JP3469223B2 - Manufacturing method of composite particles - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing composite particles. More specifically, it is suitable for paints, inks for inkjet printers, cosmetics, etc., in which water repellency, oil repellency, optical properties, UV protection, touch, safety, activity, color tone, dispersion stability, weather resistance, etc. are controlled. The present invention relates to a method for producing composite particles that can be used and the composite particles obtained by the production method.

[0002]

2. Description of the Related Art As a method for surface-treating fine particles,
A method of adding a coupling agent, an alkaline agent, etc. to a suspension of a coating agent, immersing the core fine particles in the liquid phase, and then subjecting the fine particles to a heat treatment to coat the surface of the fine particles with the coating agent (liquid Phase coating method) has been proposed. In particular, this method is generally adopted when coating the surface of the fine particles with a silicone compound or a fluorine compound for the purpose of imparting water repellency and / or oil repellency to the fine particles.

However, in the liquid phase coating method for coating fine particles with a silicone compound (Japanese Patent Laid-Open No. 61-127767, Japanese Patent Laid-Open No. 7-196946, etc.), an added alkali agent and silane coupling are used. Since the agent and the like may remain on the surface of the coated fine particles, when the skin comes into contact with the particles, there is a risk of causing trouble to the skin.

In the method of coating fine particles with a fluorine-based compound (Japanese Patent Laid-Open No. 62-250074), the effect of adsorbing the fluorine-based compound on the surface of the fine particles is utilized.
However, this method has drawbacks such as incomplete coating and weak covering power.

Further, in the liquid phase coating method using a silicone compound and a fluorine compound, the surface of fine particles is coated with these low molecular weight compounds, but the thickness of the formed film is very thin at the molecular level. Since it is difficult to completely coat the fine particles, it is difficult to make the coating amount of the fluorine-based compound and the silicone-based compound 1 weight times or more of the fine particles.

Therefore, in order to obtain thick particles of the film,
A method of coating fine particles by a liquid phase coating method using a fluorine-based polymer compound and / or a silicone-based polymer compound has been proposed. However, in this method, in order to use these polymer compounds, not only an organic solvent harmful to the human body must be used, but also the number of manufacturing steps is large and the operation is complicated. However, there is a drawback that the manufacturing cost becomes high.

As another method for coating fine particles with a polymer compound, there is known a method of coating fine particles with a general polymer compound such as acrylic resin, polyethylene or polystyrene by using supercritical carbon dioxide ( JP 11-47681
Japanese Patent Laid-Open No. 11-197494). However, since these polymer compounds are not dissolved only by supercritical carbon dioxide, it is necessary to add an organic solvent as a co-solvent. Therefore, the organic solvent remains on the coated particles, and a step of removing the residual organic solvent from the coated particles by drying or the like is required, and the water repellency and / or oil repellency is generally low.

[0008]

The present invention can produce composite particles by a simple production process without using an organic solvent harmful to the human body or removing the organic solvent by heat treatment or the like. It is an object to provide a method and composite particles obtained by the method.

[0009]

The present invention can be obtained by contacting fine particles with a fluorine-containing polymer compound and / or a silicone polymer compound in the presence of supercritical carbon dioxide or liquefied carbon dioxide. mixture is decompressed and expanded, it relates to the preparation of composite particles of the particles and fluoric polymer compound and / or silicone-based polymer compound.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the term “composite particles” means that a part or all of the fine particles are coated or covered with a fluorine-based polymer compound and / or a silicone-based polymer compound (hereinafter referred to as polymer compound). The encapsulated composite particles, the composite particles in which the fine particles of the polymer compound are present on the surface of the fine particles, and the composite particles in which the polymer compound is present inside or on the surface of the aggregated particles of the fine particles Say.

