioxane or paraformaldehyde to water. Of these, the method of adding formaldehyde in the state of an aqueous solution is more preferable.

The ratio of formaldehyde to 1 mol of the amino compound is preferably in the range of 2 to 3 mol, and more preferably in the range of 2 to 2.5 mol. If the proportion of formaldehyde is out of the above range, the amount of unreacted amino compound or formaldehyde increases, which is not preferable. The amount of the amino compound and formaldehyde added to the water, that is, the concentration of the amino compound and formaldehyde at the time of charging is preferably higher as long as the reaction is not hindered.

The pH of the reaction solution is preferably adjusted to be neutral or weakly basic using, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, aqueous ammonia and the like.
The amount of sodium carbonate or the like used is not particularly limited. By reacting an amino compound with formaldehyde in water, an amino resin precursor which is a so-called initial condensation product can be obtained. The reaction temperature is 95-
It is desirable to be in the temperature range of 98 ° C. And, in the above reaction, the viscosity of the reaction solution is, for example, 2 × 10 ^{−2 to} 5.5 ×.
At the time when it becomes within the range of 10 ⁻² Pa · s (20 to 55 cP), by performing an operation such as cooling the reaction solution,
You can finish. Specifically, in the temperature range of 95 to 98 ° C., the viscosity of the reaction solution may be measured by using the process viscosity and the like to determine the reaction end point. As a result, a reaction liquid containing the amino resin precursor, that is, an aqueous dispersion of the amino resin precursor is obtained. By setting the viscosity of the reaction solution within the above range, it is possible to obtain mother particles having a substantially uniform particle size (narrow particle size distribution). In addition, the smaller the viscosity of the reaction solution, the smaller the particle size of the mother particles produced.

The viscosity of the reaction solution at the end of the reaction is remarkably higher than the viscosity of the aqueous solution (at the start of the reaction) charged with the amino compound and formaldehyde. Hardly affected. The amino resin precursor is soluble in organic solvents such as acetone, dioxane, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, toluene, xylene. However, it is substantially insoluble in water.

The average particle size of the mother particles is more preferably in the range of 1 to 30 μm, further preferably in the range of 2 to 20 μm, and particularly preferably in the range of 3 to 15 μm. In the production method according to the present invention, the standard deviation is 6 μm or less, more preferably 4 μm or less, most preferably 2 μm.
The following can be controlled. The degree of crosslinking, the average molecular weight, the molecular weight distribution, etc. of the amino resin are not particularly limited.

The above-mentioned child particles may be made of an inorganic compound. Specific examples of the inorganic compound include silica particles, conductive carbon powder, zirconia particles, titania particles, aluminum powder, alumina sol, serie sol, Examples thereof include mica. These inorganic compounds may be used alone or in combination of two or more. Among the above-exemplified inorganic compounds, silica particles and conductive carbon powder are particularly preferable. The average particle size of the inorganic compound as the child particles is not particularly limited, but the average particle size of the inorganic particles is 0.05 to 0.00 of the average particle size of the mother particles.
1 time, more specifically, it is preferably in the range of 0.001 to 1.5 μm, more preferably in the range of 0.001 to 1 μm, and the lower limit value is 0.005 μm or more. Is more preferable, 0.01 μm or more is particularly preferable, and the upper limit is more preferably 0.5 μm or less, particularly preferably 0.2 μm or less. The shape of the child particles may be various shapes such as a plate shape, a scale shape, a rod shape, and a fiber shape, in addition to the spherical shape. Further, in the child particles of the present invention, other compounds may be fixed as the child particles together with the inorganic compound as long as the physical properties and performance of the amino resin composite particles of the present invention are not affected.

By dispersing the inorganic compound in water,
An aqueous dispersion of an inorganic compound is prepared. The proportion of the inorganic compound in the water dispersion is preferably in the range of 5 to 30% by weight. As a method for preparing the water dispersion, a known dispersion method can be adopted. The amount of the inorganic compound used with respect to the amino resin precursor is more preferably within the range of 1 to 50% by weight, and further preferably within the range of 5 to 20% by weight. If the amount of the inorganic compound used is less than 1% by weight, the amino resin composite particles in which the child particles are uniformly fixed to the mother particles may not be obtained.

As the emulsifier constituting the protective colloid,
Specifically, polyvinyl alcohol, carboxymethyl cellulose, sodium alginate, polyacrylic acid,
Examples include water-soluble polyacrylic acid salts and polyvinylpyrrolidone. All of these emulsifiers are used in the state of an aqueous solution dissolved in water, or a part of them is used in the state of an aqueous solution and the rest is in the state as it is (eg powder, granules, liquid, etc.). Used in. Among the emulsifiers exemplified above, polyvinyl alcohol is more preferable in view of stability of the emulsion, interaction with the catalyst, and the like. The polyvinyl alcohol may be a completely saponified product or a partially saponified product. The degree of polymerization of the water-soluble polymer forming the protective colloid can be set within a range that does not hinder the present invention. The larger the amount of the emulsifier used with respect to the amino resin precursor, the smaller the particle size of the resulting mother particles tends to be. The amount of the emulsifier used with respect to the amino resin precursor is more preferably in the range of 1 to 30% by weight, and further preferably in the range of 1 to 5% by weight. If the amount of the emulsifier used is out of the above range, the stability of the emulsion may be poor.

The emulsion of the amino resin precursor to which the inorganic compound is adhered is prepared by dispersing the amino resin precursor to be amino resin particles and the inorganic compound to be fixed in water in the presence of an emulsifier. It can be prepared by mixing while applying a shearing force. Specifically, by mixing an aqueous dispersion of an amino resin precursor, an emulsifier aqueous solution, and an inorganic compound within a temperature range of, for example, 70 to 100 ° C. while applying a shearing force, that is, by emulsifying the mixture. , Can be prepared. Suitably, for example, an amino resin precursor prepared by mixing an aqueous dispersion of an amino resin precursor and an aqueous emulsifier solution and applying a shearing force to the mixture to emulsify the mixture within a temperature range of, for example, 70 to 100 ° C. While adding an inorganic compound, preferably as an aqueous dispersion of an inorganic compound, to the emulsion of, while applying shearing force, for example, 20 to 100
By emulsifying in the temperature range of ℃, it is possible to obtain an emulsion of the amino resin precursor to which the inorganic compound is attached.

The aqueous dispersion of the amino resin precursor, the emulsifier aqueous solution, and the inorganic compound can be added at the same time to emulsify, but if the inorganic compound is added before emulsifying the amino resin precursor. Since the inorganic compound enters the inside of the particle composed of the amino resin precursor, in order to effectively fix the inorganic compound on the particle surface, the aqueous dispersion of the amino resin precursor and the emulsifier aqueous solution are mixed and emulsified. Thus, it is preferable to add the inorganic compound after the amino resin precursor is made into particles and the particle diameter and particle size distribution of the amino resin precursor are adjusted. In the above description, the term "after adjusting the particle size and particle size distribution of the amino resin precursor" means that the average particle size of the amino resin precursor is preferably 1
To 30 μm, more preferably 2 to 20 μm, particularly preferably 3 to 15 μm,
This is after the emulsification so that the standard deviation thereof is preferably 6 μm or less, more preferably 4 μm or less, and most preferably 2 μm or less.

The above-mentioned inorganic compound is preferably added as an aqueous dispersion of the inorganic compound. By adding the inorganic compound as an aqueous dispersion, the inorganic compound can be more efficiently fixed to the surface of the obtained amino resin particles (mother particles). Further, when the emulsifier is directly dispersed in the aqueous dispersion of the amino resin precursor, the particle formation of the amino resin precursor may not proceed efficiently, so the emulsifier is preferably added as an emulsifier aqueous solution.

The concentration of the amino resin precursor in the emulsion (that is, the solid content concentration) is more preferably in the range of 30 to 60% by weight. Further, the ratio of the inorganic compound (solid content) in the emulsion is more preferably in the range of 5 to 20% by weight. Therefore, the ratio (solid content) of the inorganic compound in the aqueous dispersion of the inorganic compound,
The concentration of the aqueous solution in the case of mixing the emulsifier in the state of an aqueous solution is not particularly limited, and the concentration that can adjust the concentration of the amino resin precursor and the proportion of the inorganic compound in the emulsion within the above range.・ Any concentration is acceptable.
If the concentration of the amino resin precursor is less than 30% by weight, the productivity of the amino resin composite particles will decrease. On the other hand, when the concentration of the amino resin precursor exceeds 60% by weight, the obtained mother particles are enlarged and the mother particles are aggregated with each other. That is, since the particle size of the amino resin composite particles cannot be controlled, it is only possible to obtain amino resin composite particles having irregular particle sizes (wide particle size distribution).

In the present invention, the amino resin particles, that is, the amino resin precursor to be the mother particles (core particles) and the inorganic compound to be fixed, for example, the inorganic compound to be the child particles, are mutually dispersed in an aqueous dispersion. By emulsifying while applying shearing force in the state of, on the surface of the amino resin precursor,
Fix the inorganic compound. A stirring device having a high shearing force is preferably used as a stirring device used when emulsifying the amino resin precursor and the inorganic compound while applying a shearing force.

As a device capable of stirring while applying a shearing force, that is, as a stirring device having a so-called high shearing force, a liquid / liquid or a solid / liquid is rotated at a high speed by blades, specifically, a tip circumference. Speed is 2m / s or more, 30m /
A device for mixing while shearing with a stirring blade rotating at s or less (shearing by high-speed stirring), a liquid / liquid or a solid / liquid, a discharge pressure of 4.9 to 49 MPa (50 to 500 kgf)
/ Cm ² ) under high pressure (shearing under high pressure) by mixing with each other, a baffle for changing the flow direction to a 90 degree angle (right angle), in a vessel where liquid or liquid or Discharge pressure of solid / liquid by pump etc. 0.19
Examples include a device (stress shearing) that mixes by pressure feeding at 6 to 1.47 MPa ( ^{2 to} 15 kgf / cm ² ) and forced circulation or liquid feeding. Specific examples of the above-mentioned stirring device include a homomixer, a TK homomixer (model name; manufactured by Tokushu Kika Kogyo Co., Ltd., the shape of stirring blades is a turbine type), a high-speed disper, a homodisper, a TK lab disper (model). Name; manufactured by Tokushu Kika Kogyo Co., Ltd. ・ Shape of stirring blade is turbine type, Ebara Milzer (model name;
The shape of the stirring blade manufactured by EBARA CORPORATION is Stut type turbine). Specific examples of the stirring device include a high-pressure homogenizer (model name; manufactured by Izumi Food Maginari Co., Ltd.). Specific examples of the stirring device include a static mixer (model name; manufactured by Noritake Company Limited). However, the stirring device is not limited to the above-exemplified device. If the device (model) of the same principle,
The same effect can be obtained. Further, in the above stirring apparatus, in the state of the emulsion of the amino resin precursor, as defined in the present application, there are few coarse particles, the average distribution of the amino resin particles is uniform, and the particle state is such that the standard deviation is small. In order to obtain stably, there is a tubular casing such as a homomixer, a TK homomixer, and an Ebara Milzer, and an apparatus in which the stirring blade rotates in the tubular casing is preferable.

In the present invention, the high shear force means (1) liquid /
When liquid or solid / liquid is mixed while being sheared by a high-speed rotating stirring blade (shearing by high-speed stirring), that is, for example, amino resin precursor and / or amino resin particles to be amino resin particles (mother particles) An aqueous dispersion (emulsion and / or suspension) containing an emulsifier, an emulsifier, and an inorganic compound to be fixed is stirred (mixed) with the above stirring device.
In more detail, more specifically, the above-mentioned amino resin precursor and / or amino resin particles are emulsified and / or suspended in the presence of an emulsifier and / or a suspension and an aqueous dispersion of an inorganic compound. When the body is mixed with the above stirring device, the peripheral speed of the tip of the stirring blade is 2 m / s or more,
Preferably 5 m / s or more (usually the upper limit is 30 m / s
s), and more preferably, in addition to the above-mentioned configuration, the diameter of the stirring blade is r, the inner diameter of the reaction vessel is R1, or there is a cylindrical casing, and the stirring blade rotates in the cylindrical casing. As for the stirrer, if the casing inner diameter is R2, r / R1 or r / R, respectively
A shearing force for making the ratio 2 to be 0.2 or more and less than 1 is shown. A more preferable form of the above ratio is that the lower limit of the above ratio is
0.4 or more, more preferable form is 0.6 or more, particularly preferable form is 0.8 or more, and most preferable form is 0.9 or more. By increasing the above ratio, in the state of the emulsion of the amino resin precursor, as defined in the present application, there are few coarse particles, the average distribution of the amino resin particles is uniform, and the standard deviation is small. It can be obtained more stably. In the example of the present case, r /
R1 and r / R2 are collectively described as r / R. Further, in the present invention, high shear force means (2) when liquid / liquid or solid / liquid are mixed by colliding with each other under high pressure of discharge pressure (shear under high pressure), specifically, Amino resin precursor and / or an emulsion and / or suspension consisting of amino resin particles and an emulsifier aqueous solution, and an aqueous dispersion containing the above inorganic compound are discharged using the above stirring device to obtain an amino resin. When the precursor and / or amino resin particles and the inorganic compound are mixed by colliding with each other (shearing under high pressure), the discharge pressure is 3 MPa or more (that is, 3 MPa).
Or more, 49 MPa or less), preferably 5 MPa or more (that is, 5 MPa or more and 49 MPa or less), (3) liquid / liquid in a tank in which a baffle that changes the flow direction to a 90 degree angle (right angle) is continuously installed. Alternatively, when the solid / liquid is mixed by pressure-feeding with a pump or the like and forced circulation or liquid-feeding (stress shearing), specifically, the amino resin precursor and / or amino resin particles are mixed in the presence of an emulsifier. When the emulsion and / or suspension obtained by emulsification and / or suspension and the aqueous dispersion of the inorganic compound are mixed using the above stirring device, the discharge pressure thereof is 0.1 MPa or more (that is, , 0.1 MPa or more and 1.47 MPa or less), preferably 0.5 MPa or more (ie 0.5
Shearing force of 1 MPa or more and 1.47 MPa or less).

