KR20170126411A - Fluororesin-metal oxide mixed dispersion and method of manufacturing the same - Google Patents

Abstract

The purpose of the present invention is to provide fluororesin particles with excellent operability and workability in the covering process and a mixed dispersion of a metal oxide particle sol. A fluororesin-metal oxide mixed dispersion of the present invention is an aqueous fluororesin-metal oxide mixed dispersion which is formed by mixing an aqueous dispersion of fluororesin particles and the metal oxide particle sol with an appropriate pH value of any one among titanium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide and tin oxide, wherein the fluororesin particles together with the metal oxide particle sol are suspended or dispersed without causing coagulation sedimentation, gelation solidification and/or phase separation, the suspension or dispersion state is stably maintained at a room temperature preservation condition for 3 days or more, and a solid obtained by evaporating and scattering a solvent from the fluororesin-metal oxide mixed dispersion has a water contact angle of 130 or less and a surface resistivity of 2.010^12 / or less.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fluororesin-metal oxide mixed dispersion,

The present invention relates to a coating liquid for coating a surface of various materials such as metal, carbon, plastic, glass, ceramics and wood, and a surface of a product made of these materials, an impregnating liquid for fibers or powders of the above materials, .

The fluororesin is superior in heat resistance and cold resistance to ordinary plastics and organic polymers such as polyethylene and polypropylene, has high resistance to various chemicals including acid and alkali, that is, it has high chemical resistance and corrosion resistance, It can be used for various materials such as moldings, containers, electric wires, thermometers, sensors, gaskets, packing and frying pans because it also repels water and oil as well as non-adhesive and non-wetting. · It is used for covering the product surface.

These coatings are usually formed by lining of a fluororesin film or coating or impregnation of a fluoropolymer fine particle dispersion, and a variety of various fluororesin films and dispersions are commercially available, and new products have been developed (see, for example, Patent Document 1).

However, compared with other organic polymers, fluorine resins are excellent in heat resistance because they are nonflammable, but they are softer than other organic polymer resins, so they are difficult to stabilize at the time of molding and are subjected to surface treatments such as coatings and formulas It is difficult to do.

In addition, since fluororesin is an excellent insulating material, it is liable to be highly charged, and is positioned as a material which is most negatively charged in a charging column. It is very important to take measures to prevent electrification and static electricity of fluorine resin because it can cause flammable gas and solvent flammable explosion and insulation breakdown of fluoric resin product itself.

Charging is usually carried out by attaching earth to a fluororesin or a product thereof or by mixing a conductive material with a fluororesin, and such a method is often difficult.

For example, in order to make it multifunctional and high-performance, coating and modification of the surface are frequently performed, and the fluororesin is very easily and strongly charged, so that the coating liquid is repelled and can not be coated in many cases.

When carbon black (CB), carbon fiber (CF), carbon nanotube (CNT) or metal fine powder (fine powder) are mixed with current conductive materials, workability is poor even if grounding is used. , The surface resulting from their incorporation may not be suitable for subsequent coating or modification.

In addition, although the fluorine resin has a great advantage that the non-wettability and non-tackiness of the fluorine resin are not well contaminated, it becomes a great obstacle because the coating liquid is difficult to be applied to the surface coating or the formula.

Generally, in order to improve workability, weatherability, durability, rigidity, impact resistance, sliding property, abrasion resistance, flame retardancy, heat resistance, sound insulation and gas shielding property, or plasticity of an organic polymer, In order to improve the surface properties, an additive (filler) is incorporated.

Examples of the filler include various kinds of metal oxide and metal such as fine particles and fibers such as talc, mica, silicon oxide, titania, alumina, magnesia, graphite, molybdenum sulfide, calcium carbonate, , They are selected and used according to purposes and countermeasures (Non-Patent Documents 1 to 3).

For example, talc, silica, calcium carbonate, alumina, montmorillonite and synthetic mica are used for mechanical and thermal reinforcement. CB, CNT and metal powder are used for electromagnetic and static electricity measures. Silica and boron nitride are used for high frequency measures. Aluminum hydroxide, magnesium hydroxide, antimony oxide, hydrotalcite, silica, etc. for the flame retardation; montmorillonite or synthetic mica for the measures against gas barrier; and silica, talc Calcium carbonate and the like, and silver, zeolite, silver and silica are used for sterilization and antibacterial, respectively (Non-Patent Document 2).

In the fluorine resin, the inorganic filler is usually glass fiber, carbon fiber, graphite, carbon, CNT, molybdenum disulfide, silica, etc. They are mainly used for abrasion resistance, compression resistance, cold flow resistance, It is added for improvement and improvement.