One of the major features of the present invention is the following. Carbon dioxide is generally non-toxic and its critical temperature is 304.2 K. Supercritical carbon dioxide refers to carbon dioxide that has a pressure equal to or higher than the critical temperature (Tc) and equal to or higher than the critical pressure (Pc), and has the property that the density changes abruptly with a slight pressure change. Therefore, when the pressure of supercritical carbon dioxide slightly exceeding the critical temperature (Tc) is increased, the density of the gas phase is rapidly increased, so that the solubility of the solute is rapidly increased in the region above the critical pressure. On the contrary, when the supercritical carbon dioxide is ejected from the container containing the supercritical carbon dioxide from the nozzle to perform the decompression expansion of the carbon dioxide, the solubility of the solute in the carbon dioxide can be rapidly reduced, Solute and supercritical carbon dioxide can be separated only by depressurization. The decompression in the present specification means reducing the pressure from a high pressure at which carbon dioxide becomes a supercritical state or a liquefied state.

[0012] Using supercritical carbon dioxide, the temperature at which the supercritical carbon dioxide is expanded under reduced pressure is preferably from 308.15 to from the viewpoint of efficiently expanding the supercritical carbon dioxide under reduced pressure.
It is 373.15K, more preferably 308.15 to 353.15K, still more preferably 308.15 to 333.15K. Further, the pressure of supercritical carbon dioxide during the decompression expansion is preferably 7.2 to 50 MPa, more preferably 10 to 40 MPa in order to efficiently perform the decompression expansion of the supercritical carbon dioxide.

Also, in the case of liquefied carbon dioxide, when the carbon dioxide is ejected from a nozzle to expand the carbon dioxide under reduced pressure as in the case of supercritical carbon dioxide, the solubility of solute in carbon dioxide can be drastically reduced. Only solute and carbon dioxide can be separated. Using liquefied carbon dioxide, the temperature at which the reduced pressure expansion of the liquefied carbon dioxide is performed is preferably 233.0 to 304.0 K, more preferably 273.0 to 304.0 from the viewpoint of efficiently performing the reduced pressure expansion of the liquefied carbon dioxide. K. The pressure of the liquefied carbon dioxide is preferably 1 to 50 MPa, more preferably in order to efficiently reduce the pressure of the liquefied carbon dioxide.
It is 3.5-40MPa.

As described above, when supercritical carbon dioxide or liquefied carbon dioxide is used, the operation can be carried out at a low temperature, so that the operation is easy and the carbon dioxide is inexpensive, so that the manufacturing cost is low. There is an advantage that can be reduced.

The use of supercritical carbon dioxide is preferable to the use of liquefied carbon dioxide from the viewpoint that the solubility of the solute can be increased.

The concentration of the polymer compound dissolved or dispersed in supercritical carbon dioxide or liquefied carbon dioxide is not particularly limited, but is preferably 0.1 to 90% by weight, preferably 1 to 30% by weight. Further, polymer compounds that dissolve or disperse at these concentrations are preferable. From the viewpoint of the uniformity of the film thickness, it is preferable that they are dissolved.

As the fine particles, inorganic fine particles and organic fine particles which are substantially insoluble in supercritical carbon dioxide or liquefied carbon dioxide can be used.

Examples of the material forming the inorganic fine particles include titanium oxide, silica, mica, talc, kaolin,
Cerisite, zinc oxide, magnesium oxide, zirconium oxide, calcium carbonate, magnesium carbonate, magnesium silicate, anhydrous silicic acid, barium sulfate, red iron oxide, yellow iron oxide, black iron oxide, carbon black, manganese violet, and their composites. These may be used alone or in admixture of two or more. Further, the particles may be particles in which the surface of the inorganic fine particles has been subjected to a surface treatment such as silicone treatment or fluorine treatment.

Examples of the organic fine particles include organic pigments and organic powders made of high molecular compounds.

Examples of organic pigments include Red No. 201,
Red No. 202, Red No. 204, Red No. 226, Orange No. 204, Yellow No. 205, Red No. 404, Red No. 405, Orange No. 401, Yellow
Examples include 401 and blue 404. Examples of the polymer compound include thermoplastic resins such as acrylic resins, polyolefins, polystyrene, fluororesins, silicone resins, polyesters and polyamides, epoxy resins, thermosetting resins such as phenolic resins, and the like. Can be used alone or in admixture of two or more. Further, the surface of the organic fine particles may be particles subjected to surface treatment such as silicone treatment and fluorine treatment.