As described above, in the present invention, when an inorganic compound, specifically, an inorganic compound as a child particle is fixed to the surface of the amino resin particle (amino resin crosslinked particle) as the mother particle (core particle). A stirring device having a high shearing force is used as the stirring device used for. However, the conventional known technique does not describe the shearing force in the stirrer having a high shearing force, because the purpose itself of fixing (firmly fixing) the inorganic compound to the amino resin surface is not clear. Further, the amino resin composite particles according to the present invention have not been clearly isolated as a target product, and the specific conditions for obtaining the particles have not been specifically examined until now. Therefore, it was very difficult to stably obtain the amino resin composite particles having a high sticking rate suitable for the purpose. In the present invention, as described above, the shearing force of the stirring device used when fixing the above-mentioned inorganic compound to the surface of the amino resin particles is determined by the peripheral speed of the tip of the blade (stirring blade) in high-speed stirring shearing, and the shearing under high pressure. Disclosed are specific stirring conditions which are defined by the discharge pressure and the discharge pressure in stress shearing to obtain amino resin composite particles (amino resin crosslinked composite particles) in which an inorganic compound is fixed to the surface of amino resin particles. The amino resin composite particles obtained by the method according to the present invention have a state in which the inorganic compound is firmly adhered to the surface of the amino resin particles. Therefore, in the present invention, this physical property is defined as the sticking rate.

The above stirring device (stirring device having high shearing force) is used when mixing an emulsion comprising an aqueous dispersion of amino resin precursor and an aqueous emulsifier solution with an aqueous dispersion of an inorganic compound. That is, it is used when stirring an emulsion composed of an amino resin precursor and an emulsifier aqueous solution and an inorganic compound while applying a shearing force. In the present embodiment, stirring performed at the time of forming the amino resin precursor does not particularly require high shearing force. In addition, a catalyst (curing catalyst) is used to improve the filterability after completion of curing when the amino resin particles are obtained by stirring at low speed (low shearing force) and curing, and when the amino resin particles are lightly aggregated. Even when charged to cure the amino resin precursor, stirring with high shearing force is not required. On the other hand, when the amino resin precursor aqueous solution and the emulsifier are mixed, that is, when the aqueous dispersion of the amino resin precursor and the emulsifier aqueous solution are mixed, a high shearing force is applied in order to form particles having a narrow particle size distribution. It is preferable to use a stirring device that can be applied. Therefore, the preferred form of the combination of the agitator and the agitator (combination of agitation types) is as follows. That is, when the (1) amino resin precursor is formed, a general stirrer is used. (2) When mixing the aqueous dispersion of the amino resin precursor and the emulsifier (aqueous emulsifier solution),
In addition, (3) when mixing the water dispersion of the amino resin precursor and the inorganic compound (water dispersion of the inorganic compound), a stirring device capable of imparting a high shearing force is used. (4) When a curing catalyst is added and the amino resin precursor is cured, a general stirrer is used.

In the present embodiment, (i) an amino compound such as benzoguanamine and formaldehyde (for example, formalin (trademark)) are heated and reacted to obtain an amino resin precursor, and an amino resin precursor The stirring means for condensing and curing the emulsion of is called a stirrer,
(ii) a stirring means for emulsifying the amino resin precursor in the presence of an emulsifier (for example, polyvinyl alcohol) is called a mixer, and (iii) an aqueous dispersion containing the amino resin precursor and / or amino resin particles, Emulsion and / or suspension comprising an emulsifier aqueous solution, that is, an amino resin precursor emulsion or a suspension comprising amino resin particles in the course of curing of the amino resin precursor and an emulsifier aqueous solution, or curing At least one of the suspensions consisting of the subsequent amino resin particles (amino resin crosslinked particles) and an emulsifier aqueous solution is mixed with a water dispersion of an inorganic compound to form a mixture on the surface of the amino resin particles (amino resin crosslinked particles). The agitating means for adhering the inorganic compound, for example, the child particles made of the inorganic compound, is referred to as an agitating device (agitating device having a high shearing force) to distinguish them.

In the present invention, a short time (for example, 1 minute to
It is possible to fix the above-mentioned inorganic compound to the surface of the amino resin precursor in about 3 minutes) and emulsify the water dispersion of the amino resin precursor and the water dispersion of the inorganic compound while applying shearing force. The time required for is not particularly limited.

According to the present invention, a catalyst is added to the emulsion containing the amino resin precursor to cure the amino resin, whereby the surface of the amino resin particles (amino resin crosslinked particles) is
It is possible to obtain amino resin composite particles (amino resin crosslinked composite particles) to which child particles made of an inorganic compound, for example, an inorganic compound, are fixed. The method of adding the catalyst at this time is not particularly limited, but in order to obtain the amino resin composite particles in which the child particles are uniformly fixed to the mother particles, it is more preferable to charge the entire amount at one time. The reaction temperature (curing temperature) is
The range of 15 (normal temperature) to 100 ° C is preferable. The end point of the reaction can be judged by sampling or visual observation.

An acid is suitable as the above catalyst (curing catalyst). Specific examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; ammonium salts of these mineral acids; sulfamic acid; benzenesulfonic acid, paratoluenesulfonic acid,
Sulfonic acids such as dodecylbenzene sulfonic acid; organic acids such as phthalic acid, benzoic acid, acetic acid, propionic acid, salicylic acid; and the like. These catalysts may be used alone or in combination of two or more kinds. The amount of the catalyst used is 0.1 to 100 parts by weight of the amino resin precursor.
The preferred range is 5 parts by weight. If the amount of the catalyst used exceeds 5 parts by weight, the emulsion state will be destroyed and the mother particles will aggregate. On the other hand, if the amount of the catalyst used is less than 0.1 part by weight, the reaction will take a long time and the curing will be insufficient.

In the present invention, the emulsion of the amino resin precursor is condensed and cured together with the inorganic compound and the catalyst to obtain amino resin composite particles having the inorganic compound fixed on the surface of the amino resin particles. That is, the amino resin composite particles according to the present invention, which are so-called two-component particles in which the child particles are fixed on the surface of the mother particles, can be obtained.

As described above, according to the present invention, the amino resin precursor is emulsified and the inorganic compound is dispersed by using high shearing force when the surface of the amino resin precursor in the emulsion state is soft,
By adhering to the surface of the amino resin precursor, the inorganic compound can be fixed (fixed) on the surface of the amino resin particles (amino resin crosslinked particles).

However, depending on the inorganic compound to be adhered, if the inorganic compound is added (input) during the emulsification of the amino resin precursor (that is, when the amino resin precursor is emulsified in the presence of an emulsifier), the amino resin is added. The emulsion particles of the precursor may be destroyed, and the destroyed emulsion particles of the amino resin precursor may aggregate. Therefore, if there is such a possibility, once the catalyst (curing catalyst) is added, the curing of the amino resin precursor is slightly advanced or completed, and the amino resin particles (amino resin crosslinked particles) are cured. It is preferable to add the inorganic compound after the formation of at least 1, and use the shearing force (high shearing force) to adhere (fix) the inorganic compound to the amino resin particles as the mother particles (core particles). However, in this case, the amino resin particles or the amino resin precursor, which are the mother particles, are hardened by curing, so that the inorganic compound is unlikely to adhere to the particles as they are. Therefore, in such a case, an emulsifier is newly added as an emulsifier aqueous solution, and an aqueous dispersion containing the amino resin precursor in the middle of curing and / or amino resin particles after curing is added in the presence of the emulsifier. By suspending, on the surface of the amino resin particles to be the mother particles (core particles),
It is preferable to form a soft layer for adhering (fixing) the inorganic compound by the shearing force. When an inorganic compound is added to the reaction liquid (suspension) containing the amino resin precursor in the process of curing, the emulsifier used for emulsifying the amino resin precursor is contained in the reaction liquid (suspension). It exists, and the particle surface of the amino resin precursor in the middle of curing is still in a soft state. Therefore, in this case, it is not always necessary to newly add an emulsifier.

In addition, during the suspension, formaldehyde is further added, for example, as an aqueous solution (formalin (trademark)), so that the amino resin precursor and //
Alternatively, it is even more preferable to suspend the aqueous dispersion containing the cured amino resin particles. When the inorganic compound is attached to the amino resin precursor during curing and / or the amino resin particles after curing, the above-mentioned amino resin precursor and / or
Alternatively, only by adding an emulsifier to an aqueous dispersion containing amino resin particles, the above-mentioned amino resin precursor and / or amino resin particle surfaces to be the mother particles (core particles) and the suspension formed on the mother particle surface are formed later. The adhesive force with the soft layer is weak, and the soft layer formed later is easily peeled off when dried. Therefore, by further adding formaldehyde, for example, as an aqueous formaldehyde solution and suspending it, the mother particle surface and the soft layer formed later on the mother particle surface by suspension can be chemically bonded,
A soft layer formed later can be prevented from peeling off during drying, and amino resin composite particles having a high sticking rate can be obtained.

Thus, in the reaction liquid during or after the curing of the amino resin precursor, the aqueous dispersion of the inorganic compound,
If necessary, an emulsifier (aqueous emulsifier solution) and further formaldehyde (an aqueous formaldehyde solution (for example, formalin (trademark))) are added and suspended while applying a shearing force. It is preferable to carry out the suspension at a temperature lower than the temperature during the curing reaction). Specifically, the temperature is 0 ° C to 20 ° C higher than the temperature during the curing reaction.
The lower the range, the better. When an inorganic compound is added to the reaction liquid during curing to suspend the reaction liquid, after the suspension, the reaction liquid is adjusted to a reaction temperature before the inorganic compound is added, and then the curing step is performed. To continue. The shearing force (high shearing force) during suspension in this case is as described above.

As the emulsifier used in this case, the emulsifiers exemplified above can be used. The emulsifier is
It may be used in the state of an aqueous solution in which the whole amount is dissolved in water, a part of it may be used in the state of an aqueous solution, and the rest may be used as it is (for example, in the form of powder, granules, liquid, etc.). Good.

When the aqueous dispersion containing the amino resin precursor in the course of curing and / or the cured amino resin particles and the inorganic compound to be fixed is suspended while applying a shearing force as described above, The amount used is preferably in the range of 0.1 to 30% by weight, and preferably in the range of 0.5 to 5% by weight, based on the amino resin precursor in the course of curing and / or the amino resin particles after curing. It is even more preferable that When the amount of the emulsifier used is out of the above range, the stability of the suspension tends to be poor, and particularly when the amount of the emulsifier used is small, the inorganic compound is an amino resin precursor in the course of curing and It may not be fixed to the amino resin particles after curing.

In the above case, the form of addition of formaldehyde (method) may be addition in the form of an aqueous solution (formalin (trademark)), or trioxane or paraformaldehyde may be added to water in the reaction solution. The form (method) of generating formaldehyde may be used. Among these, the form (method) of adding formaldehyde in the state of an aqueous solution is more preferable. In this case, formaldehyde is preferably used in a range of 1 to 10 times the amount of the emulsifier added. If the amount of formaldehyde used is less than the above range, the soft layer formed later due to suspension on the surface of the mother particles (core particles) may be easily peeled off during drying, and the effect of adding formaldehyde may not be sufficiently obtained. There is. On the other hand, if the amount of formaldehyde used exceeds the above range,
Unreacted formaldehyde increases, which is not preferable.

Even during the suspension, the solid content concentration in the suspension, that is, the total concentration of the amino resin precursor and the amino resin particles, is 30 to 60 for the above reason.
More preferably, it is within the range of wt%. Furthermore, the ratio of the inorganic compound in the suspension (solid content) is also
More preferably, it is within the range of 5 to 20% by weight. Therefore, also in this case, the ratio (solid content) of the inorganic compound in the aqueous dispersion of the inorganic compound and the concentration of the aqueous solution when the emulsifier is mixed in the aqueous solution are not particularly limited and The concentration and concentration of the amino resin precursor and amino resin particles and the proportion of the inorganic compound in the suspension may be adjusted within the above range.

Further, even during the suspension, the fixing of the inorganic compound is carried out in a short time. The time required for suspending and while applying shearing force is not particularly limited. In addition, when an inorganic compound is added to the reaction liquid during curing and suspended, the curing reaction is further continued as described above. The curing conditions such as the curing temperature and the curing time at this time are as described above. The obtained amino resin composite particles can be taken out from the reaction solution, subjected to heat treatment or the like and dried to be used.

Inorganic compounds which are preferably added after the curing of the amino resin precursor is slightly advanced or the curing is completed and some amino resin particles (amino resin crosslinked particles) are formed are as follows. Examples thereof include zirconia particles, titania particles, and serie sol.

In a preferred embodiment of the production method of the amino resin composite particles of the present invention, an inorganic compound is added to an amino resin precursor emulsion obtained by emulsifying the predetermined amino resin precursor, Before the emulsion of the amino resin precursor in which the inorganic compound is fixed to the surface of the mother particles of the amino resin precursor obtained by applying the shearing force is cured, water is added to dilute the emulsion. The form is preferred. By diluting the emulsion before the curing reaction, destruction of emulsion particles can be prevented. Moreover, the temperature of the emulsion can be lowered by the dilution, and the temperature can be adjusted to a temperature preferable for initiation of the curing reaction. In the production form of the amino resin composite particles of the present invention, in order to emulsify the amino resin precursor and fix the inorganic compound to the amino resin particle surface more efficiently, in a state where sufficient shearing force can be imparted, emulsification Set the time temperature high.

