JPWO2018154630A1 - Coating composition, coating film and air conditioner having the same - Google Patents

Abstract

A dispersion comprising an acrylic resin and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide, and a dispersion comprising a fluorine resin using a fluorine-based solvent as a dispersion medium It is a coating composition. The fluorinated solvent preferably has a Kauri-butanol value (KB value) of 5 or more and 50 or less. It is preferable that the dispersion containing the fluorocarbon resin containing the fluorocarbon solvent as the dispersion medium is 1% by mass or more and 15% by mass or less with respect to the coating composition.

Description

  The present invention relates to a coating composition and a method for producing the same, a coating film and a method for forming the same, and an air conditioner having the coating film.

  Since various stains such as dust, oil smoke and cigarette dust adhere to the surfaces of various articles used indoors or outdoors, various methods have been studied to be able to suppress this. For example, in order to suppress adhesion of dirt such as dust, it is known that electrostatic adhesion of dust can be suppressed by coating the surface of various articles with an antistatic agent. Further, it is known that, in the case of suppressing adhesion of lipophilic stains such as oil smoke, lipophilic stains can be easily removed by coating the surface of various articles with an oil-repellent fluorocarbon resin.

  However, in the method of suppressing the adhesion of various stains as described above, there has been a problem that long-term antifouling performance can not be maintained due to peeling or deterioration of the coating film. Therefore, Patent Document 1 is composed of fine particles having an average particle diameter of 1 nm to 1 mm at least the surface of which is hydrophobic and a coating of an antistatic resin composition, and the fine particles are 20 of the coating surface area of the antistatic resin composition. A water repellent film is described which is characterized in that it is exposed and fixed in a% or more area.

  In addition, Patent Document 2 describes a hard coat film provided with a hard coat layer on one side of a substrate, and in the hard coat layer, the surface of silica fine particles having an average primary particle diameter of 10 to 100 nm is reactive. A function that contains a structure in which reactive silica fine particles having a functional group a are cross-linked with each other, and a conductive antistatic agent is dissolved or dispersed in the space between the silica fine particles or an average primary particle size smaller than silica fine particles Hard coat film filled with a binder component in which the organic fine particles are dispersed, and a reactive functional group a on the surface of the silica fine particle and a reactive functional group b possessed by the binder component are partially cross-linked Is described.

  Further, Patent Document 3 includes a base material and a hard coat film formed on the base material, and the hard coat film is a silica-based particle consisting of a matrix component and silica or silica-alumina, The inorganic oxide particles, which are hollow particles having a cavity, comprise an inorganic oxide particle group in which 2 to 30 chains of average coupling number are linked and the matrix component is made of a thermosetting resin or an ultraviolet curing resin A substrate with a hard coat film characterized in that is described.

JP-A-8-134437 JP, 2010-241018, A Patent No. 4540979

  However, the technology of Patent Document 1 has a problem that sufficient water repellency can not be obtained because the water contact angle of the antistatic resin is small. In addition, the technology of Patent Document 2 has a problem that not only sufficient water repellency can not be obtained, but also the wear resistance is low. Further, in the technology of Patent Document 3, the inorganic oxide particle group in which inorganic oxide particles, which are hollow particles having a cavity inside, are linked in an average connection number of 2 to 30 in a chain form is transparent to the hard coat film. There was a problem of lowering it.

  The present invention was made to solve the problems as described above, and can provide a coating composition having antifouling performance against various stains, abrasion resistance, transparency and high water repellency. It aims to provide goods.

  The present invention is a dispersion containing a dispersion containing an acrylic resin, and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide, and a fluorine resin containing a fluorine-based solvent as a dispersion medium. And a coating composition characterized by comprising:

  According to the present invention, it is possible to provide a coating composition capable of providing a coating film having antifouling performance against various stains, abrasion resistance, transparency and high water repellency.

FIG. 1 is a schematic cross-sectional view of a dispersion A that constitutes a coating composition according to Embodiment 1. FIG. 2 is a schematic cross-sectional view of a dispersion B constituting the coating composition according to Embodiment 1. FIG. 2 is a schematic cross-sectional view of a coating film according to Embodiment 1. FIG. 2 is a schematic cross-sectional view of dispersion A (including hydrophilic silica particles) constituting the coating composition according to Embodiment 1. FIG. 1 is a schematic cross-sectional view of a coating film (including hydrophilic silica particles) according to Embodiment 1. FIG. 2 is a schematic cross-sectional view of dispersion B (including hydrophobic silica particles) constituting the coating composition according to Embodiment 1. FIG. 2 is a schematic cross-sectional view of a coating film (including hydrophobic silica particles) according to Embodiment 1. FIG. 6 is a schematic cross-sectional view of an air conditioner according to Embodiment 2.

Embodiment 1
A coating composition according to Embodiment 1 of the present invention is a dispersion containing an acrylic resin and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide (hereinafter referred to as dispersion A) and a dispersion containing a fluorocarbon resin containing a fluorocarbon solvent as a dispersion medium (hereinafter sometimes referred to as dispersion B). FIG. 1A is a schematic cross-sectional view of dispersion A. FIG. FIG. 1B is a schematic cross-sectional view of dispersion B. FIG.