These are not intended to modify the surface properties for the purpose of multifunctional and highly functionalization of the fluororesin such as adjustment and improvement of wettability, tackiness and chargeability, and therefore it is difficult to say that it is in conformity with the modification of the surface properties.

In general, a solid molded article such as a powder of fluororesin, a film and a coating film can be obtained by evaporating and drying moisture from the fine particle aqueous dispersion. In such operations and processes, it is preferable that the filler component is previously added to and mixed with the aqueous dispersion (emulsion) of the fluororesin microparticles to form a homogeneous mixed dispersion of the fluororesin microparticles and the filler component (additive).

However, the kinds of the additive which becomes a homogeneous mixed dispersion by the addition and mixing into the aqueous dispersion of the fluororesin fine particles are very small.

Patent Documents 2 to 4 disclose a colloidal sol liquid of inorganic fine particles as an additive which is uniformly dispersed by mixing with a fluorine resin emulsion. Specifically, silica, titanium oxide, zeolite, aluminum oxide (alumina) Zinc, antimony pentoxide, silicon carbide, silicon nitride, aluminum nitride, lead oxide, tin oxide, magnesium oxide and the like, and many kinds of additives are suitable for preparing a uniformly mixed dispersion with a fluororesin emulsion.

However, in the examples in the above patent documents, all the preparation of the homogeneous mixed dispersion is limited to silica, and examples of the colloid solution of the inorganic microparticles other than silica are not described, and the properties of the inorganic fine particle sol , Composition, composition and the like are not described, and only the material name of the inorganic fine particle sol is described.

Therefore, additives which are uniformly dispersed by mixing with the fluororesin emulsion are silica sol or organosilicate solutions most of which are excellent in viscosity stability, and alumina sol is known to a very small extent (Patent Documents 1 to 6).

Such addition is aimed at improving the mechanical strength, heat resistance, dimensional stability, compression creep characteristics and melt moldability of a finally obtained fluorine resin solid. It is not intended to modify or adjust the surface properties, Mixed dispersions usable for adjustment are difficult to obtain.

For the reasons described above, research and development of a filler (additive) intended to modify the surface properties for multifunctional and highly functional fluororesin, specifically to adjust or improve the wettability, tackiness and chargeability, Not only a solid such as a coating film or a molded body thereof but also an aqueous dispersion of a fluororesin fine particle as a base thereof has been developed.

Japanese Patent Application Laid-Open No. 2006-117900 Japanese Patent Application Laid-Open No. 2007-119769 Japanese Patent Application Laid-Open No. 2008-115335 Japanese Patent Application Laid-Open No. 2008-115336 Japanese Patent Application Laid-Open No. 8-258228 Japanese Patent Laid-Open Publication No. 2012-219126

Japan Rubber Society, Vol. 75, No. 8, 330-332 (2002) PLASTICS AGE, April 2006, 72-80 Journal of the Rubber Society of Japan, Vol. 82, No. 2, 61-66 (2009)

Disclosure of the Invention The present invention has been made in order to solve the problems of the prior art as described above, and the inventors of the present invention have extensively searched for a combination of an aqueous dispersion of a fine particle of a fluororesin or an emulsion and a metal oxide colloidal sol, As a result, it has been found that fluororesin fine particles and metal oxide fine particles, which enable adjustment and improvement of wettability, adhesion and chargeability of a solid surface such as a finally obtained fluororesin powder, film or coating film (Sol) which is uniformly suspended and dispersed in an aqueous solvent.

The invention according to claim 1 is characterized in that an aqueous dispersion of a fluorine resin fine particle and a fluorine-containing fluorine-containing fluorine-containing fluorine resin which are obtained by mixing a fine metal oxide fine particle sol having an appropriate pH value of any one of titanium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide, The resin-metal oxide mixed dispersion, wherein the fluororesin fine particles and the metal oxide fine particles are suspended and dispersed together without causing coagulation sedimentation, gelation, solidification and / or phase separation, and the suspended dispersion state is stably maintained for 3 days or more at room temperature characterized in that the box and, at the same time, the fluorine resin-metal oxide mixture is the water contact angle of the solid 130˚ obtained by evaporation of the solvent from the dispersion scattering more than the surface resistivity is 2.0 × 10 ¹² Ω / □ fluoride characterized in that not more than Resin-metal oxide mixed dispersion.