In addition, in the production form of the amino resin composite particles of the present invention, when the inorganic compound is added to the emulsion, the addition of the inorganic compound which may impair the stable emulsified state of the emulsion particles, In some cases, the inorganic compound is not added to the emulsion, but the inorganic compound is added in a state where the curing is preliminarily advanced to some extent. Even in this case, the above dilution may be performed before curing the emulsion of the amino resin precursor (amino resin precursor to which the inorganic compound is not fixed).

In the production form of the amino resin composite particles of the present invention, when the following curing reaction is carried out while the concentration of the amino resin precursor emulsion is high, the emulsion particles become unstable and are easily broken. However, it may be difficult to obtain the desired amino resin composite particles. Therefore, a form in which the concentration of the emulsion is reduced by diluting with water is preferable. Specifically, it is preferable to add water such that the concentration of the amino resin precursor in the emulsion after adding water is 45% or less (that is, more than 0 and 45% or less). More preferably 40
% Or less, more preferably 10 to 35%. Moreover, by diluting with water, the temperature of the said emulsion is 5-80 degreeC, More preferably, it is 10-60 degreeC,
More preferably, the temperature can be adjusted within the range of 10 to 50 ° C., and the subsequent curing reaction for forming the amino resin composite particles can be prevented from running away. Thus, the amino resin composite particles of the present invention can be manufactured more stably.

Although it is time to dilute, a predetermined amino resin precursor is emulsified, and the obtained amino resin precursor or an inorganic compound is further mixed by stirring under a shearing force. When the emulsion of the amino resin precursor obtained by liquefaction has an average particle size of 0.1 to 30 μm as measured by Coulter Multisizer II type, water is added to dilute the emulsion. More preferably 0.5 to 25 μ
m, and further when 0.5 to 20 μm is reached, water is added to dilute. The purpose of dilution is to reduce the emulsification concentration of the emulsion, and to keep the emulsion particles obtained by emulsification stable until the subsequent curing step. The preferred form is to add dilution water after the particles are firmly formed.

Further, the dilution water is preferably added in a temperature range from the temperature at which the emulsification was performed to the temperature range at which the temperature did not drop so much. If the temperature of the emulsion is lowered without dilution while the emulsification temperature is high, it becomes difficult to obtain amino resin composite particles having a desired average particle size due to aggregation of emulsion particles. Therefore, the dilution of the emulsion in the method for producing amino resin composite particles of the present invention is emulsification of the amino resin precursor, the obtained amino resin precursor, or further inorganic compound, to impart a shearing force. A preferred mode is one in which dilution water is added before the temperature of the emulsion of the amino resin precursor obtained by complexing by stirring under the original temperature decreases by 30 ° C. from the temperature at which the emulsification was performed. More preferably, the dilution water is added before the temperature drops by 20 ° C. More preferably, it is a form in which dilution water is added before the temperature drops by 10 ° C. The dilution water has an average particle size of 0.1 to 1 in particular.
It can be preferably applied when obtaining amino resin composite particles within a range of 0 μm. More preferably, the average particle size is 0.1 to
This is the case of obtaining 8 μm amino resin composite particles. More preferably, it is a case where amino resin composite particles having an average particle diameter of 0.1 to 5 μm are obtained.

In addition, the above-mentioned dilution can be carried out by batch feeding
It may be continuous or intermittent sequential feeding.

In the present invention, the amino resin composite particles may be colored if necessary. Amino resins have excellent affinity with dyes. As the dye,
Specifically, water-soluble monoazo dyes, water-soluble polyazo dyes, metal-containing azo dyes, dispersible azo dyes, anthraquinonic acid dyes, anthraquinone vat dyes, indigo dyes,
Water-soluble such as sulfur dye, phthalocyanine dye, diphenylmethane dye, triphenylmethane dye, nitro dye, nitroso dye, thiazole dye, xanthene dye, acridine dye, azine dye, oxazine dye, thiazine dye, benzoquinone dye, naphthoquinone dye, cyanine dye Alternatively, an oil-soluble dye may be used. The amino resin can also be colored with a pigment. The timing of adding the dye is not particularly limited. The dye is, for example,
It is preferably added in the state of a dispersion liquid dispersed in water or in the state of an aqueous solution dissolved in water.

The production method of the present invention may include a neutralization step of neutralizing the suspension containing the amino resin composite particles (amino resin composite crosslinked particles) obtained by the above curing step. The neutralization step is preferably performed when an acid catalyst such as sulfuric acid is used as a curing catalyst in the above curing step. By performing the neutralization step, the above acid catalyst can be removed (specifically, the acid catalyst can be neutralized),
For example, when the amino resin composite particles are heated in the heating step and the like described later, the amino resin particles that become mother particles (core particles), and thus the amino resin particles are mother particles (core particles)
Discoloration of the amino resin composite particles (for example, discoloration to yellow)
Can be suppressed. The neutralization step is also a preferred embodiment in the case of colored amino resin composite particles, which has an effect of suppressing yellowing and obtains bright colored particles having excellent heat resistance. Therefore, the amino resin composite particles produced through the neutralization step is a preferred embodiment.

The "neutralization" referred to in the neutralization step means that the pH of the suspension containing the amino resin composite particles is preferably 5 or more, more preferably 5 to 9.
When the pH of the suspension is less than 5, the acid catalyst remains, so that the amino resin composite particles are discolored in the heating step and the like described later. By adjusting the pH of the suspension within the above range by the neutralization, amino resin composite particles having high hardness, excellent solvent resistance and heat resistance, and no discoloration can be obtained.

As the neutralizing agent that can be used in the neutralizing step, for example, an alkaline substance is suitable. Examples of the alkaline substance include sodium carbonate, sodium hydroxide, potassium hydroxide, and ammonia. Among them, sodium hydroxide is preferable and an aqueous sodium hydroxide solution is preferably used because it is easy to handle. To be Although these may use only 1 type,
You may use 2 or more types together.

As a method for taking out the amino resin composite particles from the reaction solution, a method of filtering and a method of using a separator such as a centrifuge are convenient. The amino resin composite particles after being taken out from the reaction solution may be washed if necessary.

The taken out amino resin composite particles may be dried, for example, at a temperature of about 100 to 200 ° C.
The drying is carried out, for example, by adjusting the water content of the amino resin composite particles to 3
It suffices to end the process when the amount becomes less than or equal to weight%. Alternatively, the taken out amino resin composite particles may be subjected to a heat treatment for the purpose of further improving solvent resistance, water resistance and heat resistance of the amino resin composite particles simultaneously with, for example, drying. Then, after the above-mentioned drying or heat treatment, treatments such as crushing (crushing) and classification may be performed if necessary. Since the amino resin composite particles obtained by the production method according to the present invention hardly agglomerate with each other, the particles are sufficiently crushed by applying a slight force (load) even when the crushing treatment is performed. be able to.

According to the production method of the present invention, for example, an amino resin precursor which is to be a mother particle and an inorganic compound which is to be a child particle are mixed with each other in the state of an aqueous dispersion to give a shearing force. While emulsifying while curing,
Immobilizing child particles made of an inorganic compound on the surface of a mother particle made of an amino resin without increasing the number of manufacturing steps compared to the case of coating the surface (the hybrid method, microcapsule method, spray coating method, etc.). be able to. That is, the child particles can be easily and inexpensively fixed to the surface of the mother particles.

Further, according to the present invention, an emulsion and / or a suspension comprising an amino resin precursor and / or amino resin particles to be amino resin particles and an emulsifier aqueous solution, and an inorganic compound (an inorganic compound to be fixed) (Aqueous dispersion of the compound) is mixed (emulsified and / or suspended) while applying a shearing force, so that the inorganic compound, for example, the child particles made of the inorganic compound, is firmly fixed to the mother particle, and thus the inorganic compound A child particle made of a compound, for example, an inorganic compound is difficult to fall off from the mother particle. As a result, an amino resin composite particle in which the inorganic compound is fixed to the surface of the amino resin particle at a fixing rate of 10% or more, particularly, an amino resin in which the child particles are fixed to the surface of the mother particle at a fixing rate of 10% or more The composite particles can be manufactured easily and inexpensively.

Ratio of the inorganic compound attached to the amino resin particles to the used amount of the inorganic compound (adhesion rate)
Is preferably 30 to 100%, and 50 to 10%
It is more preferably 0%. If the adhesion ratio is out of the above range, an appropriate charge amount may not be obtained when the resulting amino resin composite particles are used as toner particles or an additive for toner.

The content of the inorganic compound in the amino resin composite particles according to the present invention is preferably in the range of 1 to 30% by weight, more preferably 2 to 30% by weight. When the content is out of the above range, an appropriate charge amount may not be obtained when the resulting amino resin composite particles are used as toner particles or a toner additive.

In the amino resin composite particles according to the present invention, the fixing rate of the inorganic compound is 10% or more and 1
The lower limit value is 00% or less, more preferably 30% or more, further preferably 50% or more, still more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more. "Fixation rate" in the present invention
Is a numerical value calculated by the following measuring method (procedure).

The sticking rate in the present invention is such that the inorganic compound adhered to the surface of the amino resin composite particles according to the present invention is subjected to a shearing force to the suspension containing the amino resin composite particles to remove the inorganic compound having a low sticking degree. Then, centrifugal separation is performed, and the amino resin particles from which the inorganic compound has fallen off and the inorganic compound that has fallen off are separated from the suspension after the shearing force has been applied, to calculate. In the suspension obtained in the dropping test described below, the inorganic compound (specifically, the inorganic compound particles) is in a monodispersed state, and aggregation or the like has not occurred. Therefore, since the inorganic compound migrates to the upper layer of the suspension without settling, the separated inorganic compound and the precipitated amino resin composite particles can be separated by centrifugation.

The amino resin composite particles used in the drop-off test were previously filtered with a membrane filter having a pore size of 1.0 μm, and free inorganic compounds that had not adhered were removed. It is a particle.

At this time, the inorganic compound that is not firmly fixed is removed from the surface of the amino resin composite particles by the shearing force. Also, the amino resin composite particles settle down by centrifugation. Therefore, based on the amount (B ₁ ) of the inorganic compound obtained by measuring this amount (A ₁ ) and the content of the inorganic compound in the amino resin composite particles, the following formula (1) is used, It can be shown how strongly the inorganic compound is fixed to the surface of the amino resin composite particles, and it is defined as the fixing rate. This method is called a centrifugation method.

The sticking ratio of the present invention is calculated by applying a shearing force to a suspension containing amino resin composite particles to drop off an inorganic compound having a low sticking degree, and centrifuging the mixture after the drop-off test. To do. Specifically, the suspension containing the amino resin composite particles is stirred to apply a shearing force to the amino resin composite particles. The solid content concentration of the amino resin composite particles in the suspension used when applying the shearing force is 10% by weight based on the obtained suspension.

As will be described later, the sticking ratio of the present invention can also be measured by a heat treatment method. A specific method is to apply a shearing force to the suspension containing the amino resin composite particles to drop off an inorganic compound having a low degree of fixation, as in the drop-off test. The suspension after the dropping test is filtered through a membrane filter having a pore size of 1.0 μm to separate the dropped inorganic compound from the suspension, and the amino resin composite particles are filtered off. After that, water is evaporated from the filtrate, and the organic matter is burnt out at 700 ° C. Then, the amount (A ₂ ) of the inorganic compound dropped from the amino resin composite particles is calculated from the amount of the remaining ash. Then, based on the amount (B ₂ ) of the inorganic compound child particles in the amino resin composite particles, which is calculated from the content of the inorganic compound, which is separately calculated, the sticking rate is calculated according to the following formula (2).

As described above, the fixing rate of the present invention is determined by applying a shearing force to the suspension containing the amino resin composite particles so that the inorganic compound having a low degree of fixing is dropped off, and the suspension after the dropping test is tested for the pore size. It is also calculated by filtering with a 1.0 μm membrane filter and heat treating the filtrate.
This method is called a heat treatment method.

Further, in the following centrifugal separation method and heat treatment method, the tip peripheral speed (droplet peripheral speed of the stirring blade) of the drop test of the inorganic compound is expressed by the following formula (4): the peripheral peripheral speed of the stirring blade (m / s) = Blade diameter (m) × π × stirring speed (rpm) / 60 (4)

The ratio of the container diameter to the blade diameter (container diameter (mm) / blade diameter (mm) is 2.3 times. For the measurement, a container with a diameter (φ) of 90 mm and a diameter ( φ) A stirring blade having a blade size of 40 mm is used.

First, the centrifugation method will be described.

[Centrifugation Method] More specifically, the amino resin composite particles of the present invention are more specifically amino resin composite particles in which an inorganic compound is adhered to the surface of the amino resin particles, and the amino resin composite particles are used as a nonionic surfactant. 250 g of a suspension containing 10% by weight of the amino resin composite particles containing 4% by weight of polyoxyethylene oleyl ether (for example, "Emulgen 430" (trade name) manufactured by Kao Corporation) was placed in a container having a diameter of 92 mm. , To this suspension, set the blade size to diameter (φ) 4
Using a high speed disperser set to 0 mm and the height from the bottom of the beaker to the lowest end of the blade (stirring blade) set to 10 mm, the peripheral speed of the tip of the stirring blade was 5.2 m / s for 3 minutes at a rotation speed of 2500 rpm. After the shearing force was applied under the conditions described above, the suspension was centrifuged at a centrifugal force of 1880 G (where G represents average gravity) for 2 minutes, and 25 g of the supernatant (upper layer containing an inorganic compound) Of the inorganic compound dropped from 25 g of the amino resin composite particles calculated from the weight (g) of a solid obtained by evaporating to dryness at 110 ° C. for 30 minutes: (A ₁ ), and the amino resin composite. Weight (g) of the inorganic compound in 25 g of the amino resin composite particles, determined from the content of the inorganic compound in the particles: (B ₁ ).
From the following formula (1), the sticking ratio (%) = (1−A ₁ / B ₁ ) × 100 (1), the sticking ratio is 10% or more.