The average particle size of the fine particles before complexing (the measuring method is shown in the examples) is not particularly limited, but is 0.01 to 500 μm.
m, preferably 0.02 to 100 μm, more preferably 0.04 to
50 μm is desirable. Among them, the average particle size is 0.01
One or more kinds of fine particles selected from the group consisting of mica, talc and barium sulfate having a size of up to 500 μm are preferable.

The fluorine-based polymer compound and the silicone-based polymer compound are used alone or as a mixture as a complexing agent.

General polymer compounds such as acrylic resin, polyethylene and polystyrene are difficult to dissolve in supercritical carbon dioxide or liquefied carbon dioxide. However, the fluorine-based polymer compound and the silicone-based polymer compound are easily dissolved or dispersed in supercritical carbon dioxide and liquefied carbon dioxide. The present invention utilizes the property between the fluorine-based polymer compound and the silicone-based polymer compound and carbon dioxide.

The fluorine-based polymer compound may be any polymer compound having a fluorine atom. The weight composition ratio of fluorine atoms in the fluorine-based polymer compound is 9 to 80% by weight,
Preferably 20-70% by weight, more preferably 40-65% by weight
Is desirable. Among the fluoropolymer compounds, a (meth) acrylic acid ester polymer having a fluoroalkyl group or a perfluoroalkyl group, and a (meth) acrylic acid ester having a fluoroalkyl group or a perfluoroalkyl group-long-chain alkyl ( A meth) acrylate copolymer is preferred.

Further, as the fluorine-based polymer compound, a (meth) acrylate homopolymer having a perfluoroalkyl group having 4 or more carbon atoms, a polyfluoroalkyl group or a perfluoropolyether group, and this compound and a carbon number of 8 Most preferred are copolymers with (meth) acrylates having ~ 22 alkyl groups. A fluorine-based polymer compound or a silicone-based polymer compound that is dissolved or dispersed in supercritical carbon dioxide or liquefied carbon dioxide is preferable.

The silicone polymer compound is dissolved or dispersed in supercritical carbon dioxide or liquefied carbon dioxide alone or in a mixture of supercritical carbon dioxide or liquefied carbon dioxide and a cosolvent, and is generally used in cosmetics and the like. There is no particular limitation as long as it is present. Among the silicone-based polymer compounds, methyl polysiloxane, dimethyl polysiloxane, cyclic dimethyl polysiloxane, methyl phenyl polysiloxane, methyl hydrogen polysiloxane, cyclic methyl hydrogen polysiloxane, dimethyl siloxane methyl (polyoxyethylene) siloxane Copolymer, dimethyl siloxane / methyl (polyoxypropylene) siloxane copolymer, polyether modified silicone, methylstyryl modified silicone, alkyl modified silicone, fluorine modified silicone, silicone modified acrylic resin, higher fatty acid ester modified silicone, higher alkoxy modified Silicone or the like is preferable.

Among the silicone type polymer compounds, at the terminal and / or side chain of the organopolysiloxane molecular chain,
Formula (I):

[0028]

[Chemical 4]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a carbon atom having 6 carbon atoms.
10 aryl group, X ^- represents a counter ion of the quaternary ammonium salts, Cl ^-, Br ^- or a halogen ion such ^{_{as, CH 3 SO 4 -, CH}} 3 CH 2 SO 4 - sulfuric acid ester ions, such as To be ) Or formula (II):

[0030]

[Chemical 5]

(Wherein R ¹ , R ² and X ⁻ are the same as defined above) via the group represented by the formula (III):

[0032]

[Chemical 6]