The invention according to claim 2 is characterized in that the optimum pH value of the metal oxide fine particle sol is 2.5 to 13.5 for titanium oxide, 6.5 to 9 for zirconium oxide, 7 to 10 for lanthanum oxide, 7 to 10 for neodymium oxide, 9.5, and tin oxide is 9 to 11. The present invention also relates to the fluororesin-metal oxide mixed dispersion according to claim 1.

The invention according to claim 3 is characterized in that the fluororesin-metal oxide mixed dispersion is constituted by 3 to 100 times of the fluororesin fine particles and 5 to 120 times of the water in the weight ratio with respect to the content of the metal oxide fine particles in the dispersion liquid To the fluororesin-metal oxide mixed dispersion according to claim 1 or 2.

The present invention according to claim 4 is characterized in that an aqueous dispersion of fluororesin fine particles and a metal oxide fine particle sol having an appropriate pH value of any one of titanium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide or tin oxide, Characterized in that it is produced by mixing fluorine resin fine particles at a ratio of 3 to 100 times and water at a ratio of 5 to 120 times with respect to the content of the metal oxide fine particles in the liquid at a temperature of 100 占 폚 To a process for producing the fluororesin-metal oxide mixed dispersion of the present invention.

The invention according to claim 5 is characterized in that the optimum pH value of the metal oxide fine particle sol is 2.5 to 13.5 for titanium oxide, 6.5 to 9 for zirconium oxide, 7 to 10 for lanthanum oxide, 7 to 10 for neodymium oxide, 9.5, and tin oxide is 9 to 11. The present invention relates to a process for producing a fluororesin-metal oxide mixed dispersion according to the fourth aspect of the present invention.

The fluororesin-metal oxide mixed dispersion of the present invention is a fluororesin-metal oxide mixed dispersion in which fine particles of a fluororesin and a metal oxide are free from coagulation or aggregation causing precipitation and have a size close to the original size even when their original size or somewhat coagulation occurs, , The mixed dispersion is uniformly mixed and dispersed in a water solvent in such a size as to be suspended and dispersed in a water solvent. Therefore, it is preferable that the mixed dispersion of the present invention is applied to an object to be coated, impregnated or dipped (immersed) In the work, it is possible to carry out the coating without adding any metal oxide-added fluororesin (Teflon (registered trademark)) layer to a desired thickness, and also because of the dense accumulation of fine particles.

Further, since the operation and operation using the mixed dispersion of the present invention are simple, they are very safe while being economical, and economically excellent.

<Composition of fluororesin-metal oxide mixed dispersion>

The fluororesin-metal oxide mixed dispersion of the present invention is basically an aqueous dispersion in which fluororesin fine particles and metal oxide fine particles composed of fluororesin fine particles, metal oxide fine particles, and water are suspended and dispersed. The composition of the fluororesin-metal oxide mixed dispersion is not limited to these, and other constituents may be included.

The fluororesin fine particles in the present specification are polymers of monomers selected from tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), vinylidene fluoride and vinyl fluoride, or the like It is preferable that the fine particles are resin fine particles made of these copolymers. Among them, those dispersed in water are preferably used for preparing the fluororesin-metal oxide mixed dispersion of the present invention.

In addition, monomers or copolymers other than the above-mentioned monomers may be used as long as they are dispersible in water.

In the present invention, the metal oxide fine particles mean titanium oxide (titania), zirconium oxide (zirconia), lanthanum oxide (lanthana), neodymium oxide, cerium oxide (ceria) and tin oxide, Is used to obtain the fluororesin-metal oxide mixed dispersion of the present invention.

In the case of the fluororesin fine particles or the metal oxide fine particles, the particles tend to precipitate and precipitate as their size becomes larger. Therefore, in order for the fine particles of the fluororesin and the metal oxide to retain the suspended dispersion state in the aqueous solvent for a long period of time, the particle size thereof should be small.

More specifically, in the fluororesin fine particles, the average particle diameter of the primary particles is preferably in the range of 0.1 to 0.5 占 퐉, and the average particle diameter of the metal oxide fine particles is in the range of 2 to 150 nm, preferably 2 to 50 nm . However, the size of the fine particles of the fluororesin and the metal oxide is not limited to the above, provided that the suspended dispersion state can be maintained for a long time in an aqueous solvent. The average particle diameter of the metal oxide fine particles is a median diameter measured by a dynamic light scattering particle diameter distribution measuring device LB-500 manufactured by Horiba Kogyo Co., Ltd.

It is important to consider not only affinity with the solvent but also to avoid agglomeration of the particles with respect to the uniform suspended suspension in the solvent of the particles. The cohesion increases the tackiness and causes coagulation and gelation, resulting in precipitation. Therefore, it is necessary to prevent aggregation and agglomeration of the particles. As a countermeasure therefor, there is a method in which particles are repelled by causing the particles to have the same charge (by electrification), and the particles are surrounded with a surfactant to form a complex micelle .