When the above suspension is obtained, the suspension is prepared using amino resin composite particles as described in the following examples. When the shearing force is applied for 3 minutes, the inorganic compound having a low degree of fixing falls off from the amino resin composite particles which do not satisfy the fixing rate of the present invention.

In the above measuring method, the nonionic surfactant is used in order to uniformly disperse and stabilize the amino resin composite particles and the separated inorganic compounds (child particles) in water, and to centrifuge the amino resin composite particles. This is to facilitate the separation of (and the mother particles from which the inorganic compound (child particles) has fallen off) and the separated inorganic compounds (child particles).

Therefore, for example, the solid content of the supernatant liquid obtained by using the amino resin composite particles (the content of the child particles is 20% by weight) in which the weight ratio of the mother particles and the child particles is 4: 1 is 2% by weight. If it is less than 90%, the sticking rate of the child particles is 90% or more.

However, the above-mentioned method (hereinafter referred to as the centrifugal separation method) is an inorganic compound (child particles) that has fallen off during the measurement of the sticking ratio.
If there is an aggregated inorganic compound in the powder, it may be aggregated together with the mother particles when centrifugally separated. That is, the numerical value of the sticking rate may be calculated slightly higher.

Therefore, in the case of measuring amino resin composite particles in which a relatively small inorganic compound that easily aggregates is fixed as child particles, the sticking rate can be measured by the above-mentioned method. It is more preferable to use the following method (hereinafter referred to as heat treatment method).

Next, the heat treatment method will be described.

[Heat Treatment Method] Amino Resin Composite Particles of the Present Invention
Shows that an inorganic compound is fixed on the surface of amino resin particles.
The mino resin composite particles are nonionic surfactants.
0.4 wt% polyoxyethylene oleyl ether
(For example, "Emulgen 430" manufactured by Kao Corporation (Product
Containing 10% by weight of the amino resin composite particles containing
250 g of the suspension was placed in a container with a diameter of 92 mm and
Use a turbid liquid with a blade size of 40 mm in diameter and
-Set the height from the bottom of the car to the bottom of the blade (stirring blade)
Using a high speed disperser set to 10 mm, the rotation speed
The peripheral speed of the tip of the stirring blade is 5.
After applying a shearing force at a condition of 2 m / s, the suspension is punctured.
Filter under reduced pressure using a filter with a diameter of 1.0 μm.
The filtrate of 1 was evaporated to dryness at 110 ° C for 30 minutes and then air-dried.
Weight of ash obtained by holding at 700 ° C for 1 hour in an atmosphere
Amount (g): (A₂), Specifically, 25 g of amino resin compound
The amount of inorganic compounds that have fallen off from the combined particles, and the amino
The value obtained from the content of the inorganic compound in the resin composite particles
Weight of inorganic compound in 25 g of the amino resin composite particles
(G): (B ₂) To the following formula (2) Sticking rate (%) = (1-A₂/ B₂) × 100 (2) Is characterized in that the sticking ratio determined by is 10% or more.
Amino resin composite particles.

However, the content of the inorganic compound in the amino resin composite particles is determined from the weight (g) (C) of the ash obtained by holding 2 g of the amino resin composite particles at 700 ° C. for 1 hour in the air atmosphere as follows. Formula (3) Content (%) = C / 2 * 100 ... (3) It shall be calculated | required.

In the heat treatment method as well, in the same manner as in the centrifugal separation method, when the suspension is obtained, the suspension is prepared by using amino resin composite particles as described in the following examples. To prepare. When the shearing force is applied for 3 minutes, the inorganic compound having a low degree of fixing falls off from the amino resin composite particles which do not satisfy the fixing rate of the present invention.

Further, as the suspension used in the above-mentioned drop test, the amino resin composite particles in a dry state are used as described and suspended under predetermined conditions, and a shearing force is applied.
If it is a suspension containing the amino resin composite particles, adjust the solid content concentration, add an extra surfactant and water as necessary, or remove water until the solid content concentration reaches a predetermined value. In the same manner, put into a container, apply a shearing force for 3 minutes under the condition that the peripheral speed of the tip of the stirring blade is 5.2 m / s, and perform a drop test.

In the present invention, the amino resin composite particles are taken out (separated) from the reaction solution during the manufacturing process.
Amino resin composite particles are obtained through the steps and drying steps. Therefore, the sticking rate can be measured by performing a drop test for dropping the child particles (inorganic compounds) from the amino resin composite particles by the above method. Further, for a composition in which the amino resin composite particles and a fine particle compound such as an inorganic compound are in a mixed state, after the composition (mixture) is previously separated using a membrane filter, the amino resin composite particles are separated. The sticking rate is measured by the drop test of the inorganic compound using the above heat treatment method. The conditions of the membrane filter used when separating the amino resin composite particles from the composition in which the amino resin composite particles and the fine particle compound such as an inorganic compound are in a mixed state are the average particle diameter of the above composition and The distribution may be measured and a membrane filter capable of separating the desired amino resin composite particles may be selected.

The amino resin composite particles according to the present invention are particularly useful when used as toner particles or toner additives because the charge amount of the toner can be controlled, and silica (inorganic compound) fixed to the mother particles is used. ) By appropriately adjusting the amount, the charge amount of the toner can be set to a desired value. For example, when the charge amount of the amino resin composite particles is set so that the blow-off charge amount is within the range of −50 to +50 μC / g, and more preferably within the range of −20 to +10 μC / g, the charge amount of the toner is appropriately adjusted. The toner can be adjusted, and the developability and transferability of the toner can be improved.

Therefore, the amino resin composite particles according to the present invention are used as toner particles or toner additives.
Alternatively, the toner composition containing the amino resin composite particles according to the present invention is one of the preferred embodiments of the application of the amino resin composite particles.

As the components (blends) other than the amino resin composite particles in the above-mentioned toner additives and toner compositions, components generally used in these additives and compositions may be used, if necessary. You can Examples of the component include pigments, dyes, dispersants, binder resins, surfactants, coupling agents and the like. The blending amount of these components may be appropriately set according to desired physical properties and the like. That is, the compounding amount of the amino resin composite particles in the toner additive or the toner composition may be appropriately set according to the desired physical properties and the like, and is not particularly limited, but 1 to 10
The range of 0 wt% is preferable, and the range of 5-100 wt% is more preferable. By appropriately adjusting the compounding amounts of the amino resin composite particles and the above components in the toner additive or toner composition, a toner additive or toner composition having desired physical properties can be obtained.

As described above, the amino resin composite particles obtained by the production method according to the present invention have a sticking ratio of 10%.
That is, the dropout rate is less than 90%. Therefore, for example, even when an external force is applied, the amount of the inorganic compound (child particles) falling off is smaller than that of the conventional amino resin composite particles. In addition, the amino resin composite particles have the surface of the amino resin particles (mother particles) modified by an inorganic compound (child particles), are excellent in solvent resistance, water resistance and heat resistance, and have high hardness. Further, since the inorganic compound (child particles) is less likely to fall off from the amino resin particles (mother particles), the charging characteristics of the amino resin composite particles can be made stable. Therefore, for example, matting agents for paints, light diffusing agents, rheology control agents, column packings, I
It can be suitably used as a C filler, a film coating agent, a wax additive, or an antibody, conductive particles, cosmetics, toner particles, a toner additive, an abrasive, and the like.

As described above, the amino resin composite particles of the present invention were prepared by placing a suspension containing 10% by weight of the amino resin composite particles in a container having a diameter of 92 mm and using a stirring blade having a blade size of 40 mm. Then, the inorganic compound was dropped from the amino resin composite particles by stirring under the condition that the tip peripheral speed of the stirring blade was 5.2 m / s, and the inorganic compound was obtained by measuring the amount of the dropped inorganic compound. The sticking rate of is 10% or more.

The amount of the inorganic compound that has fallen off the surface of the amino resin composite particles can be measured by performing a centrifugal separation method or a heat treatment method. That is, more specifically, the amino resin composite particles of the present invention are amino resin composite particles in which an inorganic compound is fixed to the surface of the amino resin particle, and the fixation ratio of the inorganic compound is 10% or more, The sticking rate was such that the suspension containing 10% by weight of the amino resin composite particles was placed in a container having a diameter of 92 mm and a stirring blade having a blade size of 40 mm was used, and the peripheral speed of the tip of the stirring blade was 5.
Shearing is applied by stirring under the condition of 2 m / s,
It is the sticking rate obtained from a drop-out test in which the inorganic compound having a low sticking degree adhered to the surface of the amino resin composite particles is dropped off and the amount of the dropped inorganic compound is measured by performing a centrifugation method or a heat treatment method. It is a composition.

In the amino resin composite particles of the present invention, the amino resin particles contain 40% by weight or more of at least one compound selected from the group consisting of benzoguanamine, cyclohexanecarboguanamine, cyclohexenecarboguanamine, and melamine. It is preferably composed of a reaction product of a compound and formaldehyde.

Furthermore, the amino resin composite particles of the present invention are
It is preferable that the above-mentioned inorganic compound is fixed to the surface of the mother particle as the mother particle by using the amino resin particle as the mother particle as a child particle. That is, in the amino resin composite particles of the present invention, the child particles made of the inorganic compound are fixed on the surface of the mother particles made of the amino resin, and the sticking rate of the child particles is preferably 10% or more.

Furthermore, the amino resin composite particles of the present invention are
The average particle size of the inorganic compound which is a child particle is 0.05 to 0.0.1 of the average particle size of the amino resin particle which is a mother particle.
It is preferably 001 times. That is, the amino resin composite particles of the present invention, the inorganic compound, the amino resin particles as a mother particle is fixed as a child particle on the surface of the mother particle, the average particle size of the inorganic compound is a mother particle. 0.05 to 0.001 of the average particle size of certain amino resin particles
It is preferably double.

The average particle size of the amino resin particles is in the range of 1 to 30 μm, and the average particle size of the inorganic compound is in the range of 0.001 to 1.5 μm.
Further, the average particle size of the mother particles is preferably larger than the average particle size of the child particles.

According to the above constitution, the amino resin composite particles have an inorganic compound, for example, a child particle made of an inorganic compound having a sticking ratio of 10% or more. Therefore, for example, even when an external force is applied, the drop-off of the child particles, that is, the drop-off of the inorganic compound is smaller than that of the conventional amino resin composite particles. Therefore, an amino resin composite particle in which an inorganic compound is stably adhered to the surface of an amino resin particle, for example, an amino resin composite in which child particles made of an inorganic compound are stably adhered to the surface of a mother particle composed of amino resin particles Particles can be provided.

The method for producing amino resin composite particles of the present invention is, as described above, a method for producing amino resin composite particles in which an inorganic compound is fixed to the surface of amino resin particles, and should be amino resin particles. At least one selected from an amino resin precursor, an amino resin precursor in the process of being cured to become amino resin particles, and an amino resin particle, and an inorganic compound to be fixed are dispersed in water in the presence of an emulsifier. , At least one surface selected from amino resin precursors which are mixed while applying shearing force to become the above amino resin particles, amino resin precursors in the middle of curing which become amino resin particles, and amino resin particles The method comprises an inorganic compound fixing step of fixing

As one form of the method, for example, in the inorganic compound fixing step, the amino resin precursor to be amino resin particles and the inorganic compound to be fixed are dispersed in water and the emulsifier is added. A method (form) is a step of mixing in the presence of a shearing force, and further comprising a curing step of adding a catalyst to cure the amino resin precursor.

The method for producing the amino resin composite particles of the present invention is preferably a method of mixing the emulsifier in the range of 1 to 30% by weight with respect to the amino resin precursor.

In the inorganic compound fixing step, an amino resin precursor emulsion is prepared by mixing an aqueous dispersion of an amino resin precursor to be amino resin particles with an aqueous solution of an emulsifier and emulsifying the mixture. It is preferable to include an emulsion preparation step, and an inorganic compound mixing step of mixing the emulsion obtained in the emulsion preparation step and the inorganic compound while applying a shearing force.

Furthermore, in the step of mixing the inorganic compound, it is preferable that the inorganic compound is mixed with the emulsion in a state of being dispersed in water.

For example, the method for producing amino resin composite particles of the present invention is a method for producing amino resin composite particles in which child particles made of an inorganic compound are fixed on the surface of mother particles made of amino resin. An emulsion consisting of an aqueous dispersion of an amino resin precursor to be formed and an aqueous emulsifier solution, and an aqueous dispersion of an inorganic compound to be formed into child particles are mixed and emulsified while applying a shearing force, and then the catalyst The method of adding and curing is preferred.

According to the above method, at least one selected from an amino resin precursor to be amino resin particles, a curing amino resin precursor to be amino resin particles, and an amino resin particle and an inorganic resin to be fixed. Since the compound and the compound are dispersed in water and mixed in the presence of an emulsifier while applying a shearing force to emulsify or suspend while applying a shearing force, these amino resin precursor and / or amino resin The surface of the particles (that is, at least one selected from amino resin precursors to be amino resin particles, amino resin precursors in the process of curing to be amino resin particles, and amino resin particles) becomes soft due to emulsion or suspension. The surface of these amino resin precursors and / or amino resin particles in the state of It may be attached to (secured). Therefore, according to the above method, the inorganic compound can be firmly fixed (fixed) to the surface of the amino resin precursor and / or the amino resin particles, and therefore, the inorganic compound is removed even when external force is applied. It is possible to easily and inexpensively provide the amino resin composite particles having a smaller amount.