(In the formula, R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
n is 2 or 3) and a molecular chain of poly (N-acylalkyleneimine) consisting of a repeating unit represented by the formula (1) is bonded to the molecular chain of the poly (N-acylalkyleneimine) and a molecule of organopolysiloxane. A silicone-based polymer compound having a weight ratio with the chain of preferably 1/50 to 50/1, more preferably 1/20 to 20/1 is particularly preferable. For example, R ¹ and R ² in formula (I) are each a hydrogen atom, X
^- is ^{_{CH 3 CH 2 SO 4 -,}} R 3 in formula (III) is CH ₂
Γ- (N-propionylpolyethyleneimino) aminopropylmethylsiloxane / dimethylsiloxane copolymer having CH ₃ and n = 2 [poly (N-propanoylethyleneimine) graft-dimethylsiloxane / γ-aminopropylmethylsiloxane, hereinafter Same].
The weight average molecular weight of the polymer compound is preferably 500 to 500000.

The method of bringing the fine particles and the polymer compound into contact with each other in the presence of supercritical carbon dioxide or liquefied carbon dioxide and then expanding the mixture under reduced pressure is as follows.
A polymer compound and supercritical carbon dioxide or liquefied carbon dioxide are mixed, to supercritical carbon dioxide or liquefied carbon dioxide,
A method of completely dissolving or dispersing the polymer compound and the fine particles and then reducing the pressure of the system can be mentioned. For example, by spraying from the nozzle into the atmosphere, carbon dioxide is decompressed and expanded into a gas to reduce the dissolving power of carbon dioxide for polymer compounds and fine particles, and to dissolve or disperse the carbon dioxide without heat treatment. The molecular compound can be separated from carbon dioxide to obtain fine particles complexed with the polymer compound.

The concentration of fine particles dispersed in supercritical carbon dioxide or liquefied carbon dioxide is not particularly limited, but is 0.01
It is desirable that the content is -40% by weight, preferably 0.1-20% by weight.

When the polymer compound is difficult to dissolve or disperse in supercritical carbon dioxide or liquefied carbon dioxide, the co-solvent is mixed with supercritical or liquefied carbon dioxide to convert the polymer compound into supercritical carbon dioxide. Alternatively, it can be dissolved or dispersed in liquefied carbon dioxide.

The cosolvent is preferably a polar solvent. Among the polar solvents, alcohol and water, which are considered to be almost harmless to the human body, are preferable. As the alcohol, ethanol and 1-propanol are preferable, and ethanol is more preferable. Even when the co-solvent is used, a general polymer compound is separated from the co-solvent when sprayed in the air from the nozzle, and therefore it is not necessary to perform a desolvent treatment such as a heat treatment to remove the co-solvent.

As described above, according to the method of the present invention, since it is not necessary to perform heat treatment after coating unlike the conventional liquid phase coating method, it is possible to reduce the number of processing steps, and therefore the operability is very excellent. It is a method.

By the above operation, composite particles composed of the fluorine-based polymer compound and / or the silicone-based polymer compound and the fine particles can be obtained.

The morphology of the obtained composite particles varies depending on the operating conditions of the composite and the like. Examples thereof include composite particles in which fine particles are partially or wholly coated or included with a fluorine-based polymer compound and / or a silicone-based polymer compound, and fine particles are a fluorine-based polymer compound and / or a silicone-based polymer compound. Embedded particles, composite particles in which fine particles of the polymer compound are present on the surface of the fine particles, composite particles in which the polymer compound is present inside or on the surface of the aggregated particles of the fine particles Can be mentioned.

The composite particles may contain a third component other than the organic compound and the fine particles. Examples of the third component include stabilizers and colorants other than the fine particle coating component. The third component may be one or more types. The third component is dissolved in supercritical carbon dioxide or liquefied carbon dioxide.
By dispersing, it can be contained in the composite particles.

Examples of the container include an autoclave and a pressure cell.

The average particle diameter of the composite particles cannot be unconditionally determined because it depends on the amount of the polymer compound as the composite agent, etc., but 0.01 to 1000 μm, more preferably 0.02 to 500 μm, and further It is preferably 0.04 to 100 m.

The thickness of the coating of the composite particles is not particularly limited, but is preferably 0.1 nm to 500 μm, more preferably 0.5 nm to 10 μm, and particularly preferably 1 nm to 1 μm.