In the case of a metal oxide colloid, even in the case of using a complex micelle, many particles are repelled and dispersed by charging.

Generally, the charge amount of the particles is closely related to the pH of the solution, and is very sensitive to pH. Therefore, the pH of the metal oxide sol used in the preparation of the fluororesin-metal oxide mixed dispersion of the present invention also has an appropriate range for preventing the flocculation, which differs depending on the kind of the metal.

The pH of the metal oxide sol used in the present invention is 2.5 to 13.5, preferably 3 to 13 in titania, 6.5 to 9, preferably 7 to 8.5 in zirconia, 7 to 10, preferably 7.5 to 9.5 in lanthana, It is preferably 7 to 10, preferably 7.5 to 9.5 in neodymium oxide, 6.5 to 9.5, preferably 7 to 9 in ceria, and 9 to 11, preferably 9.5 to 10.5 in tin oxide.

The pH of the fluororesin fine particle aqueous dispersion to be used for preparing the fluororesin-metal oxide mixed dispersion is generally preferably 7 to 11.

The pH range of the fluororesin-metal oxide mixed dispersion is preferably 1 to 13. The pH range is more preferably 3 to 12. The kind and the amount of the fluororesin fine particle aqueous dispersion and the metal oxide sol are appropriately set so that the pH range of the fluororesin-metal oxide mixed dispersion obtained by mixing the both is within the above range and the predetermined dispersion stability and other characteristics are obtained . When the pH range of the resulting fluororesin-metal oxide mixed dispersion is out of the range of 1 to 13, it is preferable to adjust to the above-mentioned pH range using a suitable acid or alkali.

In the present specification, the suspended dispersion state of the fluororesin-metal oxide mixed dispersion liquid is stably maintained means that fluororesin fine particles and metal oxide fine particles in the fluororesin-metal oxide mixed dispersion liquid are coagulated and precipitated together at a room temperature storage condition for at least three days, Quot; refers to a state in which suspended and dispersed state is maintained without causing gelation, solidification and / or phase separation.

The fluororesin-metal oxide mixed dispersion liquid according to the present invention is characterized in that the water contact angle of the solid obtained when the solvent is evaporated from the fluororesin-metal oxide mixed dispersion is 130 ° or less and the surface resistivity is 2.0 x 10 ¹² ? /? Or less . The preferable range of the water contact angle is 120 DEG or less.

Each value of the water contact angle and surface resistivity in the present invention is obtained by the following measuring method.

The water contact angle is measured by coating an obtained fluororesin-metal oxide mixed dispersion on a glass substrate and drying the coated film at 150 DEG C for 30 minutes by an automatic contact angle meter.

The surface resistivity was measured by coating a fluororesin-metal oxide mixed dispersion on a glass substrate with a spin coater (number of revolutions: 16.67 s ^-1 / 10 seconds) and blowing and drying it at 150 캜 for 30 minutes using a high resistivity meter do.

As described above, addition of a surfactant is often very effective for stabilizing the suspended dispersion state of fine particles.

The surfactant to be added is selected in consideration of the affinity between the metal oxide and the fine particles of the fluororesin and the solvent, the electrostatic repulsion property of the generated complex micelles, etc. By simply mixing the fluororesin fine particle aqueous dispersion and the metal oxide sol, When obtained, the surfactant is not an essential ingredient.

However, the addition of an appropriate amount of a suitable surfactant may prolong the period of stably maintaining the dispersed state, so that the present invention does not exclude the addition of the surfactant. Rather, a surfactant effective for a stable extension of the period, for example, a commonly used nonionic surfactant such as polyoxyalkylene alkyl ether or polyoxyalkylene alkyl phenyl ether may be used.

When the pH range of the fluororesin-metal oxide mixed dispersion is out of the range of 1 to 13 by the addition of the surfactant, it is preferable to adjust the pH to the above range using a suitable acid or alkali.

When a surfactant is present in the fluororesin-metal oxide mixed dispersion, the surfactant may perform any kind of intermolecular association with the metal oxide fine particles and / or fluororesin fine particles through van der Waals interaction or electrostatic interaction Thereby maintaining a uniform dispersion state.

Instead of the surfactant, the surface of the metal oxide fine particles and / or the fluorine resin fine particles may be modified in advance with a substance having a similar action. Alternatively, a modifier having such a function may be added to the metal oxide fine particles and / It is also effective to maintain the uniform suspended dispersion state of the fluororesin-metal oxide mixed dispersion for a long period of time by adding it to the dispersion, and such treatment may be carried out.