  As shown in FIG. 1A, the dispersion A is composed of a solvent 1 in which an acrylic resin is dissolved, and metal oxide particles 2 dispersed in the solvent 1 in which the acrylic resin is dissolved. The dispersion A preferably contains an acrylic resin in an amount of 10% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass. When the content of the acrylic resin is less than 10% by mass, it may be difficult to obtain a sufficient film thickness when the coating film is formed, and the performance may not be sufficiently exhibited. On the other hand, when the content of the acrylic resin exceeds 80% by mass, the viscosity of the coating composition may be too high. The mass ratio of the acrylic resin to the metal oxide particles is preferably 60:40 to 98: 2, and more preferably 80:10 to 95: 5. If the mass ratio of the acrylic resin to the metal oxide particles is less than 60:40, the coating film may be too thin and the substrate may be exposed. On the other hand, if the mass ratio of the acrylic resin to the metal oxide particles exceeds 98: 2, cracks may occur in the coating film.

  As shown in FIG. 1B, the dispersion B is composed of the fluorine-based solvent 4 and the fluorine resin particles 3 precipitated in the fluorine-based solvent 4. Dispersion B preferably contains 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 90% by mass or less. When the content of the fluorine-based solvent is less than 50% by mass, aggregation of the fluorine resin particles may occur. On the other hand, if the content of the fluorinated solvent exceeds 99% by mass, defects may occur in the coating film. Dispersion B preferably contains 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 45% by mass or less. If the content of the fluorocarbon resin particles is less than 1% by mass, defects may occur in the coating film. On the other hand, when the content of the fluorocarbon resin particles exceeds 50% by mass, aggregation of the fluorocarbon resin particles may occur. The average particle diameter of the fluorine resin particles is preferably 10 nm or more and 1.0 μm or less, and more preferably 20 nm or more and 900 nm or less. If the average particle diameter of the fluorine resin particles is less than 10 nm, the production may be difficult and the cohesive force of the fluorine resin particles may be so strong that a good coating film may not be formed. On the other hand, when the average particle diameter of the fluorine resin particles exceeds 1.0 μm, the volume ratio occupied by the fluorine resin particles becomes large, and the coating film may become cloudy or charged. The average particle diameter of the fluorine resin particles is a value measured by a laser light scattering method. When a coating film is formed from the coating composition obtained by mixing the dispersion A and the dispersion B, as shown in FIG. 2, it is composed of the acrylic resin 5 including the metal oxide particles 2 and the fluorine resin particles 3. A coating film on which the fluororesin particles 3 are scattered can be formed on the substrate 6. The coating film of such a form can exhibit excellent water repellency while maintaining the antifouling performance and the transparency.

  Examples of the acrylic resin include UV curable acrylic resin, one-component curable acrylic resin, and two-component curable acrylic resin. As the UV curable acrylic resin, urethane acrylate and acrylic resin acrylate are preferable, and specifically, "UNIDIC (registered trademark) V-4005" and "UNIDIC (registered trademark) V-4018" manufactured by DIC Corporation. "Unidic (R) V-4025", "Unidic (R) V-4026", "Unidic (R) V-4205", "Unidic (R) 15-829", " Unitic (registered trademark) 17-813, "unidic (registered trademark) 17-806" and "unidic (registered trademark) 17-824-9", "Hitaloid (registered trademark) 7902" manufactured by Hitachi Chemical Co., Ltd. -1, "Hitaloid (registered trademark) 7909-1", "TA24-195H", "Hitaloid (registered trademark) 7903-1 “Hitaloid® 7906D-3E”, “Hitaloid® 7975”, “Hitaloid® 7988” and “Hitaloid® 7975D”, “8 BR-600” manufactured by Taisei Fine Chemical Co., Ltd. And “8 BR-930 MB” and the like. These UV curable acrylic resins may be used alone or in combination of two or more. Among these, from the viewpoint of quick drying and solubility, "Unidic (registered trademark) 15-829", "Unidic (registered trademark) 17-813", "Unidic (registered trademark) 17-806" and "Unidic (registered trademark) 17-806" Unidic® 17-824-9 "is preferred.

  As a specific example of the one-component curable acrylic resin, "Acricic (registered trademark) A-1300", "Acrydic (registered trademark) A-1370", "Acrydic (registered trademark) A-" manufactured by DIC Corporation are available. 1371 "," ACRIDIC (registered trademark) A-1380 "," ACRIDIC (registered trademark) A-181 "and" ACRIDIC (registered trademark) A-165 "," Plus Plus # 1200 "manufactured by Cashew Corporation. And “Plus Rack CV-1” and “Plus Rack # 1800 series (CP-1M CP-1X)”. These one-component curable acrylic resins may be used alone or in combination of two or more.