In particular, according to the present invention, for example, an emulsion comprising an amino resin precursor to be mother particles and an aqueous emulsifier solution, and an inorganic compound to be child particles are mixed with each other in an aqueous dispersion state. The emulsion is emulsified while applying a shearing force and then cured, so that the surface of the mother particles made of the amino resin is formed on the surface of the mother particles made of an amino resin without increasing the number of manufacturing steps compared to the case of coating the surface. The particles can be fixed. That is, the child particles can be easily and inexpensively fixed to the surface of the mother particles. Moreover, since the emulsion is emulsified while applying a shearing force, the child particles are firmly fixed to the mother particles, so that the child particles are hard to fall off from the mother particles. This makes it possible to easily and inexpensively produce the amino resin composite particles in which the child particles are fixed to the surface of the mother particles.

Further, as another embodiment of the method for producing amino resin composite particles of the present invention, the inorganic compound fixing step comprises mixing an aqueous dispersion of an amino resin precursor to be amino resin particles with an aqueous solution of an emulsifier. An emulsion preparation step of preparing an emulsion of an amino resin precursor by emulsification, and a curing step of performing a curing reaction by adding a catalyst to the emulsion obtained in the emulsion preparation step. A method (form) including an inorganic compound mixing step of mixing a suspension containing an amino resin precursor in the middle of curing and an inorganic compound to be fixed while applying a shearing force.

The inorganic compound fixing step may be provided with an emulsifier aqueous solution adding step of further adding an emulsifier aqueous solution to the suspension containing the amino resin precursor in the middle of curing before the inorganic compound mixing step. preferable.

It is preferable that the inorganic compound fixing step further comprises a formaldehyde aqueous solution adding step of adding an aqueous formaldehyde solution before the inorganic compound mixing step.

Further, in the step of mixing the inorganic compound, it is preferable that the inorganic compound is mixed with the suspension in a state of being dispersed in water.

As still another embodiment of the method for producing amino resin composite particles of the present invention, in the inorganic compound fixing step, the amino resin particles and the inorganic compound to be fixed are
In the state of being dispersed in water, it is a step of mixing in the presence of an emulsifier while applying a shearing force, and the inorganic compound fixing step is performed by mixing an aqueous dispersion of the amino resin particles and an aqueous solution of an emulsifier. A suspension preparation step of preparing a suspension of amino resin particles by turbidity, a suspension obtained in the emulsion preparation step, and an inorganic compound to be fixed are mixed while applying a shearing force. The method (form) including the inorganic compound mixing step of In the suspension preparation step,
The suspension is preferably prepared in the presence of formaldehyde.

As the amino resin particles, commercially available amino resin particles may be used, or the amino resin precursor may be cured and used. That is, as the method for producing amino resin composite particles of the present invention, the inorganic compound fixing step comprises the amino resin particles and the inorganic compound to be fixed,
In a state of being dispersed in water, in the presence of an emulsifier, it is a step of mixing while applying a shearing force, before the inorganic compound fixing step, an aqueous dispersion of an amino resin precursor to be amino resin particles and an emulsifier. The emulsion preparation step of preparing an emulsion of the amino resin precursor by mixing and emulsifying the aqueous solution of the above, and adding the catalyst to the emulsion obtained in the above emulsion preparation step A curing step of curing a resin precursor, the inorganic compound fixing step, the suspension containing the amino resin particles obtained by the curing step, an emulsifier aqueous solution addition step of further adding an aqueous solution of an emulsifier, and The method (form) may include an inorganic compound mixing step of mixing the suspension obtained in the emulsifier aqueous solution adding step and the inorganic compound to be fixed while applying a shearing force.

It is preferable that the inorganic compound fixing step further comprises a formaldehyde aqueous solution adding step of adding the formaldehyde aqueous solution before the inorganic compound mixing step. In the inorganic compound mixing step, the inorganic compound is preferably mixed with the suspension in a state of being dispersed in water.

That is, depending on the inorganic compound to be adhered, if it is added during the emulsification of the amino resin precursor (that is, when the amino resin precursor is emulsified in the presence of an emulsifier), the emulsion particles of the amino resin precursor are destroyed. The broken emulsion particles of the amino resin precursor may aggregate. Therefore, if there is such a possibility, once the catalyst (curing catalyst) is added to cure the amino resin precursor to some extent or completely, the inorganic compound is treated with the amino resin particles, that is, It is preferable to adhere (fix) to the mother particles. However, in this case, since the amino resin particles or the amino resin precursor serving as the mother particles are hardened by curing, the inorganic compound is hard to adhere. Therefore, by suspending the aqueous dispersion in the presence of an emulsifier, a soft layer for adhering (fixing) the inorganic compound by the shearing force can be formed on the surface of the mother particle. At this time, by further adding formaldehyde, for example, as an aqueous formaldehyde solution and suspending it, the mother particle surface and the soft layer formed later on the mother particle surface by suspension can be chemically bonded. It is possible to prevent the formed soft layer from peeling off during drying, and to obtain amino resin composite particles having a high sticking rate. According to the present invention, even in this case,
Amino resin composite particles in which child particles made of an inorganic compound are fixed to the surface of mother particles made of amino resin particles can be obtained.

In the present invention, the above-mentioned inorganic compound is a particulate inorganic compound, and it is preferable that child particles made of an inorganic compound are fixed to the surfaces of mother particles made of amino resin particles.

In the present invention, the shearing force may be, for example, an amino resin precursor to be amino resin particles, an amino resin precursor being cured to be amino resin particles,
And at least one selected from amino resin particles,
An inorganic compound to be fixed is dispersed in water, and in the presence of an emulsifier, the tip peripheral speed is 2 m / s or more, 30 m / s
It is applied by shearing with a stirring blade rotating below. Alternatively, the shearing force is at least one selected from an amino resin precursor to be amino resin particles, an amino resin precursor in the course of curing to be amino resin particles, and an amino resin particle, and an inorganic compound to be fixed. , In the state of being dispersed in water, in the presence of an emulsifier, 3 MPa or more,
It can also be applied by colliding with each other at a discharge pressure of 49 MPa or less. Further, the shearing force is to be an amino resin precursor to become amino resin particles, and amino resin particles to become amino resin particles in the tank in a stirring device having a tank in which a baffle that changes the flow direction at a right angle is continuously installed. At least one selected from the amino resin precursor and the amino resin particles which are being cured, and the inorganic compound to be fixed are dispersed in water in the presence of an emulsifier to give 0.1M.
It can also be applied by pressure-feeding at a discharge pressure of Pa or more and 1.47 MPa or less and forcibly circulating or liquid feeding.

Further, in the present invention, a catalyst is added to an emulsion obtained by emulsifying an amino resin precursor to cure the amino resin precursor, and a suspension containing amino resin particles or amino resin composite particles is prepared. A suspension is obtained. Then, if necessary, separation and drying steps are performed to obtain solid amino resin particles or amino resin composite particles. Further, in the present invention, a stage in the middle of the above step, that is, a suspension containing amino resin particles or amino resin composite particles obtained by a curing reaction is extracted from the reaction system to cure according to the present invention. A suspension containing the amino resin particles or the cured amino resin composite particles may be purified, if necessary, and then used. It is an embodiment of the present invention to use the amino resin particles or the amino resin composite particles as a solid as a suspension containing the cured amino resin particles or the cured amino resin composite particles without going through a separation / drying step. .
Further, if there is no problem in the above-mentioned use, the suspension containing the amino resin composite particles can be used for the above use without isolating the amino resin composite particles obtained through the curing step. Specifically, an abrasive or a film coating agent formed from a suspension containing amino resin composite particles is a preferred form.

[0133]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The oil absorption amount (ml / 100 g), the powder resistance value (Ω · cm), the charge amount (μC / g), and the average particle diameter (μm) described in the examples were measured by the following methods.

[Oil Absorption] The oil absorption of the amino resin composite particles was measured by employing the oil absorption measuring method described in JIS K 5101 “Pigment Test Method”.

[Powder Resistance Value] Fourth Edition Experimental Chemistry Lecture 9 The powder resistance of amino resin composite particles was measured by using the resistivity measurement method by the four-terminal method described in Electricity and magnetism (publishing company Maruzen Co., Ltd.). The value was measured. The measurement sample was prepared as follows. That is, a predetermined cell (vertical (length) 4 cm × horizontal (width) 4 c in which electrodes are provided at the bottom and the center (two places)
(m × height 1 cm), the amino resin composite particles were put in the cell, and the tapping operation was performed to fill the amino resin composite particles into the cell. Next, a lid provided with electrodes was attached to the cell to obtain a measurement sample. The bottom electrode and the lid electrode were used as current introducing terminals, and the center electrode was used as a voltage measuring terminal. Then, a constant current was made to flow between the current introducing terminals using a DC constant voltage power source, and the potential difference between the voltage measuring terminals was measured using a voltmeter (measurement condition: temperature 20
C, relative humidity 20%). Then, the powder resistance value of the amino resin composite particles was determined from the current value, the distance between the voltage measurement terminals, and the potential difference.

The amino resin composite particles used for the measurement of the powder resistance value were used after drying the amino resin composite particles after the dropping test. The powder resistance value of the amino resin composite particles of the present invention is preferably 1.0 × 10 ⁹ Ω · cm or less, more preferably 1.0 × 10 ⁸ Ω · cm or less,
1.0 × 10 ⁷ Ω · cm or less is more preferable. By lowering the powder resistance value of the amino resin composite particles, it can be preferably used as a conductive filler in applications such as conductive plastics or conductive paints.

[Charge Amount] The charge amount of the amino resin composite particles was measured by using the suction blow-off method. That is, 1.15 g of amino resin composite particles and 28.95 g of iron oxide powder (manufactured by Dowa Iron Powder Co., Ltd .; trade name DSP-128) have a capacity of 50 m.
The amino resin composite particles were charged by placing them in a polyethylene container of 1 and stirring for 30 seconds using a paint shaker (manufactured by Toyo Seiki Co., Ltd.). By stirring the amino resin composite particles and the iron oxide powder, the amino resin composite particles are positively charged and the iron oxide powder is negatively charged, and the amino resin composite particles adhere to the surface of the iron oxide powder. . Then, the above mixture was put into a predetermined cell having a mesh on the bottom surface, and pressure blowing and suction were carried out simultaneously to remove the amino resin composite particles adhering to the iron oxide powder. This iron oxide powder 1.
About 0 g, the residual charge amount was measured using a suction type blow-off device (manufactured by Toshiba Chemical Co., Ltd.), and the charge amount of the amino resin composite particles was determined from this value. The amino resin composite particles used for measuring the charge amount were used after drying the amino resin composite particles after the above-mentioned drop test.

[Average Particle Size] The average particle size of the above-mentioned amino resin precursor (average particle size of the amino resin precursor dispersed in the emulsion obtained by emulsification) and the target amino resin composite particles The average particle diameter is a value measured by using a Coulter Multisizer II type described in Examples below.

The sticking rate was determined by a drop test using the following centrifugal separation method or heat treatment method. The amino resin composite particles used in the dropping test are amino resin composite particles in a state in which the free inorganic compound that has not been fixed is removed by filtering with a membrane filter having a pore size of 1.0 μm in advance. .

[Centrifugation method] A beaker (diameter (φ) 92 mm) with a capacity of 500 ml was charged with 25 g of amino resin composite particles.
And 224 g of pure water, and a nonionic surfactant as a dispersion aid (manufactured by Kao Corporation; trade name Emulgen 430).
Put 1g of 5wt% aqueous solution and set the blade size to diameter (φ).
Blades (stirring blades) to 40 mm and from the bottom of the beaker
Shearing force was applied by stirring for 3 minutes at a rotation speed of 2500 rpm using a high-speed disper whose height to the lowermost end was set to 10 mm.

In this way, a shearing force was applied to the suspension containing 10% by weight of the amino resin composite particles to remove the inorganic compound having a low degree of fixing. Under the above stirring conditions, a suspension containing 10% by weight of the amino resin composite particles was placed in a container having a diameter of 92 mm, a stirring blade having a blade size of 40 mm was used, and the tip peripheral speed of the stirring blade was 5 mm. ．
This means that the mixture was agitated under the condition of 2 m / s and a shearing force was applied.

Next, 12.5 g of the suspension was evenly placed in four 15 ml settling tubes each having a length of 12.5 g, and a small tabletop centrifuge (manufactured by Nisseon Medical Science Equipment Co., Ltd .; model name) Using NT-4), centrifugation was performed at a rotation speed of 4100 rpm (centrifugal force 1880 G) for 2 minutes to precipitate the amino resin composite particles. Although the above-mentioned centrifugal separation conditions are used, even when the type of the centrifugal separator is different, centrifugal separation can be performed under the same conditions by setting the centrifugal force. Then, the amino resin composite particles 2 were calculated from the weight (g) of a solid obtained by evaporating and drying 25 g of the supernatant (upper layer containing an inorganic compound) at 110 ° C. for 30 minutes.
Amount of inorganic compound dropped from 5 g: (A ₁ ), and weight (g) of inorganic compound in 25 g of the amino resin composite particle, determined from the content of the inorganic compound in the amino resin composite particle: (B ₁ ). From the following formula (1) Adhesion rate (%) = (1-A ₁ / B ₁ ) × 100 (1) However, A ₁ : Amount of inorganic compound (child particles) dropped from 25 g of the amino resin composite particles (g) ) B _1: inorganic compounds (determined from the content of the child particles), was calculated adhesion ratio based on the amount of the inorganic compound of the amino resin composite in particles 25 g (child particles) (g).