More specifically, the treatment may be performed by modifying the surface of the metal oxide fine particles with a silane coupling agent or the like, or adding a silane coupling agent or the like to the metal oxide fine particle sol. It may be a modified method used.

The aggregation of fine particles is closely related to its concentration.

When the concentration is increased, the tackiness is increased to cause coagulation and gelation, and cohesive precipitation tends to occur. Therefore, in order to attain the homogeneous mixed dispersion state of the fluororesin fine particles and the metal oxide fine particles in the fluororesin-metal oxide mixed dispersion and to maintain them for a long period of time, it is effective to lower the liquid concentration of both fine particles, that is, low particle concentration.

However, when the particle concentration is low, the film obtained by the application such as coating or impregnation is thin and consumes a large amount of energy for evaporation of the solvent relatively in the heat treatment step such as drying and firing, .

From such a viewpoint, it is preferable that the fluororesin-metal oxide mixed dispersion is composed of 3 to 100 times of the fluororesin fine particles and 5 to 120 times of the water based on the weight of the metal oxide fine particles in the liquid, May be selected at any weight ratio to achieve properties.

&Lt; Method of producing fluororesin-metal oxide mixed dispersion >

The fluororesin-metal oxide mixed dispersion according to the present invention is prepared by mixing an aqueous dispersion of the fluororesin fine particles and a metal oxide fine particle suspension with stirring.

It is preferable that the composition of the mixed solution is prepared such that the fluororesin fine particles have a particle size of 3 to 100 times and water has a particle size of 5 to 120 times with respect to the content of the metal oxide fine particles.

The stirring at the time of mixing is not particularly specified, and the optimum stirring conditions are appropriately selected in consideration of the particle concentration at the time of mixing, the viscosity of the mixed solution, the liquid temperature, and the like.

The temperature at the time of stirring is usually room temperature, but it may be lower or higher than room temperature in consideration of the viscosity of the mixed solution, and the stirring temperature is appropriately selected depending on the situation.

The pressure at the time of mixing and stirring is not particularly specified, and is usually carried out under atmospheric pressure. However, when pressurization or depressurization is required from the viewpoint of the viscosity or concentration of the solvent, the pressure can be appropriately selected according to the purpose.

<About raw materials>

In preparing the fluororesin-metal oxide mixed dispersion according to the present invention, the following aqueous dispersion or emulsion of fluorine fine particles and colloidal sol of metal oxide fine particles were used. In the present specification, symbols A-1 to A-3 and B-1 to B-7 are attached.

· Fluorine resin fine particle aqueous dispersion

A-1: Mitsui-DuPont Fluorochemical product, PTFE 31-JR (PTFE solid content: 60% by weight, average molecular weight: 2 x 10 ⁴ to 1 x 10 ⁷ , average particle diameter of PTFE primary particles: pH: 10.5)

A-2: 60% by weight, average molecular weight: 2 x 10 ⁴ to 1 x 10 ⁷ , average particle diameter of PTFE primary particles: 0.1 to 0 (trade name, manufactured by Daikin Industries, , PH: 9.7)

A-3: Asahi glass product, Fluon (registered trademark) PTFE Dispersion AD911E (PTFE solid content: 60% by weight, average particle diameter of PTFE primary particles: 0.1 to 0.5 탆, average molecular weight: 2 10 ⁴ to 1 10 ⁷ , pH: 10)

· Metal oxide sol

B-1: Taki Chemical Co., Tai-knol A-6 (TiO ₂ weight%: 6, average particle diameter: 20 nm, pH: 12)

B-2: manufactured by Taki Chemical Co., Ltd., Tai-Rok AM-15 (TiO ₂ weight%: 15, average particle diameter: 20 nm, pH: 4)

B-3: Barium Zr-C20 (ZrO ₂ wt%: 20, average particle diameter: 40 nm, pH: 8)

B-4: Bayer La-C10 (La ₂ O ₃ wt%: 10, average particle diameter: 40 nm, pH: 8)

B-5: Taki Chemical product, Vial Nd-C10 (Nd ₂ O ₃ wt%: 10, average particle diameter: 20 nm, pH: 9)

B-6: Nidoral B-10 (CeO ₂ weight%: 10, average particle diameter: 20 nm, pH: 8)

B-7: CERAMES S-8 (SnO ₂ wt%: 8, average particle diameter: 8 nm, pH: 10)