  Specific examples of the two-component curable acrylic resin include “Acridic (registered trademark) A-837”, “Acridic (registered trademark) A-814”, and “Acridic (registered trademark) A-” manufactured by DIC Corporation. 829 ′ ′, “Acridic® A-875-55”, “Acridic® A-870”, “Acridic® A-871”, and “Acridic® 52-” 668-BA "and the like. These two-component curable acrylic resins may be used alone or in combination of two or more.

  As a solvent for dissolving the acrylic resin, methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, diethyl ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl acetate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, Butyl acetate, isopentyl acetate, pentyl acetate, acetic acid 3 Methoxybutyl, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, toluene and the like. . These solvents may be used alone or in combination of two or more. Among these, methyl acetate, ethyl acetate and acetic acid isopropyl are preferable from the viewpoint of solubility and quick drying.

Examples of the metal oxide particles include tin oxide (SnO ₂ ), antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), antimony oxide (Sb ₂ O ₅ ), tungsten oxide and the like. These metal oxide particles may be used alone or in combination of two or more. Among these, antimony-doped tin oxide (ATO) is preferable from the viewpoint of dispersion stability in the coating composition.

  The average particle diameter of the metal oxide particles is preferably 5 nm or more and 60 nm or less, and more preferably 10 nm or more and 45 nm or less. If the average particle size of the metal oxide particles is less than 5 nm, production becomes difficult, which is not preferable. On the other hand, when the average particle size of the metal oxide particles exceeds 60 nm, cracks or defects may occur in the coating film. Furthermore, since the inorganic oxide particles linked in a chain like in Patent Document 3 are not used, the fouling substance is not caught on the coating film, and the antifouling performance is enhanced. The average particle size of the metal oxide particles is a value measured by laser light scattering measurement.

  Furthermore, as shown in FIG. 3, the dispersion A may further include dispersed hydrophilic silica particles 8. When the dispersion A further includes the hydrophilic silica particles 8, the antistatic performance of the coating film can be improved, and the antifouling performance of the coating film can be further improved. When a coating film is formed from a coating composition obtained by mixing such dispersion A and dispersion B, as shown in FIG. 4, metal oxide particles 2, fluorine resin particles 3 and hydrophilic silica particles are obtained. A coating film can be formed on the substrate 6, which is made of an acrylic resin 5 containing C.I. 8 and the fluororesin particles 3 are scattered on the surface. The content of the hydrophilic silica particles is preferably 0.5% by mass to 10% by mass with respect to the dispersion A, and more preferably 1% by mass to 8% by mass. If the content of the hydrophilic silica particles is less than 0.5% by mass, the effect of improving the antifouling performance may not be obtained. On the other hand, when the content of the hydrophilic silica particles exceeds 10% by mass, the water repellency of the coating film may be reduced, or the coating film may become cloudy and the gloss may be reduced.

  As the hydrophilic silica particles, those known in the art can be used. Specific examples of hydrophilic silica particles include “Organosilica sol-MA-ST-M”, “Organosilica sol-MA-ST-L” and “Organosilica sol-IPA-ST-L” manufactured by Nissan Chemical Industries, Ltd., "Organo silica sol-IPA-ST-ZL", "organo silica sol-IPA-ST-UP", "organo silica sol-EG-ST", "organo silica sol-NPC-ST-30", "organo silica sol-PGM-ST" “Snowtex (registered trademark) -IPA-ST” and “Snowtex (registered trademark) -DMAC-ST”, “ADELITE (registered trademark) AT-30” manufactured by ADEKA CORPORATION, “ADELITE (registered trademark) AT” -40 "and" ADELITE® AT-50 "," Cataloid (registered trademark) "manufactured by JGC Co., Ltd. SI-550 "and" CATALOID (registered trademark) SI-50 ", and the like.

  The average particle size of the hydrophilic silica particles is preferably 5 nm or more and 500 nm or less, and more preferably 10 nm or more and 200 nm or less. If the average particle size of the hydrophilic silica particles is less than 5 nm, production becomes difficult, which is not preferable. On the other hand, when the average particle size of the hydrophilic silica particles exceeds 500 nm, the coating film may be cracked or the coating film may become cloudy.

  As the fluorine resin constituting the fluorine resin particles, polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene /. Tetrafluoroethylene copolymer (ETFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), fluoroethylene vinyl ether Copolymers, fluoroethylene-vinyl ester copolymers, mixtures of these, and mixtures of these fluororesins with other resins are listed. Among these, fluoroethylene-vinyl ether copolymers are preferable from the viewpoint of being dispersed in a solvent, having strong binding energy to prevent decomposition by ultraviolet light, and being stable over a long period of time.

The fluorinated solvent preferably has a Kauri-butanol value (KB value) of 5 or more and 50 or less. When the KB value of the fluorine-based solvent is less than 5, the fluorine resin particles may be difficult to precipitate and the water repellency may be reduced. On the other hand, when the KB value of the fluorine-based solvent exceeds 50, the production cost is undesirably increased. As a fluorinated solvent, hydrochlorofluorocarbons (HCFC) such as CF ₃ CF ₂ CHCl ₂ (HCFC-225ca), hydrofluoroethers (HFE) such as CHF ₂ CF ₂ OCH ₂ CF ₃ (HFE-347 pc-f), Hydrofluorocarbon (HFC) etc. are mentioned. Among these, from the viewpoint of suppressing global warming, compounds having an ozone destruction coefficient (ODP) of zero are preferable.