[Heat Treatment Method] A beaker (diameter (φ) 92 mm) with a capacity of 500 ml was charged with 25 g of amino resin composite particles.
And 224 g of pure water, and a nonionic surfactant as a dispersion aid (manufactured by Kao Corporation; trade name Emulgen 430).
Put 1g of 5wt% aqueous solution and set the blade size to diameter (φ).
Blades (stirring blades) to 40 mm and from the bottom of the beaker
Shearing force was applied by stirring for 3 minutes at a rotation speed of 2500 rpm using a high-speed disper whose height to the lowermost end was set to 10 mm.

In this way, a shearing force was applied to the suspension containing the amino resin composite particles as a solid content in an amount of 10% by weight to remove inorganic compounds having a low degree of fixation. Under the above stirring conditions, a suspension containing 10% by weight of the amino resin composite particles was placed in a container having a diameter of 92 mm, a stirring blade having a blade size of 40 mm was used, and the tip peripheral speed of the stirring blade was 5 mm. This means that the mixture was agitated under the condition of 0.2 m / s and a shearing force was applied.

Next, this suspension was filtered under reduced pressure using a membrane filter (manufactured by Toyo Roshi Kaisha, Ltd., pore size: 1.0 μm, material: cellulose mixed ester).

The obtained filtrate was collected in an aluminum cup and the water was evaporated to obtain a solid. The solid is transferred to a crucible and kept in an electric furnace at 700 ° C. for 1 hour under an air atmosphere. After cooling, the ash content was measured. And
The amount of the ash was taken as the amount (A ₂ ) of the inorganic compound (child particles) that had fallen off from the amino resin composite particles, and the ratio was determined to obtain the following formula (2) fixation rate (%) = (1-A ₂ / B ₂ ). × 100 (2) However, A ₂ : amount (g) of the inorganic compound (child particles) dropped from the amino resin composite particles B ₂ : 25 g of the amino resin composite particles obtained from the content rate of the inorganic compound (child particles) The sticking rate was calculated based on the amount (g) of the inorganic compound (child particles) in it.

The content of the inorganic compound (sub-particles) of B ₂ in the above formula (2) is determined by measuring 2 g of the amino resin composite particle sample before applying shearing force in the electric furnace in the electric furnace for the sticking rate measurement. Amino resin composite obtained by holding at 700 ° C. for 1 hour in an atmosphere, and from the ash content: C (g), based on the following formula (3) content rate (%) = C / 2 × 100 (3) It is the content rate of the inorganic compound (child particles) in the particle sample.

Among the stirrers, mixers, and stirrers used in the following Examples and Comparative Examples, the stirrer, that is, the emulsion of the amino resin precursor, the amino resin precursor during the curing of the amino resin, And a reaction liquid (water dispersion) containing at least one kind of amino resin particles (crosslinked amino resin particles) after curing, and an inorganic compound to be fixed, for example, an aqueous dispersion of an inorganic compound to be child particles. The stirrer used when mixing the above and fixing the above inorganic compound to the surface of the amino resin particles is a stirrer having a high shearing force.

The stirrer or mixer is used when the reaction liquid is prepared or mixed in the steps other than the above. Specifically, a stirrer is used when the amino resin precursor is produced or when the emulsion of the amino resin precursor is condensed and cured, and the amino resin precursor is milked in the presence of an emulsifier (for example, polyvinyl alcohol). A mixer is used for turbidity.

Example 1 Reflux condenser, stirrer, thermometer, vibrating viscometer (MIVI ITS Japan Co .; model name MIVI
3250.0 g of benzoguanamine (17.
4 mol) and formalin 2818.3 with a concentration of 37% by weight
g (formaldehyde 34.8 mol) and sodium carbonate 10% by weight aqueous solution 10 g (sodium carbonate 0.01 mol) were charged, and the temperature was raised with stirring to 95 to 97.
The reaction was carried out at ° C.

The viscosity of the reaction solution is 4 × 10 ^-2 Pa ·
The reaction was terminated by cooling the reaction solution when s (40 cP) was reached. As a result, a reaction liquid containing an amino resin precursor which is an initial condensate of benzoguanamine and formaldehyde (water dispersion of amino resin precursor)
Got The viscosity was measured using a process viscometer attached to the reaction kettle.

Next, a reflux condenser, a mixer for emulsifying the reaction solution containing the amino resin precursor, and a high shearing force for fixing the child particles made of the inorganic compound to the amino resin particles as the mother particles. Polyvinyl alcohol (manufactured by Kuraray Co., Ltd .; trade name PVA205) as an emulsifier in a reaction kettle having a capacity of 25 L equipped with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) as a stirrer and a thermometer.
An aqueous solution prepared by dissolving 0 g in 7,000 g of water was charged, and the temperature was raised to 75 ° C. with stirring. Then, after the above reaction solution was added to the reaction kettle, the contents were vigorously stirred at a rotation speed of 7,000 rpm using the above stirring device having a high shearing force while maintaining the temperature at 77 ° C. The resin precursor was emulsified. Then, in the reaction kettle, an emulsion of the amino resin precursor and a supercolloid # 1 having a solid content concentration of 22% by weight as an aqueous dispersion of an inorganic compound.
6 (trade name; conductive carbon manufactured by Nippon Graphite Co., Ltd., 1
After adding 1480 g of an aqueous dispersion having a secondary particle diameter of 0.3 μm), the content was kept for 5 minutes at a rotation speed of 7,000 rpm using a TK homomixer, which is a stirring device having the same high shearing force, while maintaining at 77 ° C. , Stirred vigorously. Therefore,
The amount of the inorganic compound used with respect to the amino resin precursor is 8% by weight. As a result, the concentration of the amino resin precursor becomes 3
An 8.6% by weight emulsion was obtained. Pure water 1 in the obtained emulsion.
200 g was added and cooled to 30 ° C.

Then, an aqueous solution prepared by dissolving 80 g of dodecylbenzenesulfonic acid as a catalyst in 1500 g of pure water was added to the above emulsion, and the temperature was raised to 90 ° C. at 10 ° C./hr while stirring, and 90 After reaching 0 ° C., this temperature was maintained for 1 hour to condense and cure the amino resin precursor and / or the amino resin particles (amino resin crosslinked particles) together with the inorganic compound. Therefore, the total reaction (curing) time is 7
It's time.

After the curing was completed, the amino resin composite particles of the present invention (amino resin crosslinked composite coated particles) were taken out from the reaction solution by filtering. After heat-treating the taken out amino resin composite particles at 130 ° C. for 3 hours,
It was crushed by placing it in a mortar and applying light force with a pestle. As a result, black powdery amino resin composite particles were obtained. When the amino resin composite particles were measured with Multisizer (manufactured by Coulter; Coulter Multisizer II type), the average particle diameter (d50) was 9.1 μm, and the standard deviation was 4.8 μm. Further, the average particle size of the amino resin particles (amino resin crosslinked particles) as the mother particles, measured in the same manner, was 6.5 μm. The adherence rate measured by the centrifugal separation method is 96%, the adherence rate measured by the heat treatment method is 94%, and the oil absorption is 150 ml / 10.
0 g, the powder resistance value was 7.5 × 10 ⁵ Ω · cm, and the charge amount was −8.0 μC / g. The results are summarized in Table 1.

Example 2 First, an TK homomixer was used as a mixer to obtain an amino resin precursor emulsion. After that, a stirring device having a high shearing force, which is used when the aqueous dispersion of the inorganic compound is added to the emulsion of the amino resin precursor and stirred, is prepared from TK Homomixer to TK Lab Disper Black powdery amino resin composite particles were obtained by performing the same reaction and operation as in Example 1 except that the product was manufactured by the company. The results of measuring various physical properties of the amino resin composite particles are summarized in Table 1.

Example 3 A TK homomixer was used as a mixer to obtain an amino resin precursor emulsion, and then an aqueous dispersion of an inorganic compound was added to the amino resin precursor emulsion and stirred. The stirring device with high shearing force used when
Black powdery amino resin composite particles were obtained by performing the same reaction and operation as in Example 1 except that the TK homomixer was changed to Ebara Milzer (manufactured by Ebara Corporation) and the rotation speed was set to 4000 rpm. Got The results of measuring various physical properties of the amino resin composite particles are summarized in Table 1.

Example 4 An TK homomixer was used as a mixer to obtain an amino resin precursor emulsion, and then an aqueous dispersion of an inorganic compound was added to the amino resin precursor emulsion and stirred. The stirring device with high shearing force used when
Change from TK homomixer to high pressure homogenizer (made by Izumi Food Maginari Co., Ltd.) and discharge pressure 6.86MP
Example 1 except that a (70 kgf / cm ² ) was set.
Black powdery amino resin composite particles were obtained by performing the same reaction / operation, etc. The results of measuring various physical properties of the amino resin composite particles are summarized in Table 1.

Example 5 A TK homomixer was used as a mixer to obtain an amino resin precursor emulsion, and then an aqueous dispersion of an inorganic compound was added to the amino resin precursor emulsion and stirred. The stirring device with high shearing force used when
TK homomixer was changed to static mixer (manufactured by Noritake Co., Ltd.), and the discharge pressure was adjusted to 0.
Other than setting to 98 MPa (10 kgf / cm ² ),
By performing the same reaction and operation as in Example 1, black powdery amino resin composite particles were obtained. The results of measuring various physical properties of the amino resin composite particles are summarized in Table 1.

Example 6 As an aqueous dispersion of an inorganic compound, an aqueous dispersion of Aerosil 200 (trade name; silica manufactured by Nippon Aerosil Co., Ltd., primary particle diameter: 0.01 μm) having a solid content concentration of 10% by weight. Other than using 3256g,
By performing the same reaction and operation as in Example 1, white powdery amino resin composite particles were obtained. The amount of the inorganic compound used with respect to the amino resin precursor is 8% by weight. The results of measuring various physical properties of the amino resin composite particles are summarized in Table 2. 1 and 2 are electron micrographs (7500 times) of the amino resin composite obtained in this example.

Example 7 As an aqueous dispersion of an inorganic compound, 2900 g of an aqueous dispersion of Aerogel 200 (same as above) having a solid content concentration of 10% by weight was used, and before the addition of the aqueous dispersion of the inorganic compound. , 2 amino resin precursor emulsions
Mixer for emulsifying the reaction liquid containing the amino resin precursor and stirring with high shearing force for fixing the child particles made of the inorganic compound to the amino resin particles as the mother particles while cooling to 5 ° C. Ebara Milzer (manufactured by EBARA CORPORATION) is used as the device, and the rotation speed is 50.
The same reaction as in Example 1 except that it was set to 00 rpm.
By performing operations and the like, white powdery amino resin composite particles were obtained. That is, in this example, the above-mentioned Ebara Milzer was used as a mixer and a stirrer to emulsify the mixed solution of the amino resin precursor and the emulsifier at a rotation speed of 5000 rpm, and then the emulsion was heated to 25 ° C. After that, the water dispersion 290 of Aerosil 200 having a solid content concentration of 10% by weight as a water dispersion of an inorganic compound is placed in a reaction kettle.
At the same time as inputting 0 g, at the above Ebara Milzer,
The contents were stirred at a rotation speed of 5000 rpm. The amount of the inorganic compound used with respect to the amino resin precursor is 7% by weight. The results of measuring various physical properties of the amino resin composite particles are summarized in Table 2.

Further, in order to confirm the adherence of silica (child particles) in the obtained amino resin composite particles, an X-ray micro analyzer (manufactured by Shimadzu Corporation; model name EPMA-16) was used.
The silica Kα was mapped in (10) (magnification: 2000).
However, adhesion of silica was observed on the amino resin particles.

[Comparative Example 1] An TK homomixer was used as a mixer to obtain an amino resin precursor emulsion, and then an aqueous dispersion of an inorganic compound was added to the amino resin precursor emulsion and stirred. The stirring device with high shearing force used when
Black powdery amino resin composite particles were obtained by performing the same reaction and operation as in Example 1 except that the TK homomixer was changed to a four-paddle, which is a general stirrer, and the rotation speed was set to 200 rpm. Obtained. The results of measuring various physical properties of the comparative amino resin composite particles are summarized in Table 2.

[Comparative Example 2] As an aqueous dispersion of an inorganic compound, 2900 g of an aqueous dispersion of Aerosil 200 (same as above) having a solid content of 10% by weight was used, and a TK homomixer was used as a mixer to prepare an amino resin precursor. After obtaining the body emulsion, a stirring device having a high shearing force, which is used when the aqueous dispersion of the inorganic compound is added to the emulsion of the amino resin precursor and stirred, is generally used from the TK homomixer. A white powdery amino resin composite particle was obtained by performing the same reaction and operation as in Example 1 except that the paddle was changed to a four-paddle which is a typical stirrer and the rotation speed was set to 200 rpm. The amount of the inorganic compound used is 7% by weight based on the amino resin precursor.
Is. The results of measuring various physical properties of the comparative amino resin composite particles are summarized in Table 2.

[Example 8] As an aqueous dispersion of an inorganic compound, the above Aerogel 200 having a solid content concentration of 10% by weight.
In place of, alumina having a solid content concentration of 10% by weight (manufactured by Nippon Aerosil Co., Ltd .; trade name: aluminum oxide C, 1
Amino resin composite particles in the form of white powder were obtained by performing the same reaction and operation as in Example 7, except that 2900 g of an aqueous dispersion having a secondary particle diameter of 0.01 μm) was used. The amount of the inorganic compound used with respect to the amino resin precursor is 7% by weight. The average particle size (d50) measured in the same manner as in Example 1 was 9.2 μm, the average particle size of the mother particles was 9.1 μm, and the standard deviation was 5.0 μm. The adhered rate was 95%. The results of these measurements are summarized in Table 3. The charge amount measured in the same manner as in Example 1 was +2.6 μC / g.