The ratio of the fluorine-based polymer compound and / or the silicone-based polymer compound to the fine particles in the composite particles is not particularly limited, but is usually 1 weight of the fluorine-based polymer compound and / or the silicone-based polymer compound. To the department
Fine particles 0.001 to 1000 parts by weight, preferably 0.005 to 500
It is desirable that the amount is, by weight, more preferably 0.7 to 500 parts by weight.

[0046]

EXAMPLES Example 1 The apparatus shown in FIG. 1 was used. The device shown in FIG.
It is an apparatus used in a method for producing composite particles by a reduced pressure expansion method of carbon dioxide. Such a device can be divided into a pressurizing section on the upstream side and a dissolving / dispersing section on the downstream side with a stop valve V-2 described later as a boundary.

In the booster, a cylinder 1 with a siphon filled with liquid carbon dioxide is used as a supply source of liquid carbon dioxide.

Water contained in the liquid carbon dioxide supplied from the cylinder 1 is removed while passing through the drying tube 2. The liquid carbon dioxide from which water has been removed is sent to the cooling unit 4 after impurities such as dust are removed by the filter 3.

The cooling unit 4 is filled with ethylene glycol cooled to 261.15K. As a result, the dehydrated liquid carbon dioxide is cooled and sent to the pressurizing pump 5. A cooling device (not shown) may be attached to the head portion of the boosting pump 5 in order to prevent vaporization of liquid carbon dioxide.

Filter 3 in the carbon dioxide booster
A pressure regulating valve V-1 is provided downstream of the. With this pressure adjusting valve V-1, the pressure in the system of the pressure rising section and the dissolution / dispersion section can be set to an arbitrary pressure. With this pressure control valve V-1, the pressure of the dissolution / dispersion part is ± 0.1MPa.
The pressure in the system can be controlled so as to be within the tolerance range.

A pressure gauge 6a is provided downstream of the boosting pump in the boosting section. The pressure in the booster system can be measured with this pressure gauge 6a. The pressure gauge 6a is provided with an upper limit contact output terminal, and is set to turn off the power of the boosting pump 5 when the designated pressure is reached.

A stop valve V-2 is arranged between the pressurizing section and the dissolving / dispersing section. The stop valve V-2 can control the outflow of the liquid in the dissolution / dispersion section.

A safety valve 7a is provided in the dissolution / dispersion section in order to ensure safety.

The dissolving / dispersing section is installed in a constant temperature water tank 16 capable of adjusting the height of the entire tank. The internal volume of the constant temperature water tank 16 is 80 dm ² , and the temperature controller "DB100" manufactured by Chino Co.
The water temperature is controlled by "0" (trade name) so that it is within a tolerance of ± 0.1 ° C. Further, the temperature of the constant temperature water tank 16 can be measured by the thermometer 13.

The liquid carbon dioxide supplied from the stop valve V-2 of the pressurizing section is sent to the preheating column 8 installed in the constant temperature water tank 16, and the equilibrium temperature of carbon dioxide is used as a solvent for coating. Is preheated to.

The carbon dioxide heated by the preheating column 8 passes through the check valve 7b which prevents the reverse flow of the fluid and passes through the stop valve V-3 to the dissolution cell 9 containing the solute to be extracted.
Will be introduced to.

The dissolution cell 9 is filled with 2- (perfluorooctyl) ethyl methacrylate polymer, which is a fluorine-based polymer compound, and zinc oxide, which is an inorganic fine particle, and is then filled with carbon dioxide as a solvent and a dispersion medium. It is filled.

Further, the dissolution cell 9 has a motor 12 for stirring.
Is installed. The motor 12 stirs the 2- (perfluorooctyl) ethyl methacrylate polymer, zinc oxide and carbon dioxide in the dissolution cell 9. An electromagnetic non-seal stirrer is connected to the motor 12, and a stirrer is attached to the tip of the stirrer.