  Although the fluorocarbon resin is dissolved in the above-mentioned fluorocarbon solvent, in order to prevent the solid matter from remaining, the fluorocarbon resin 3 previously dissolved in the solvent may be used. Specifically, "Lumiflon (registered trademark) LF200", "Lumiflon (registered trademark) LF800" and "Lumiflon (registered trademark) LF916" manufactured by Asahi Glass Co., Ltd., and "Fluorate (registered trademark) K-" manufactured by DIC Corporation. 700, "Fluorate (registered trademark) K-702", "Fluorate (registered trademark) K-704", "Fluorate (registered trademark) K-705", "Fluorate (registered trademark) K-707" and the like. .

  Furthermore, the dispersion B may further include hydrophobic silica particles 7. As shown in FIG. 5, the hydrophobic silica particles 7 may be attached to the surface of the fluorocarbon resin 3 or some of the hydrophobic silica particles 7 may be incorporated into the fluorocarbon resin 3. Hydrophobic silica particles can improve the water repellency by providing an uneven structure on the surface of the coating film and reducing the contact area with water droplets. When a coating film is formed from a coating composition obtained by mixing such dispersion B and dispersion A, as shown in FIG. 6, fluorine containing metal oxide particles 2 and hydrophobic silica particles 7 is obtained. It is possible to form on the substrate 6 a coating film which is made of an acrylic resin 5 containing resin particles 3 and on which the fluorocarbon resin particles 3 incorporating the hydrophobic silica particles 7 are scattered. The content of the hydrophobic silica particles is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less with respect to the dispersion B. If the content of the hydrophobic silica particles is less than 5% by mass, the effect of improving the water repellency may not be obtained. On the other hand, if the content of the hydrophobic silica particles exceeds 50% by mass, cracks may occur in the coating film.

The hydrophobic silica particles are not particularly limited, and those known in the art can be used. Specifically, as the hydrophobic silica particles, those obtained by subjecting hydrophilic silica particles to hydrophobic treatment can be used. The hydrophilic silica particles are not particularly limited, and various silica particles produced by a dry method (for example, a combustion method), a wet method (for example, a sol-gel method or a precipitation method) can be used. In addition, the silica particles may be silica particles which are partially or entirely melted. Here, the dry process silica can be generally produced by burning a silicon compound such as silicon tetrachloride in an oxyhydrogen flame, and is also referred to as fumed silica. In the dry method, it is possible to obtain silica particles having a specific surface area in the range from about 50m ² / g~500m ² / g by changing the manufacturing conditions. The average particle size of the silica particles calculated from the specific surface area is in the range of about 5 nm to 200 nm, but is usually present as an aggregate of 1 μm or more. Wet process silica can be generally produced by precipitating the silica in solution by neutralizing sodium silicate with a mineral acid, also called white carbon. Moreover, it can also manufacture using the sol gel process which neutralizes a sodium silicate with an acid instead of a mineral acid. Even a wet method, it is possible to obtain silica particles having a specific surface area in the range from about 50m ² / g~1000m ² / g by changing the manufacturing conditions. Among hydrophilic silica particles, those having an appropriate average particle diameter may be selected and used from the above-mentioned various silica particles according to the application. From the viewpoint of easy availability, it is preferable to use dry method silica particles.

  The hydrophobization treatment of the hydrophilic silica particles is not particularly limited and can be carried out according to a method known in the art, but it is preferable to carry out the hydrophobization treatment using a trimethylsilylating agent. By using a trimethylsilylating agent, high water repellency can be maintained for a long time. The trimethylsilylating agent is not particularly limited, and those known in the art can be used. Examples of trimethylsilylating agents include trimethylsilanol, trimethylmethoxysilane, trimethylchlorosilane, aminomethyltrimethylsilane, hexamethyldisilazane, dimethylaminotrimethylsilane, diethylaminotrimethylsilane and the like. Among these, hexamethyldisilazane is preferably used. These trimethylsilylating agents may be used alone or in combination of two or more.

  The average particle diameter of the hydrophobic silica particles is preferably 5 nm or more and 30 nm or less. In addition, the average particle diameter of hydrophobic silica particle means the value of the average particle diameter of the primary particle of hydrophobic silica particle when it measures with the particle size distribution analyzer of a laser beam scattering type or a dynamic light scattering type. When the average particle diameter of the hydrophobic silica particles is less than 5 nm, a fine uneven structure can not be sufficiently formed on the surface of the coating film, and a desired water repellency performance may not be obtained. On the other hand, when the average particle diameter of the hydrophobic silica particles exceeds 30 nm, the surface unevenness structure becomes too large, and the durability of the coating film decreases, and the light scattering of the coating film increases, and the substrate Design may be reduced.