Further, in order to confirm the adherence of alumina (child particles) in the obtained amino resin composite particles,
When aluminum Kα was mapped with an X-ray microanalyzer (same as above) (magnification: 2000 times), aluminum adhesion was observed on the amino resin particles.

Example 9 As an aqueous dispersion of an inorganic compound, the supercolloid # having a solid concentration of 22% by weight was prepared.
In place of 16, except for using 3250 g of an aqueous dispersion of titania (manufactured by Ishihara Sangyo Co., Ltd .; trade name TTO-55 (N), primary particle diameter 0.04 μm) having a solid content concentration of 10% by weight, was carried out. By performing the same reaction and operation as in Example 1, white powdery amino resin composite particles were obtained. The amount of the inorganic compound used with respect to the amino resin precursor is 8% by weight. The average particle diameter (d50) and the average particle diameter of the mother particles measured in the same manner as in Example 1 were 8.9 μm, the standard deviation was 4.7 μm, and the sticking ratio measured by the heat treatment method was 75%. Met. The results of these measurements are summarized in Table 3. The charge amount measured in the same manner as in Example 1 was +2.0 μC / g.

Further, in order to confirm the fixing condition of titania (child particles) in the obtained amino resin composite particles,
When titanium Kα was mapped with an X-ray microanalyzer (same as above) (magnification: 2000 times), titanium adhesion was observed on the amino resin particles.

Example 10 First, resinification was carried out in the same manner as in Example 1 to obtain a reaction solution containing an amino resin precursor,
A TK homomixer was used as a mixer for emulsifying the reaction liquid containing the amino resin precursor, and emulsification was performed at a temperature of 77 ° C. in the same manner as in Example 1 to obtain an emulsion containing the amino resin precursor. .

Then, the emulsion was cooled to 25 ° C. without adding an aqueous dispersion of an inorganic compound to the emulsion. Then, while stirring this emulsion, to the emulsion,
An aqueous solution prepared by dissolving 80 g of dodecylbenzenesulfonic acid as a catalyst in 1500 g of pure water was added and the temperature was raised to 40 ° C., and the temperature was maintained for 1 hour to allow condensation and curing of the amino resin precursor to proceed. . Subsequently, an aqueous solution prepared by dissolving 160 g of dodecylbenzenesulfonic acid in 3000 g of pure water was added to the reaction liquid in the course of this reaction (curing), and then 10 ° C. was added to 50 ° C. while stirring.
The temperature was raised at / hr.

Then, to this reaction liquid during the reaction (curing), an aqueous solution obtained by dissolving 100 g of polyvinyl alcohol (same as in Example 1) as an emulsifier in 700 g of water, heated to 50 ° C., was added. A TK homomixer was used as a mixer for suspending the reaction solution containing the amino resin precursor (amino resin precursor and / or amino resin particles (amino resin crosslinked particles)) being cured while maintaining the temperature at 0 ° C. The mixture was stirred at a rotation speed of 7000 rpm for 3 minutes, and then 500 g of formalin (same as in Example 1) was added and similarly stirred for 3 minutes. Next, in this reaction liquid, as an aqueous dispersion of an inorganic compound, ceria (manufactured by CI Kasei Co., Ltd .; trade name NanoTek CeO ₂ , primary particle diameter 0.01 μm)
A dispersion prepared by dispersing 450 g of water in 4000 g of water is gently added, and while maintaining the reaction solution at 50 ° C., high shearing for fixing the child particles made of an inorganic compound to the amino resin particles as the mother particles. A TK homomixer was used as a stirrer having power, and the mixture was stirred for 5 minutes at a rotation speed of 5000 rpm.

Thereafter, the reaction solution was heated to 90 ° C. for 1 hour.
The temperature was raised at 0 ° C./hr, and after reaching 90 ° C., the temperature was kept at this temperature for another hour to condense and cure the amino resin precursor in the course of curing with an inorganic compound. That is, the amino resin precursor and the inorganic compound which were being cured were brought into contact with each other as an aqueous dispersion while maintaining the particle state. As a result, amino resin composite particles in which the surfaces of the mother resin, ie, the amino resin particles, were covered with the child particles made of the inorganic compound, and the child particles made of the inorganic compound were fixed to the surfaces of the amino resin particles were obtained.

After the completion of curing, the heat treatment and the like were carried out in the same manner as in Example 1 to obtain brown powdery amino resin composite particles. The amount of the inorganic compound used with respect to the amino resin precursor and amino resin particles (amino resin crosslinked particles) is 10% by weight. The average particle size (d50) measured in the same manner as in Example 1 was 8.6 μm, the average particle size of the mother particles was 8.5 μm, and the standard deviation was 4.8 μm, which was measured by the heat treatment method. The adhered rate was 93%.
The results of these measurements are summarized in Table 3.

Further, in order to confirm the fixing condition of ceria (child particles) in the obtained amino resin composite particles, X
When cerium Lα was mapped with a line microanalyzer (same as above) (magnification: 2000 times), cerium adherence was observed on the amino resin particles.

Example 11 First, resinification was carried out in the same manner as in Example 1 to obtain a reaction solution containing an amino resin precursor,
A TK homomixer was used as a mixer for emulsifying the reaction liquid containing the amino resin precursor, and emulsification was performed at a temperature of 77 ° C. in the same manner as in Example 1 to obtain an emulsion containing the amino resin precursor. .

Subsequently, the emulsion was cooled to 25 ° C. without adding an aqueous dispersion of an inorganic compound to the emulsion. Then, while stirring this emulsion, to the emulsion,
An aqueous solution prepared by dissolving 80 g of dodecylbenzenesulfonic acid as a catalyst in 1500 g of pure water was added and the temperature was raised to 40 ° C., and the temperature was maintained for 1 hour to allow condensation and curing of the amino resin precursor to proceed. . Subsequently, an aqueous solution prepared by dissolving 160 g of dodecylbenzenesulfonic acid in 3000 g of pure water was added to the reaction liquid in the course of this reaction (curing), and then stirred at 10 ° C. until it reached 90 ° C.
After the temperature was raised at 90 ° C./hr and the temperature reached 90 ° C., the temperature was maintained for 1 hour to condense and cure the amino resin precursor to obtain amino resin particles (amino resin crosslinked particles).

After completion of the above curing, 100 g of polyvinyl alcohol (same as in Example 1) as an emulsifier, heated to 90 ° C., was added to 700 g of water in the reaction solution after completion of the curing.
A TK homomixer was used as a mixer for suspending the reaction liquid containing the amino resin particles (amino resin crosslinked particles) while maintaining the temperature at 90 ° C. at a rotation speed of 5000 rpm. The mixture was stirred for 3 minutes, then 500 g of formalin (same as in Example 1) was added, and the mixture was similarly stirred for 3 minutes. Next, to this reaction liquid, as an aqueous dispersion of an inorganic compound, a dispersion liquid obtained by dispersing 450 g of NanoTek CeO ₂ (same as above) in 4000 g of water was gently added, while maintaining the reaction liquid at 90 ° C. A TK homomixer was used as a stirrer having a high shearing force for fixing the child particles made of an inorganic compound to the amino resin particles as the mother particles, and the mixture was stirred at a rotation speed of 5000 rpm for 5 minutes. Next, the TK homomixer was replaced with a general stirrer at 90 ° C.
It was stirred for 1 hour.

Thereafter, this reaction solution was cooled to 30 ° C., and then filtered, heat-treated and the like in the same manner as in Example 1 to obtain brown powdery amino resin composite particles. The amount of the inorganic compound used with respect to the cured amino resin particles (amino resin crosslinked particles) is 10% by weight. The average particle diameter (d50) measured in the same manner as in Example 1 and the average particle diameter of the mother particles were 8.8 μm, and the standard deviation was 4.5 μm.
The adhesion rate measured by the heat treatment method was 91%. The results of these measurements are summarized in Table 3.

Further, in order to confirm the adherence of ceria (child particles) in the obtained amino resin composite particles, X
When cerium Lα was mapped with a line microanalyzer (same as above) (magnification: 2000 times), cerium adherence was observed on the amino resin particles.

Comparative Example 3 White powdery amino resin composite particles were obtained in the same manner as in Example 11 except that the polyvinyl alcohol aqueous solution as an emulsifier was not added to the reaction solution after completion of curing.

Cerium Lα was mapped by an X-ray microanalyzer (same as above) in order to confirm the degree of fixation of ceria (child particles) in the obtained amino resin composite particles (magnification: 2000 times). Little cerium sticking was observed on top. Also, in the same manner as in Example 1, the average particle diameter (d50) of the amino resin composite particles, the average particle diameter of the mother particles, and the standard deviation,
The results of measuring the sticking ratio and the like are summarized in Table 3.

Example 12 Volume 1 equipped with a reflux condenser, stirrer, thermometer, vibrating viscometer (same as in Example 1), etc.
In a 0 L reactor, 3000 g (16 mol) of benzoguanamine as an amino compound, 2600 g of formalin having a concentration of 37% by weight (32 mol of formaldehyde), and 10 g of a 10% by weight sodium carbonate aqueous solution (0.01 mol of sodium carbonate) were added. Charge, raise the temperature with stirring,
The reaction was carried out at 95 ° C.

The viscosity of the reaction solution is 4.5 × 10 ^-2 P
The reaction (resinification step) was completed by cooling the reaction solution at the time of a · s (45 cP). As a result, a reaction liquid containing an amino resin precursor which is an initial condensate of benzoguanamine and formaldehyde (an aqueous dispersion of the amino resin precursor) was obtained. The viscosity was measured using a process viscometer attached to the reaction kettle.

Next, a reflux condenser, a mixer for emulsifying the reaction solution containing the amino resin precursor, and a high shearing force for fixing the child particles made of the inorganic compound to the amino resin particles as the mother particles. 150 g of polyvinyl alcohol (same as in Example 1) as an emulsifier was dissolved in 2200 g of water in a reaction kettle having a capacity of 25 L equipped with a TK homomixer (the same as in Example 1) as a stirrer having the above, a thermometer and the like. Was added and the temperature was raised to 75 ° C. with stirring. Then, after adding the above reaction liquid to the reaction kettle, the liquid temperature is raised to 77 ° C., and while maintaining this temperature, the contents are prepared by using the above stirring device having a high shearing force. By vigorous stirring at a rotation speed of 7,000 rpm, the amino resin precursor was emulsified to obtain an emulsion having a concentration of the amino resin precursor of 56.6% by weight, and the emulsification process was completed. When the emulsion was measured with Coulter Multisizer II (same as above), the average particle size (d50) of the amino resin precursor in the emulsion was 2.0 μm. Further, 10000 g of water at room temperature (25 ° C.) was added to the obtained emulsion all at once, and the emulsion was cooled to 30 ° C. with stirring.

Subsequently, 3256 g of the water dispersion of Aerosil 200 (same as above) having a solid content of 10% by weight, as a water dispersion of silica which is an inorganic compound, was added to the reaction kettle, and then the same high shearing force was applied. Using a TK homomixer, which is a stirrer, the contents are rotated at a rotation speed of 4000 rpm for 5 minutes.
Stir for minutes.

Then, 40 g of sulfuric acid as a catalyst (0.6 g
An aqueous solution obtained by dissolving 1200 mol of (mole) in pure water (1200 g) was added to the emulsion (the temperature of the contents was 30 ° C.), and the temperature was raised at 90 ° C. at 10 ° C./hr with stirring. And
After the temperature reached 90 ° C., the temperature was maintained for 1 hour to condense and cure the amino resin precursor together with the inorganic compound. Therefore, the reaction (curing) time is 7 hours in total.

After the curing (curing step) was completed, the obtained suspension containing the amino resin composite particles (amino resin crosslinked composite coated particles) was cooled to 30 ° C. Then, a neutralization process was performed using a 5 wt% sodium hydroxide aqueous solution to adjust the pH of the suspension to 7.5. Then, the suspension containing the amino resin composite particles was separated from the reaction liquid (reaction system), and it was confirmed that the suspension can be used as the suspension containing the amino resin composite particles. Then, the amino resin composite particles according to the present invention were taken out from the reaction solution by filtering. Remove the amino resin composite particles at 150 ° C
After heating for 3 hours, the mixture was placed in a mortar and crushed by applying light force with a pestle. As a result, white powdery amino resin composite particles were obtained. The average particle size (d50) of the amino resin composite particles measured by Coulter Multisizer II type (same as above) was 2.2 μm. The average particle size (d50) of these amino resin composite particles, the average particle size of the mother particles, the standard deviation, and the sticking ratio were measured in the same manner as in Example 1, and the results are summarized in Table 4.

Example 13 Capacity 1 equipped with a reflux condenser, stirrer, thermometer, vibrating viscometer (same as in Example 1), etc.
In a 0 L reactor, 3200 g (17.1 mol) of benzoguanamine as an amino compound, 2810 g of formalin having a concentration of 37% by weight (34.7 mol of formaldehyde), and 10 g of 10% by weight sodium carbonate aqueous solution (0.01 sodium carbonate) Mol) was added, the temperature was raised with stirring, and the mixture was reacted at 95 ° C.