&Lt; Use of fluorine resin-metal oxide mixed dispersion >

The fluororesin-metal oxide mixed dispersion of the present invention is preferably used as a coating liquid for coating a surface of various materials such as metals, carbon, plastic, glass, ceramics, and wood, and a surface of a product made of these materials, or an impregnation liquid for fibers or powders of the above- Specifically, it exhibits excellent performance as an undercoating material for coating and coating materials for various materials and products such as electric wires, thermometers, various sensors, gaskets and packing, and multi-layer and multi-layer coatings for multi-function and high performance.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The surface resistivity and the water contact angle of the solid obtained in the fluororesin-metal oxide mixed dispersion shown in the examples were measured as follows. The surface resistivity was measured by applying the mixed solution on a glass substrate with a spin coater (number of revolutions: 16.67 s ^-1 / 10 seconds) and drying with a ventilating drier (150 ° C for 30 minutes) to form a coated thin film. (MCP-450 manufactured by Mitsubishi Chemical Corporation), the surface resistivity of the coating film was measured. The water contact angle was measured by applying the mixed solution to a SUS substrate including a glass substrate (without adhesive) or a phenolic adhesive and drying (100 ° C / 60 minutes or 150 ° C / 30 minutes) &Lt; / RTI &gt; Dms-400).

&Lt; Influence of metal type of metal oxide sol in fluororesin-metal oxide mixed dispersion >

(Example 1)

Fluorine resin fine particle aqueous dispersion: A-1; 30g

Metal oxide fine particle sol: B-1; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The prepared dispersion of fluororesin - titania did not cause coagulation gelation, flocculation, sedimentation and phase separation for more than 15 days at room temperature. Further, the fluidity was very good, and there was no problem even after 15 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 2)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-1; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The prepared dispersion of fluororesin - titania did not cause coagulation gelation, flocculation, sedimentation and phase separation for more than 15 days at room temperature. Furthermore, the fluidity was very good, and there was no problem even after 15 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 3)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-1; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The prepared dispersion of fluororesin - titania did not cause coagulation gelation, flocculation, sedimentation and phase separation for more than 15 days at room temperature. Furthermore, the fluidity was very good, and there was no problem even after 15 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 4)

Fluorine resin fine particle aqueous dispersion: A-1; 30g

Metal oxide fine particle sol: B-2; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of fluororesin - titania did not cause coagulation gelation, aggregation precipitation and phase separation for more than 5 days at room temperature. Further, the fluidity was very good, and there was no problem even after 5 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 5)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-2; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

RESULTS: The pH of the prepared dispersion of fluororesin-titania was 4.8, and the viscosity did not change for more than 5 days at room temperature after coagulation gelation, flocculation, and phase separation. Further, the fluidity was very good, and there was no problem even after 5 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

Using a prepared dispersion liquid of a fluororesin-titania mixture, a glass substrate (drying: 150 ° C / 30 minutes) or a SUS substrate (drying: 100 ° C / 60 minutes or 150 ° C / 30 minutes) The water contact angles of the coating films were 90.7 °, 105.3 ° and 102.9 °, respectively, which were significantly lower than 130 ° to 140 ° of the fluororesin membrane PTFE membrane. The surface resistivity of the film formed on a glass substrate (drying: 150 ° C / 30 minutes) by spin coating was 6.9 × 10 ¹¹ Ω / □, and the fluororesin microparticle aqueous dispersion (A-2: The surface resistivity of the film obtained from polyphenol D-111 (polyphron D-111) was considerably smaller than 2.5 x 10 ¹² ? / ?.

(Example 6)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-2; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of fluororesin - titania did not cause coagulation gelation, aggregation precipitation and phase separation for more than 5 days at room temperature. Further, the fluidity was very good, and there was no problem even after 5 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 7)

Fluorine resin fine particle aqueous dispersion: A-1; 30g

Metal oxide fine particle sol: B-3; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The prepared dispersion of fluororesin - zirconia did not cause coagulation gelation, aggregation precipitation and phase separation for more than 10 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 8)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-3; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The pH of the prepared dispersion of fluorocarbon resin - zirconia was 8.6, and the viscosity did not change during storage at room temperature for 10 days or more, without causing coagulation gelation, flocculation, and phase separation. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

The water contact angle was measured using a glass substrate (drying: 150 占 폚 / 30 minutes) or a SUS substrate containing a phenolic adhesive (manufactured by Fuji Photo Film Co., Ltd.) with the use of a fluororesin-zirconia mixed dispersion prepared by the same procedure as in Example 5, 104.8 °, and 99.3 ° in the case of drying at 100 ° C / 60 minutes or 150 ° C / 30 minutes, respectively, and the surface resistivity of the film by the spin coating method was 2.6 × 10 ¹¹ Ω / □.