  The mixing ratio of the dispersion A containing an acrylic resin and metal oxide particles to the dispersion B containing a fluorine resin using a fluorine-based solvent as the dispersion medium is 1 mass% of the dispersion B with respect to the coating composition. The content is preferably 15% by mass or less, and more preferably 2% by mass or more and 12% by mass or less. When the mixing ratio of the dispersion B is less than 1% by mass, sufficient water repellency may not be obtained. On the other hand, when the mixing ratio of the dispersion B exceeds 15% by mass, the coating film is easily charged, which is not preferable. In addition, mixing of the dispersion A and the dispersion B is performed such that the fluorine-based solvent contained in the coating composition is 0.5% by mass or more and 14.0% by mass or less with respect to the coating composition. More preferable. When the content of the fluorine-based solvent is less than 0.5% by mass, the fluorine resin particles may not precipitate. On the other hand, when the content of the fluorine-based solvent exceeds 14.0% by mass, the viscosity of the coating composition may be low or the evaporation rate may be too fast, which may cause defects in the film formed after drying.

  A coating composition according to Embodiment 1 of the present invention prepares a dispersion A containing an acrylic resin and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide. A coating composition is obtained by mixing the dispersion of the first step and the dispersion of the second step with the dispersion of the first step and the second step of preparing the dispersion B containing the fluorocarbon resin containing the fluorocarbon solvent as the dispersion medium. And a third step. Preparation of the dispersion in the first step and the second step may be carried out by mixing the above-mentioned components using a mixer known in the art. In the third step, Dispersion A and Dispersion B may be mixed using a mixer known in the art.

  The coating film which concerns on Embodiment 1 of this invention can be formed by the method provided with the process of apply | coating the coating composition mentioned above to a base material, and drying, and the process of hardening a dry coating film.

  The application of the coating composition may be any method as long as the surface of the substrate can be covered with a coating of the coating composition, and examples include immersion, spray coating, brushing, bar coater, hanging sink and the like. Also, after the coating composition is applied to the surface of the substrate, excess coating composition may be removed by air flow. When the excess coating composition is retained on the surface of the substrate, the film thickness of the coating film formed on that portion becomes thick, and the coating film may be cracked or the coating film may become cloudy. Furthermore, it is not preferable because it takes time to dry the excess coating composition and the antifouling performance may not be sufficiently obtained. In the method of removing the excess coating composition by air flow, the drying acceleration effect by the air flow is also obtained, and there is also an advantage that a good coating film is easily formed.

  100 degreeC or less is preferable and, as for the temperature of airflow, 60 degrees C or less is more preferable. If the temperature of the air stream is too high, the acrylic resin or the fluorocarbon resin may be altered to lower the performance of the coating film. On the other hand, if the temperature of the air flow is 25 ° C. or less, the drying time may be undesirably long. The time for blowing the air flow is not particularly limited because it depends on the temperature of the air flow and the shape of the base material, but in the case of a base having a simple shape, 2 seconds or more and 20 seconds or less is preferable. In the case of a substrate having a complicated shape having a minute gap or hole, the blowing time of the air flow is preferably 5 seconds or more and 50 seconds or less. If the time for blowing the air stream is too short, excess coating composition may remain. On the other hand, if the time for blowing the air stream is too long, the antifouling performance may not be obtained sufficiently.

When the acrylic resin is a UV curable acrylic resin, it is preferable to cure the coating by irradiating the dried coating with ultraviolet light. The irradiation intensity is preferably 30 W / cm ² or more and 300 W / cm ² or less, and the irradiation time is preferably 3 minutes or more and 10 minutes or less. If the irradiation intensity is less than 30 W / cm ² , the curing reaction may not proceed sufficiently. On the other hand, if the irradiation intensity exceeds 300 W / cm ² , the coating film may be cracked or yellowed. When the irradiation time is less than 3 minutes, the curing reaction may not proceed sufficiently. On the other hand, if the irradiation time exceeds 10 minutes, cracks or defects may occur in the coating film.
When the acrylic resin is a one-component curable acrylic resin or a two-component curable acrylic resin, it is preferable to cure the coated film by heating the dried coating film at 100 ° C. or less, preferably 60 ° C. or less for 30 minutes or more.

  It is preferable that the film thickness of the coating film formed on a base material is 0.1 micrometer or more and 10 micrometers or less. If the thickness of the coating film is less than 0.1 μm, the antifouling performance may not be sufficiently obtained. On the other hand, when the film thickness of a coating film exceeds 10 micrometers, a crack may arise in a coating film.

  As a base material, parts of various products that require antifouling performance, abrasion resistance, transparency, and high water repellency can be used. Examples of such components include an air conditioner heat exchanger, a fan, a vane, a flap, an air passage forming member, a cover and the like. Moreover, as a material of a base material, plastics, such as a polypropylene, a polystyrene, an ABS resin, ASG resin, metals, such as stainless steel and aluminum, glass, etc. are mentioned, for example.