The pressure in the melting cell 9 is controlled by the pressure gauge 6b.
Can be measured by Further, on the upstream side of the melting cell 9, a safety valve 7c is installed in order to prevent an explosion due to a pressure increase in the melting cell 9. This safety valve 7
c is controlled so that it operates when the pressure in the melting cell 9 system reaches 34.3 MPa.

The carbon dioxide in the dissolution cell 9 passes through the stop valve V-4, the heating pipe 10 and the constant temperature air chamber 11.
Will be introduced to. Since the polymer compound dissolved or dispersed in carbon dioxide may be solidified under reduced pressure accompanying release from the dissolution cell 9 or carbon dioxide may become dry ice, the stop valve V-4 is a heater. Is being heated by.

When the stop valve V-4 is opened, carbon dioxide in which the polymer compound and the fine particles, which have been heated to the operating temperature by the heating pipe 10, are dissolved and dispersed, is jetted from the nozzle. By being injected, the fluid is decompressed and expanded under reduced pressure, and the dissolving power of the solute is dramatically reduced. As a result, the composite particles 15 coated with the 2- (perfluorooctyl) ethyl methacrylate polymer are collected.

Using the apparatus set as described above,
The following operations were performed. Zinc oxide fine particles (average particle size 0.04μ
m, Sakai Chemical Industry Co., Ltd., trade name: FINEX25] 2 g and 2- (perfluorooctyl) ethyl methacrylate polymer 20 g were filled in the dissolution cell 9. As carbon dioxide,
Carbon dioxide [Fukuoka Oxygen Co., Ltd., purity 99.5% or more]
It was used. The temperature of the constant temperature water tank was controlled at 318.15 ± 0.2 K, and the temperature of the heating tube 10 was controlled at 350.15 ± 0.5 K.

Carbon dioxide was supplied from the cylinder 1 with the stop valves V-2 to V-5 closed, and the upper limit pressure of carbon dioxide was adjusted by the pressure adjusting valve V-1.

Next, with the stop valve V-4 closed, the stop valve V-2 was opened and carbon dioxide gas was sent to the dissolution / dispersion section.

The pressure inside the dissolution cell 9 was adjusted to the operating pressure using the pressure control valve V-1. The inside of the dissolution cell 9 was pressurized and adjusted to the operating pressure, and after the pressure became constant, the mixture was stirred for 60 minutes and then left for about 30 minutes.

Then, the stop valve V-4 was opened, injection was performed, and the pressure was reduced and expanded from 20 MPa to 15 MPa. As a result, the 2- (perfluorooctyl) ethyl methacrylate polymer dissolved in carbon dioxide and the zinc oxide fine particles were jetted from the nozzle 14, and the composite material coated with the 2- (perfluorooctyl) ethyl methacrylate polymer was injected between them. The compound 15 was obtained.

The composite particles 15 deposited on the bottom surface were collected and observed by a scanning electron microscope (magnification: 25000 times). The result is shown in FIG. From the results shown in FIG. 2, it was found that composite particles having an average particle diameter of 2 μm were obtained.

Further, the X-ray diffraction of the 2- (perfluorooctyl) ethyl methacrylate polymer, the obtained composite particles and zinc oxide was examined. Figure 4 shows the results in order.
(A), (b) and (c).

From the X-ray diffractogram shown in FIG. 4, the obtained composite particles [FIG. 4 (b)] include 2- (perfluorooctyl) ethyl methacrylate polymer [FIG. 4 (a)] and It was confirmed that zinc oxide [Fig. 4 (c)] was present.

When the surface element of the obtained composite particles was examined by X-ray photoelectron spectroscopy, the zinc concentration on the particle surface was below the detection limit (0.1 atm%), and most of the surface of the zinc oxide fine particles was found. Alternatively, it was found that all of them were coated with the polymer compound.

A transmitted light electron micrograph (magnification: 10,000 times) of the obtained composite particles is shown in FIG. The black part is zinc oxide and the gray part is 2- (perfluorooctyl) ethyl methacrylate. From the results shown in FIG. 3, it can be seen that the obtained composite particles are composite particles containing zinc oxide fine particles.