(Example 9)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-3; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The prepared dispersion of fluororesin - zirconia did not cause coagulation gelation, aggregation precipitation and phase separation for more than 10 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 10)

Fluorine resin fine particle aqueous dispersion: A-1; 30g

Metal oxide fine particle sol: B-4; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The viscosity of the prepared dispersion of fluororesin - lanthanum mixture did not change during storage at room temperature for more than 7 days, did not cause coagulation gelation, aggregation precipitation, and phase separation. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 11)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-4; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The pH of the prepared dispersion of fluorocarbon resin - lanthanum was 9.2, and the viscosity did not change after preservation test without causing coagulation gelation, flocculation and phase separation for more than 7 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

Using the prepared fluororesin-lanthana mixed dispersion, a coating film was formed in exactly the same manner as in Example 5, and as a result, the water contact angle was measured using a glass substrate (drying: 150 DEG C / 30 minutes) or a SUS substrate 122.9 ° and 121.4 ° in the case of the spin coating method (drying: 100 ° C / 60 minutes or 150 ° C / 30 minutes), respectively, and the surface resistivity of the film by spin coating was 2.5 × 10 ¹¹ Ω / □.

(Example 12)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-4; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 30 minutes

Results: The viscosity of the prepared dispersion of fluororesin - lanthanum mixture did not change during storage at room temperature for more than 7 days, did not cause coagulation gelation, aggregation precipitation, and phase separation. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 13)

Fluorine resin fine particle aqueous dispersion: A-1; 30g

Metal oxide fine particle sol: B-5; 9g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of neodymium fluoride resin - neodymium did not cause coagulation gelation, flocculation, sedimentation and phase separation for more than 7 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 14)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-5; 9g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of neodymium fluoride resin - neodymium did not cause coagulation gelation, flocculation, sedimentation and phase separation for more than 7 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

Using the prepared dispersion of fluorocarbon resin-neodymium oxide, the coating film was formed in the same manner as in Example 5, and as a result, the water contact angle was measured using a glass substrate (drying: 150 DEG C / 30 minutes) or a SUS substrate (dry: 150 ℃ / 30 minutes), and 82.6 ° and 115.2 ° in each film surface resistivity by the spin coating method is 2.8 × 10 ¹¹ Ω / □, respectively.

(Example 15)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-5; 9g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of neodymium fluoride resin - neodymium did not cause coagulation gelation, flocculation, precipitation and phase separation for more than 7 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 10 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

As can be seen from the above examples, any of the fluororesin fine particle aqueous dispersions is well compatible with each sol of titania, zirconia, lanthana and neodymium oxide, and a homogeneous mixed dispersion can be easily formed.

(Example 16)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-6; 10g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of fluorocarbon resin - ceria did not cause coagulation gelation, aggregation precipitation and phase separation for more than 3 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 4 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

Using the prepared fluororesin-ceria mixed dispersion, a coating film was formed in exactly the same manner as in Example 5, and as a result, the water contact angle was measured using a glass substrate (drying: 150 DEG C / 30 minutes) or a SUS substrate (dry: 150 ℃ / 30 min.) and 116.9 ° and 124.5 ° in each film surface resistivity by the spin coating method is 0.9 × 10 ¹¹ Ω / □, respectively.

(Example 17)

Fluorine resin fine particle aqueous dispersion: A-3; 30g

Metal oxide fine particle sol: B-6; 10g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The prepared dispersion of fluorocarbon resin - ceria did not cause coagulation gelation, aggregation precipitation and phase separation for more than 3 days at room temperature. Further, the fluidity was very good, and there was no problem even after 4 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

(Example 18)

Fluorine resin fine particle aqueous dispersion: A-2; 30g

Metal oxide fine particle sol: B-7; 24g

Mixing conditions: room temperature, normal pressure

Stirring time: 60 minutes

Results: The pH of the prepared dispersion of fluorocarbon resin - tin oxide was 9.8, and the viscosity did not change much after storage test without causing coagulation gelation, flocculation and phase separation for more than 3 days at room temperature. Further, the fluidity was extremely good, and there was no problem even after 3 days of use as a coating liquid or impregnation liquid for fluorine resin coating.

The coating film was formed in the same manner as in Example 5 using the prepared mixed fluororesin-tin oxide dispersion. As a result, the water contact angle was found to be a glass substrate (drying: 150 DEG C / 30 minutes) And 113.0 °, 121.1 ° and 126.6 ° in each of the substrate (drying: 100 ° C / 60 minutes or 150 ° C / 30 minutes), and the surface resistivity of the film by the spin coating method was 1.9 × 10 ¹¹ Ω / □.