Second Embodiment
FIG. 7 is a schematic cross-sectional view of an air conditioner according to Embodiment 2 of the present invention. In FIG. 7, the air conditioner 100 mainly includes a housing 10, a blower fan 20, and a heat exchanger 30. The housing 10 has a suction port 11 for sucking air and a blow port 14 for blowing air. A front grill 12 is attached to the front of the housing 10 so as to be openable and closable. The blower fan 20 disposed in the housing 10 is configured to send out the air sucked from the suction port 11 and heat-exchanged by the heat exchanger 30 from the blowout port 14. In the vicinity of the suction port 11, a filter 40 for supplementing dust contained in the sucked air is disposed. The casing portion 15 extends from the rear of the blower fan 20 to the blower outlet 14 and determines the blowing direction of the blower fan 20.

  The heat exchanger 30 is disposed between the suction port 11 and the blower fan 20, and performs heat exchange with the refrigerant in the refrigeration cycle to harmonize (cooling, heating, dehumidifying, blowing, and the like) the sucked air. The heat exchanger 30 is a finned tube type heat exchanger including a heat transfer pipe 31 and a heat dissipating fin 32 through which the heat transfer pipe 31 is inserted. Moreover, the heat exchanger 30 is a substantially reverse V-shape (cross-sectional shape in a side view) including a front upper heat exchanger, a front lower heat exchanger, and a rear heat exchanger.

  A wind having a high wind velocity may collide with the casing portion 15, and dew blown away via the heat exchanger 30 may adhere to the casing portion 15. In the vicinity of the suction side of the casing portion 15 near the blower fan 20, dew is often attached in a horizontal row if the heat insulation from the back surface of the housing 10 is insufficient or warm air intrudes.

  In the vicinity of the blowout port 14, left and right vanes 13 for bending air blown out from the blowout port 14 in the left and right direction, and upper and lower flaps 17 for bending in the up and down direction are installed. The left and right vanes 13 are flat wind direction plates of various outer shapes formed of resin, and a plurality of the left and right vanes 13 are installed in the width direction (left and right direction) of the indoor unit (referred to as the air conditioner 100 in FIG. 7). The upper and lower flaps 17 are wind direction plates having a substantially arc-shaped cross section formed of resin, and are installed across the width direction (left and right direction) of the outlet 14 of the indoor unit. The left and right vanes 13 and the upper and lower flaps 17 can be automatically changed in angle by a motor. The upper and lower flaps 17 may be divided into upper and lower flaps, or a plurality of upper and lower flaps 17 may be provided.

  In addition, in FIG. 7, although the heat exchanger 30 is arrange | positioned so that the top | upper surface side and front side of the ventilation fan 20 may be surrounded, this Embodiment is not limited to this arrangement. Moreover, although the heat exchanger 30 has shown as an example what has the heat exchanger tube 31 and the radiation fin 32 by which the heat exchanger tube 31 is penetrated, this Embodiment is not limited to this. Moreover, although the air conditioner 100 of FIG. 7 is a wall hanging type, this Embodiment is not limited to this.

  The air conditioner according to the second embodiment of the present invention includes the front grille 12, the left and right vanes 13, the casing 15, the upper and lower flaps 17, the blower fan 20 and the heat exchanger 30 according to the first embodiment. Such a coating film is formed. The coating film which concerns on Embodiment 1 is optimal for using for various members of an air conditioner in order to show the outstanding antifouling performance. Therefore, the air conditioner according to Embodiment 2 of the present invention can effectively prevent the performance degradation of the air conditioner and the adhesion of dirt and the like to the air conditioner.

  Although Embodiment 2 describes an example in which the coating film according to Embodiment 1 is formed on the surface of parts of an air conditioner, the present invention is applied to each part of electric equipment such as a ventilation fan, an elevator, a refrigerator, and a solar cell. The coating film which concerns on aspect 1 can also be formed.

  EXAMPLES The present invention will be specifically described by way of the following examples. However, the present invention is not limited thereby, and various applications are possible without departing from the technical scope of the present invention.

In the following examples and comparative examples, a plastic substrate (ABS resin substrate) of 100 mm × 30 mm × 1 mm was used as a substrate.
Example 1
A fluorocarbon resin "Fluoronate (registered trademark) K-702 manufactured by DIC Corporation" (fluororesin concentration: 50% by mass, solvent: toluene) and a fluorinated solvent "Asahiclin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd." (CHF Dispersion 2 was prepared by dissolving in ₂ CF ₂ OCH ₂ CF ₃ , KB value: 12). In the dispersion B, fluororesin particles having an average particle diameter of 520 nm were precipitated. Subsequently, a metal oxide particle "JGC Catalysts & Chemicals Co., Ltd." is made of an acrylic resin "UNIDIC (registered trademark) 17-824-9" (concentration of urethane acrylate: 79.8 mass%, solvent: isopropyl alcohol) manufactured by DIC Corporation. Dispersion A was prepared by mixing ELCOM (registered trademark) -V350 "(antimony-doped tin oxide particle concentration: 15% by mass, average particle size: 40 nm) and isopropyl alcohol.
Thereafter, Dispersion A and Dispersion B were mixed to produce the coating composition of Example 1 having the composition shown in Table 1. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.2 μm.