Example 2 Zinc oxide fine particles used in Example 1 [Sakai Chemical Industry Co., Ltd.
Made, trade name: FINEX25] 2 g and 2- (perfluorooctyl) ethyl methacrylate polymer 20 g instead of
Stearyl methacrylate-2- (perfluorooctyl) ethyl methacrylate copolymer (weight ratio 1: 9) 20
g and titanium oxide fine particles [average particle diameter 0.25 μm, manufactured by Ishihara Sangyo Co., Ltd., trade name: CR-50] 2 g were used, and composite particles were obtained in the same manner as in Example 1.

X-ray diffraction of the stearyl methacrylate-2- (perfluorooctyl) ethyl methacrylate copolymer, the obtained composite particles and titanium oxide was examined. The results are shown in order of (a), (b) and (c) of FIG. 5, respectively.
Shown in.

From the X-ray diffraction pattern shown in FIG. 5, the obtained composite particles [FIG. 5 (b)] are shown to have stearyl methacrylate / 2- (perfluorooctyl) ethyl methacrylate copolymer [FIG. a)] and titanium oxide [Fig. 5
It was confirmed that (c)] was present.

With respect to the obtained composite particles, titanium was not detected by the measurement of the surface elements of the particles by X-ray photoelectron spectroscopy, and most or all of the surface of the titanium oxide fine particles was stearyl methacrylate 2- (perfluoro). It was found to be coated with an octyl) ethyl methacrylate copolymer.

A scanning electron micrograph (magnification: 25000 times) of the obtained composite particles is shown in FIG. From the results shown in FIG. 6, it was found that composite particles having an average particle diameter of 3 μm were obtained. Also, a transmitted light electron micrograph (magnification:
5000 times) is shown in FIG.

Example 3 Zinc oxide fine particles used in Example 1 [Sakai Chemical Industry Co., Ltd.
Made, trade name: FINEX25] 2 g and 2- (perfluorooctyl) ethyl methacrylate polymer 20 g instead of
The same operation as in Example 1 was performed except that 3 g of γ- (N-propionyl polyethyleneimino) aminopropylmethyl siloxane / dimethyl siloxane copolymer and 15 g of mica (average particle size 10 μm) were used.

A scanning electron micrograph (magnification: 5000 times) of the obtained composite particles is shown in FIG. From the results shown in FIG. 8, it was found that composite particles of mica having an average particle diameter of 11 μm were obtained.

Further, in the measurement of the surface element of the composite particles by X-ray photoelectron spectroscopy, aluminum derived from mica was reduced from 16 atm% to 4 atm%.

Example 4 The same operation as in Example 1 was carried out except that 6 g of 2- (perfluorooctyl) ethyl methacrylate polymer and 20 g of mica (average particle size 10 μm) were used.

A scanning electron micrograph (magnification: 10,000 times) of the obtained composite particles is shown in FIG. From the results shown in FIG. 9, it can be seen that composite particles of mica having an average particle diameter of 12 μm were obtained.

Further, the atomic ratio of fluorine to aluminum derived from mica was found to be 12.0 by measuring the surface element of the obtained composite particles by X-ray photoelectron spectroscopy. In the case of a simple mixture of the polymer and mica, the atomic ratio is 1.3, which means that the polymer is present in large amounts on the surface of the composite particles.

Although the case where the inorganic fine particles are used has been described above, the composite particles can be obtained even when the same treatment is performed using the organic pigment instead of the inorganic fine particles.

[0084]

EFFECTS OF THE INVENTION According to the method of the present invention, the use of an organic solvent harmful to the human body is suppressed, and the fluorine-based polymer compound is produced by a simple manufacturing process without removing the organic solvent by heat treatment or the like. And / or forming composite particles of a silicone-based polymer, and the average particle size of the composite particles is 0.
The effect that particles controlled to 01 to 100 μm can be obtained is exhibited.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of an apparatus used in the method of the present invention.