From the above-described Examples 16 to 18, the fluororesin fine particle aqueous dispersion A-2 has good compatibility with ceria and tin oxide, and a homogeneous mixed dispersion can be easily formed. In addition, the fluororesin fine particle aqueous dispersion A-3 has good compatibility with ceria and can easily form a homogeneous mixed dispersion.

&Lt; Advantage of invention &

As seen from the above examples, it has been found that the metal oxide mixed with the fluororesin is effective for suppressing the charging of the fluororesin and lowering the water contact angle, that is, improving and adjusting the wettability and non-tackiness.

&Lt; Application and efficacy of the present invention >

According to the present invention, it is possible to suppress and control the charging of the fluororesin, and to improve and improve the wettability and the tackiness. This was confirmed in the peeling of the coating film on the SUS substrate by cross-cut adhesion test. That is, a coating film formed by applying a fluororesin-titania mixed dispersion to a SUS substrate containing a phenolic adhesive and a PTFE membrane was attached to the same SUS substrate using the same adhesive (see Example 5) was knife- And as a result, it was confirmed that the former was easily peeled off completely, whereas the former was not peeled off at all. This shows that the incorporation of a metal oxide such as titania into the fluorine resin greatly improves the wettability and adhesion.

It has also been shown that the incorporation of metal oxides makes it possible to perform surface modification and treatment for subsequent functionalization and multi-functionalization of the fluororesin.

In addition, if only the fluorine resin is used, the surface of the fluorine resin is soft, so that it is likely to be easily scratched if it is contacted with a hard one. The incorporation of this kind of metal oxide makes the fluorine resin harder and increases the heat resistance, It also has an effect.

The fluororesin-metal oxide mixed dispersion of the present invention can be used as a coating liquid for coating various surface materials of metal, carbon, plastic, glass, ceramic, graphite, carbon fiber, carbonized fiber and the like, Lt; / RTI &gt;

Specifically, it is used as coating material and coating material for coating of various materials such as electric wire, thermometer, various sensors, gaskets and packing, and for making the surface of product highly functional and multifunctional.

Claims (5)

An aqueous dispersion of the fluororesin fine particles; A mixed aqueous fluororesin-metal oxide dispersion comprising a metal oxide fine particle sol having an appropriate pH value of any one of titanium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide or tin oxide,
Characterized in that the fluorine resin particles and the metal oxide fine particles are suspended and dispersed together without causing cohesion, gelation, solidification and / or phase separation, and the suspended dispersion state is stably maintained for three days or more at room temperature storage, the fluorine resin-metal oxide is a water contact angle of the solid obtained by evaporation of the non-solvent from the mixed dispersion 130˚ or less, the surface resistivity is 2.0 × 10 fluorine resin of ¹² Ω / □ or less characterized in that - the metal oxide mixed dispersion. The method according to claim 1,
The optimum pH value of the metal oxide fine particle sol is 2.5 to 13.5 for titanium oxide, 6.5 to 9 for zirconium oxide, 7 to 10 for lanthanum oxide, 7 to 10 for neodymium oxide, 6.5 to 9.5 for cerium oxide, Lt; RTI ID = 0.0 &gt; 11. &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
Wherein the fluororesin-metal oxide mixed dispersion has a weight ratio of the fluororesin-metal oxide mixture to the fluororesin-metal oxide mixed dispersion of 3 to 100 times and water of 5 to 120 times the weight of the metal oxide fine particles in the dispersion. Dispersion. An aqueous dispersion of the fluororesin fine particles; The metal oxide fine particle sol having a suitable pH value of any one of titanium oxide, zirconium oxide, lanthanum oxide, neodymium oxide, cerium oxide or tin oxide is subjected to a treatment at a temperature of 5 to 100 ° C with respect to the content of the metal oxide fine particles in the liquid The method for producing the fluororesin-metal oxide mixed dispersion according to any one of claims 1 to 3, wherein the fluororesin-metal oxide mixed dispersion is produced by mixing 3 to 100 times of the fluororesin fine particles and 5 to 120 times of the water at a weight ratio . 5. The method of claim 4,
The optimum pH value of the metal oxide fine particle sol is 2.5 to 13.5 for titanium oxide, 6.5 to 9 for zirconium oxide, 7 to 10 for lanthanum oxide, 7 to 10 for neodymium oxide, 6.5 to 9.5 for cerium oxide, 11. The method for producing a fluororesin-metal oxide mixed dispersion according to claim 1,