Example 2
In the same manner as in Example 1, the coating composition of Example 2 having the composition shown in Table 1 was produced. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.5 μm.

[Example 3]
The coating composition of Example 3 having the composition shown in Table 1 was produced in the same manner as Example 1. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.0 μm.

Example 4
A fluorocarbon resin "Fluoronate (registered trademark) K-702 manufactured by DIC Corporation" (fluororesin concentration: 50% by mass, solvent: toluene) and a fluorinated solvent "Asahiclin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd." (CHF ₂ CF ₂ OCH ₂ CF ₃ , KB value: 12) and then hydrophobic silica particles “Aerosil RX300 manufactured by Nippon Aerosil Co., Ltd.” (specific surface area: 210 ± 20 m ² / g) are mixed to obtain dispersion B Was prepared. In the dispersion B, fluororesin particles having an average particle diameter of 532 nm were precipitated. Subsequently, a metal oxide particle "JGC Catalysts & Chemicals Co., Ltd." is made of an acrylic resin "UNIDIC (registered trademark) 17-824-9" (concentration of urethane acrylate: 79.8 mass%, solvent: isopropyl alcohol) manufactured by DIC Corporation. Dispersion A was prepared by mixing ELCOM (registered trademark) -V350 "(antimony-doped tin oxide particle concentration: 15% by mass, average particle size: 40 nm) and isopropyl alcohol.
Thereafter, Dispersion A and Dispersion B were mixed to produce the coating composition of Example 4 having the composition shown in Table 1. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.9 μm.

[Example 5]
The coating composition of Example 5 having the composition shown in Table 1 was prepared in the same manner as Example 1. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 2.9 μm.

[Example 6]
In the same manner as in Example 1, the coating composition of Example 6 having the composition shown in Table 1 was produced. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.0 μm.

[Example 7]
A fluorocarbon resin "Fluoronate (registered trademark) K-702 manufactured by DIC Corporation" (fluororesin concentration: 50% by mass, solvent: toluene) and a fluorinated solvent "Asahiclin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd." (CHF Dispersion 2 was prepared by dissolving in ₂ CF ₂ OCH ₂ CF ₃ , KB value: 12). In the dispersion B, fluororesin particles having an average particle diameter of 568 nm were precipitated. Subsequently, a metal oxide particle "JGC Catalysts & Chemicals Co., Ltd." is made of an acrylic resin "UNIDIC (registered trademark) 17-824-9" (concentration of urethane acrylate: 79.8 mass%, solvent: isopropyl alcohol) manufactured by DIC Corporation. ELCOM (registered trademark)-V 350 "(antimony-doped tin oxide particle concentration: 15% by mass, average particle diameter: 40 nm), hydrophilic silica particles" Organosilica sol IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd. "(silica particles) Dispersion A was prepared by mixing 30% by mass, an average particle size of 100 nm) and isopropyl alcohol.
Thereafter, Dispersion A and Dispersion B were mixed to produce the coating composition of Example 7 having the composition shown in Table 1. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.0 μm.

Comparative Example 1
Acrylic resin "UNIDIC (registered trademark) 17-824-9 manufactured by DIC Corporation" (urethane acrylate concentration: 79.8% by mass, solvent: isopropyl alcohol) and metal oxide particles "ELCOM (manufactured by JGC Catalysts & Chemical Co., Ltd.) Dispersion A of the composition shown in Table 1 was prepared by mixing (registered trademark)-V350 "(antimony-doped tin oxide particle concentration: 15% by mass, average particle diameter: 40 nm) and isopropyl alcohol. This dispersion A was applied to a substrate and dried. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 4.2 μm.

Comparative Example 2
The coating composition of Comparative Example 2 having the composition shown in Table 1 was prepared in the same manner as in Example 1 except that the metal oxide particles "ELCOM (registered trademark) -V350 manufactured by JGC Catalysts Chemical Corporation" were not blended. Manufactured. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 5.2 μm.

Comparative Example 3
The coating composition of Comparative Example 3 having the composition shown in Table 1 was prepared in the same manner as in Example 1 except that the acrylic resin "UNIDIC (registered trademark) 17-824-9 manufactured by DIC Corporation" was not blended. Manufactured. The coating composition was applied to a substrate and allowed to dry. Furthermore, after drying at 70 ° C. for 1 minute, the dried coating was irradiated with ultraviolet light (80 W / cm ² ) for 1 minute using a high-pressure mercury lamp to be cured, thereby producing a substrate with a coating film. The film thickness of the coating film was 2.2 μm.

  The antifouling performance, water contact angle, total light transmittance, haze and abrasion resistance of the obtained substrate with a coating film were evaluated according to the following methods. The results are shown in Table 2.