FIG. 2 is a scanning electron micrograph showing the particle structure of the composite particles obtained in Example 1.

FIG. 3 is a transmission electron micrograph showing the particle structure of the composite particles obtained in Example 1.

FIG. 4 is an X-ray diffraction diagram of composite particles obtained by using zinc oxide and 2- (perfluorooctyl) ethyl methacrylate used in Example 1.

5 is an X-ray diffraction diagram of titanium oxide and a fluorine-based polymer compound used in Example 2, and the obtained composite particles. FIG.

6 is a scanning electron micrograph showing the particle structure of the composite particles obtained in Example 2. FIG.

7 is a transmission electron micrograph showing the particle structure of the composite particles obtained in Example 2. FIG.

FIG. 8 is a scanning electron micrograph showing the particle structure of the composite particles obtained in Example 3.

FIG. 9 is a scanning electron micrograph showing the particle structure of the composite particles obtained in Example 4.

[Explanation of symbols]

1 cylinder 2 drying tubes 3 filters 4 Cooling unit 5 Booster pump 6a Pressure gauge 6b pressure gauge 7a Safety valve 7b Check valve 7c safety valve 8 Preheating column 9 Melting cell 10 heating tube 11 Air bath 12 motors 13 Thermometer 14 nozzles 15 Composite particles 16 constant temperature water tank V-1 Pressure control valve V-2 stop valve V-3 stop valve V-4 stop valve V-5 stop valve

Front Page Continuation (72) Inventor Kenji Mishima 2-6-15-304, Koshinmachi, Minami-ku, Fukuoka-shi, Fukuoka (56) References JP-A-2002-210356 (JP, A) JP-A-5-57166 (JP, A) French patent application publication 2791580 (FR, A 1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/12 C08L 27/12-27/20 C08L 83/04-83/12

Claims (6)

(57) [Claims] 1. Fine particles obtained by contacting fine particles with a fluoropolymer compound and / or a silicone polymer compound in the presence of supercritical carbon dioxide or liquefied carbon dioxide, and then expanding the resulting mixture under reduced pressure. A method for producing composite particles of a fluoropolymer compound and / or a silicone polymer compound. 2. The method for producing composite particles according to claim 1, wherein the weight composition ratio of fluorine atoms in the fluorine-containing polymer compound is 9 to 80% by weight. 3. The fine particles have an average particle diameter of 0.01 to 500.
3. One or more kinds of fine particles selected from the group consisting of mica, talc and barium sulfate having a size of μm.
A method for producing the composite particle as described. 4. The amount of fine particles in the composite particles is 0.7 to 500 parts by weight with respect to 1 part by weight of the fluorine-based polymer compound and / or the silicone-based polymer compound.
4. The method for producing the composite particle according to any one of 3 to 3. 5. A (meth) acrylic acid ester polymer having a fluoroalkyl group or a perfluoroalkyl group, or a (meth) acrylic acid ester having a fluoroalkyl group or a perfluoroalkyl group, wherein the fluorine-containing polymer compound is a long chain. It is an alkyl (meth) acrylate copolymer, The manufacturing method of the composite particle in any one of Claims 1-4. 6. A silicone-based polymer compound is added to the organopolysiloxane at the terminal and / or side chain of the molecular chain of formula (I): (In the formula, R ¹ and R ² are each independently a hydrogen atom,
(Alkyl group having 1 to 18 carbon atoms or aryl group having 6 to 10 carbon atoms, X ⁻ represents a counter ion of a quaternary ammonium salt)
Or formula (II): (In the formula, R ¹ , R ² and X ⁻ are the same as the above), and the group represented by the formula (III): (In the formula, R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or 7 to 10 carbon atoms.
Aralkyl group or an aryl group having 6 to 10 carbon atoms, n is 2 or 3) is bonded to the molecular chain of poly (N-acylalkyleneimine),
The method for producing composite particles according to any one of claims 1 to 5, wherein the weight ratio of the molecular chain of (acylalkyleneimine) to the molecular chain of organopolysiloxane is 1/50 to 50/1.