Then, the viscosity of the reaction solution is 4.0 × 10 ^-2 P
The reaction (resinification step) was completed by cooling the reaction solution at the time of a · s (40 cP). on the other hand,
Dispersion aid (Kao Corporation; trade name Emulgen 92)
0) An oil-soluble dye (manufactured by Arimoto Chemical Co., Ltd .; trade name: FluorescentR) in an aqueous solution prepared by dissolving 0.5 g in 70 g of pure water.
ed 632) 50 g was added and sufficiently dispersed to prepare a dispersion liquid. Then, the prepared dispersion liquid was added to the above reaction liquid and stirred. As a result, a colored reaction liquid containing an amino resin precursor which is an initial condensate of benzoguanamine and formaldehyde (water dispersion of amino resin precursor)
Got The viscosity was measured using a process viscometer attached to the reaction kettle.

Next, a reflux condenser, a mixer for emulsifying the reaction solution containing the amino resin precursor, and a high shearing force for fixing the child particles made of the inorganic compound to the amino resin particles as the mother particles. 120 g of polyvinyl alcohol (same as in Example 1) as an emulsifier was dissolved in 300 g of water in a reactor having a capacity of 15 L equipped with a TK homomixer (the same as in Example 1) as a stirrer having the above, a thermometer and the like. Was added and the temperature was raised to 75 ° C. with stirring. Then, after adding the above reaction liquid to the reaction kettle, the liquid temperature is raised to 77 ° C., and while maintaining this temperature, the contents are prepared by using the above stirring device having a high shearing force. The amino resin precursor was emulsified by vigorous stirring at a rotation speed of 7,000 rpm to obtain a pink emulsion having a concentration of the amino resin precursor of 47.6% by weight, and the emulsification step was completed. When the emulsion was measured with Coulter Multisizer II (same as above), the average particle diameter (d50) of the amino resin precursor in the emulsion was 2.9 μm. Further, 5000 g of water at room temperature (25 ° C.) was added to the obtained emulsion all at once, and the emulsion was cooled to 30 ° C. with stirring.

Subsequently, 3256 g of an aqueous dispersion of aluminum oxide C (same as above) having a solid content of 10% by weight as an aqueous dispersion of alumina, which is an inorganic compound, was added to the reaction kettle, and then the same high shearing force was applied. The contents were stirred for 5 minutes at a rotation speed of 4000 rpm using a TK homomixer, which is a stirring device having a.

Next, as a water-soluble dye, "acid Red 5
2 "7 g was dissolved in 650 g of pure water to prepare an aqueous solution. Then, add the prepared aqueous solution to the above emulsion and add 5
Stir for minutes. Then, an aqueous solution obtained by dissolving 40 g of dodecylbenzenesulfonic acid as a catalyst in 1200 g of pure water was added to the above emulsion (the temperature of the contents was 30 ° C.), and the mixture was stirred at 10 ° C./hr until the temperature reached 90 ° C. The temperature was raised.
Then, after reaching 90 ° C., the temperature was maintained for 1 hour to condense and cure the amino resin precursor together with the inorganic compound. Therefore, the reaction (curing) time is 7 hours in total.

After the curing (curing step) was completed, the obtained suspension containing the amino resin composite particles (amino resin cross-linked composite coated particles) was cooled to 30 ° C. Then, a neutralization process was performed using a 5 wt% sodium hydroxide aqueous solution to adjust the pH of the suspension to 7.5. And after the neutralization step,
In the same manner as in Example 12, the above suspension containing amino resin composite particles (however, colored) can be separated from the reaction solution (reaction system) and used as a suspension containing amino resin composite particles. Was confirmed. Then, the amino resin composite particles according to the present invention were taken out from the reaction solution by filtering. The taken out amino resin composite particles were heat-treated at 150 ° C. for 3 hours, then put into a mortar and crushed by applying light force with a pestle. As a result, red powdery amino resin composite particles were obtained. When the amino resin composite particles were measured with a Coulter Multisizer II (same as above), the average particle diameter (d50) was 3.1 μm. Average particle size (d50) of these amino resin composite particles
In addition, Table 4 shows a summary of the results obtained by measuring the average particle size, standard deviation, sticking rate and the like of the mother particles in the same manner as in Example 1.

[0193]

[Table 1]

[0194]

[Table 2]

[0195]

[Table 3]

[0196]

[Table 4]

In Tables 1 to 4, r is the diameter of the stirring blade (φ: cm), R is the inner diameter of the reaction vessel or the casing inner diameter (cm) in the stirring device having a casing.
Indicates.

The present invention is not limited to the above-described embodiments, but various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the disclosed technical means are also included in the present invention. It is included in the technical scope of the invention.

[0199]

As described above, the amino resin composite particles of the present invention are amino resin composite particles in which an inorganic compound is fixed to the surface of the amino resin particles, and the amino resin composite particles contain 10% by weight of the amino resin composite particles. The turbid liquid was placed in a container having a diameter of 92 mm, and the stirring blade having a blade size of 40 mm in diameter was used to stir at a tip peripheral speed of the stirring blade of 5.2 m / s to obtain the amino resin composite particles. The sticking rate of the inorganic compound obtained by dropping the inorganic compound from the surface and measuring the amount of the dropped inorganic compound is 10%.
The above is the configuration.

As described above, the amino resin composite particles of the present invention have a structure in which the amount of the inorganic compound that has fallen off the surface of the amino resin composite particles is measured by the centrifugal separation method.

As described above, the amino resin composite particles of the present invention are structured so that the amount of the inorganic compound that has fallen off the surface of the amino resin composite particles is measured by the heat treatment method.

Furthermore, the amino resin composite particles of the present invention are
As described above, the inorganic compound is fixed as a child particle on the surface of the mother particle using the amino resin particle as a mother particle, and the average particle diameter of the inorganic compound is the average of the amino resin particle that is the mother particle. It is 0.05 to 0.001 times the particle size, and the average particle size of the amino resin particles is 1
The average particle diameter of the inorganic compound is in the range of 0.001 to 1.5 µm, and the average particle diameter of the mother particles is larger than the average particle diameter of the child particles.

According to the above-mentioned constitution, the amino resin composite particles have a sticking ratio of the inorganic compound, for example, the child particles made of the inorganic compound, of 10% or more. Therefore, for example, even when an external force is applied, the drop-off of the child particles, that is, the drop-off of the inorganic compound is smaller than that of the conventional amino resin composite particles. Therefore, an amino resin composite particle in which an inorganic compound is stably fixed to the surface of an amino resin particle, for example, an amino resin composite in which a child particle made of an inorganic compound is stably fixed to the surface of a mother particle made of amino resin particles An effect is that particles can be provided.

In the amino resin composite particles of the present invention, as described above, the amino resin precursor contains the amino compound and formaldehyde in the temperature range of 95 to 98 ° C.
The viscosity of the reaction liquid is 2 × 10 ^{-2 to} 5.5 × 10 ^-2 Pa ·
It is a structure obtained by reacting until the time point falls within the range of s.

According to the above constitution, by setting the viscosity of the reaction liquid within the above range, it is possible to obtain amino resin composite particles (mother particles) having substantially uniform particle diameters (narrow particle size distribution). Play.

As described above, the amino resin composite particles of the present invention include the amino resin precursor to be amino resin particles, the amino resin precursor in the middle of curing to be amino resin particles, and At least one kind selected from amino resin particles and an inorganic compound to be fixed are dispersed in water in the presence of an emulsifier in the presence of an emulsifying agent, and the composition is obtained by mixing them. .

As described above, the amino resin composite particles of the present invention have the above-mentioned shearing force as the amino resin precursor to become the amino resin particles, the amino resin precursor in the process of curing to become the amino resin particles, and the amino resin. At least one selected from particles and an inorganic compound to be fixed are sheared by a stirring blade rotating at a tip peripheral velocity of 2 m / s or more and 30 m / s or less in the presence of an emulsifier in a state of being dispersed in water. This is the configuration provided by the above.

As described above, the amino resin composite particles of the present invention have the above-mentioned shearing force as the amino resin precursor to be amino resin particles, the amino resin precursor in the middle of curing to be amino resin particles, and the amino resin. At least one selected from particles and an inorganic compound to be fixed are dispersed in water, in the presence of an emulsifier, 3 MPa or more, 49MP
It is a structure which is given by colliding with each other at a discharge pressure of a or less.

[0209] As described above, the amino resin composite particles of the present invention can be produced by mixing the amino resin in the tank in a stirring device having a tank in which baffles for changing the flow direction to a right angle are continuously installed. Amino resin precursor to be particles, amino resin precursor in the course of curing to be amino resin particles,
And at least one selected from amino resin particles,
An inorganic compound to be fixed is dispersed in water, and in a presence of an emulsifier, it is applied by pressure-feeding at a discharge pressure of 0.1 MPa or more and 1.47 MPa or less and forced circulation or liquid feeding. is there.

According to the above constitution, at least one selected from an amino resin precursor to be amino resin particles, an amino resin precursor in the process of curing to be amino resin particles, and an amino resin particle, and an inorganic resin to be fixed. The compound and the compound are dispersed in water and mixed in the presence of an emulsifying agent in the presence of an emulsifying agent to give an emulsion or suspension while imparting the shearing force. Therefore, these amino resin precursors and / or amino resins The surface of the particles (that is, at least one selected from amino resin precursors to be amino resin particles, amino resin precursors in the process of curing to be amino resin particles, and amino resin particles) becomes soft due to emulsion or suspension. The surface of these amino resin precursors and / or amino resin particles in the state of It may be attached to (secured). Therefore, according to the above configuration, the inorganic compound can be firmly fixed (fixed) to the surface of the amino resin precursor and / or the amino resin particles, and therefore the inorganic compound is removed even when an external force is applied. It is possible to easily provide the amino resin composite particles having a smaller number of particles at a low cost.

[Brief description of drawings]

FIG. 1 is a view showing a structure of an amino resin composite particle according to an embodiment of the present invention by an electron micrograph (7500 times).

FIG. 2 is a diagram showing a structure of another amino resin composite particle according to one embodiment of the present invention by an electron micrograph (7500 times).

Continued front page    (72) Inventor Hideki Oishi             Hyogo prefecture Himeji city             1 Within Nippon Shokubai Co., Ltd. F-term (reference) 4F070 AA57 AC23 AD04 AE27 AE28                       DB03 DB04 DB06

Claims (9)

[Claims] 1. An amino resin composite particle having an inorganic compound adhered to the surface of an amino resin particle, wherein a suspension containing 10% by weight of the amino resin composite particle is placed in a container having a diameter of 92 mm and having a diameter of 40 mm. By using a stirring blade having a blade size and stirring at a tip peripheral speed of the stirring blade of 5.2 m / s, the inorganic compound was dropped from the surface of the amino resin composite particles, and the amount of the dropped inorganic compound An amino resin composite particle having a sticking ratio of the inorganic compound of 10% or more as determined by measuring. 2. The amino resin composite particles according to claim 1, wherein the amount of the inorganic compound dropped from the surface of the amino resin composite particles is measured by a centrifugal separation method. 3. The amino resin composite particles according to claim 1, wherein the amount of the inorganic compound dropped off from the surface of the amino resin composite particles is measured by a heat treatment method. 4. The above-mentioned inorganic compound is fixed to the surface of the above-mentioned mother particles as mother particles by using the above-mentioned amino resin particles as mother particles, and the average particle size of the above-mentioned inorganic compound is the average of the amino resin particles as mother particles. It is 0.05 to 0.001 times the particle size, and the average particle size of the amino resin particles is 1 to
It is in the range of 30 μm, the average particle size of the inorganic compound is in the range of 0.001 to 1.5 μm, and the average particle size of the mother particles is larger than the average particle size of the child particles. The amino resin composite particle according to any one of claims 1 to 3. 5. The amino resin composite particles are fixed to at least one selected from an amino resin precursor to be amino resin particles, a curing amino resin precursor to be amino resin particles, and amino resin particles. 5. An inorganic compound to be obtained, which is obtained by mixing, in a state of being dispersed in water, in the presence of an emulsifier while applying a shearing force. Amino resin composite particles according to. 6. The amino resin precursor comprises an amino compound and formaldehyde in a temperature range of 95 to 98 ° C.
The viscosity of the reaction liquid is 2 × 10 ^{-2 to} 5.5 × 10 ^-2 Pa ·
The amino resin composite particles according to claim 5, wherein the amino resin composite particles are obtained by reacting until the time point falls within the range of s. 7. The shear force is at least one selected from an amino resin precursor to be amino resin particles, an amino resin precursor in the course of curing to be amino resin particles, and an amino resin particle, and an inorganic substance to be fixed. The compound and the compound are dispersed in water, and the tip peripheral speed is 2 m in the presence of an emulsifier.
7. The amino resin composite particles according to claim 5 or 6, wherein the amino resin composite particles are provided by shearing with a stirring blade rotating at a speed of not less than / s and not more than 30 m / s. 8. The shear force is at least one selected from an amino resin precursor to be amino resin particles, an amino resin precursor in the course of curing to be amino resin particles, and an amino resin particle, and an inorganic substance to be fixed. In the presence of an emulsifier, the compound and the compound are dispersed in water, 3 MPa or more, 4
The amino resin composite particles according to claim 5 or 6, wherein the amino resin composite particles are provided by colliding with each other at a discharge pressure of 9 MPa or less. 9. The shearing force is an amino resin precursor or amino resin particles to be amino resin particles in the tank in a stirrer having a tank in which baffles for changing the flow direction to a right angle are continuously installed. 0.1 MPa or more in the presence of an emulsifier in a state in which at least one selected from the amino resin precursor in the course of curing and amino resin particles to be fixed and the inorganic compound to be fixed are dispersed in water. 47MP
The amino resin composite particles according to claim 5 or 6, wherein the amino resin composite particles are provided by being forcedly circulated or liquid-fed at a discharge pressure of a or less.