  With regard to the antifouling performance, adhesion of a mixture (simulating composite stain) of a hydrophilic fouling substance, sand dust (JIS Kanto loam dust having a central particle size of 1 to 3 μm) and a hydrophobic contaminant, carbon black It did by evaluating the sex. After a mixture of sand dust and carbon black is blown to the coating film with air under conditions of temperature 25 ° C./humidity 50%, it is collected by a mending tape (Sumitomo 3M Co., Ltd.) and collected by a spectrophotometer (UV manufactured by Shimadzu Corporation) Absorbance (wavelength 550 nm) by -3100 PC was measured and evaluated in accordance with the following criteria. The smaller the absorbance, the better the antifouling performance.

<Absorbance>
1: less than 0.1 2: 2: 0.1 or more and less than 0.2: 3: 0.2 or more and less than 0.3: 4: 0.3 or more and less than 0.4: 5: 0.4 or more Things

  Regarding the water contact angle, for a coating film left at room temperature (25 ° C.) for 1 hour, using a contact angle meter (CX-150 type manufactured by Kyowa Interface Science Co., Ltd.), PTFE (polytetrafluoroethylene having an inner diameter of 0.1 mm) A water droplet of about 5 μL was dropped from the tip of the coated needle onto the surface of the coating film, and the contact angle was measured and evaluated according to the following criteria. It can be said that the larger the water contact angle, the better the water repellency.

<Water contact angle>
1: 120 degrees or more but less than 150 degrees 2: 100 degrees or more but less than 120 degrees 3: 80 degrees or more but less than 100 degrees 4: 60 degrees or more but less than 80 degrees 5: less than 60 degrees

  The total light transmittance and haze were measured with a haze meter (NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd.), and evaluated according to the following criteria. The smaller the haze value and the larger the transmittance, the better the transparency.

<Haze value>
1: 0 or more and less than 1.0 2: 2: 1.0 or more and less than 3.0: 3: 3.0 or more and less than 5.0: 4: 5.0 or more and less than 7.0: 5: 7 0 or more

<Transmittance>
1: 95% to less than 100% 2: 90% to less than 95% 3: 80% to less than 90% 4: 60% to less than 80% 5: less than 60%

The abrasion resistance was measured by reciprocating the surface of the coating film 500 times with a load of 1000 gf / cm ² using a crock meter (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and then evaluating the peeling state of the coating film. The peeling state of the coating film after the abrasion test was subjected to image processing of the peeling state of the coating film using an electron microscope, and the peeling area ratio was calculated and evaluated according to the following criteria.

<Abrasion resistance>
1: When the peeling area ratio of the coating film is less than 1% 2: When the peeling area ratio of the coating film is 1% or more and less than 20% 3: When the peeling area ratio of the coating film is 20% or more and less than 60% The peeling area ratio of the coating film is 60% or more and less than 90% 5: the peeling area ratio of the coating film is 90% or more

  As shown in Table 2, the coating films formed from the coating compositions of Examples 1 to 7 have good antifouling performance, transparency, water repellency and abrasion resistance. Among them, the coating film formed from the coating composition of Example 4 was the best in antifouling performance, transparency, water repellency and abrasion resistance.

  On the other hand, the coating film formed from the coating composition of Comparative Example 1 resulted in the deterioration of water repellency. Moreover, the coating film formed from the coating composition of Comparative Example 2 resulted in the deterioration of the antifouling performance. The coating film formed from the coating composition of Comparative Example 3 was inferior in all of antifouling performance, transparency, water repellency and abrasion resistance.

  As can be seen from the above results, according to the present invention, a coating film having antifouling performance, abrasion resistance, transparency and high water repellency can be provided.

  Reference Signs List 1 solvent in which acrylic resin is dissolved, 2 metal oxide particles, 3 fluorocarbon resin particles, 4 fluorocarbon solvent, 5 acrylic resin, 6 base material, 7 hydrophobic silica particles, 8 hydrophilic silica particles, 10 housing, 11 suction Mouth, 12 front grille, 13 right and left vanes, 14 outlets, 15 casing parts, 17 upper and lower flaps, 20 air blowers, 30 heat exchangers, 31 heat transfer tubes, 32 heat radiation fins, 40 filters, 100 air conditioners.

Claims (11)

A dispersion comprising an acrylic resin and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide,
What is claimed is: 1. A coating composition comprising: a dispersion containing a fluorocarbon resin as a dispersion medium.   The coating composition according to claim 1, wherein the fluorinated solvent has a Kauri-butanol value (KB value) of 5 or more and 50 or less.   The coating composition according to claim 1 or 2, wherein a mass ratio of the acrylic resin to the metal oxide particles is 60:40 or more and 98: 2 or less.   The dispersion containing a fluorine resin containing the fluorine-based solvent as a dispersion medium is 1% by mass or more and 15% by mass or less with respect to the coating composition, as described in any one of 1 to 3 Coating composition.   The coating composition according to any one of claims 1 to 4, wherein an average particle size of the fluorine resin is 10 nm or more and 1.0 μm or less.   The coating composition according to any one of claims 1 to 5, wherein the dispersion containing a fluorine resin containing the fluorine-based solvent as a dispersion medium further comprises hydrophobic silica particles.   The coating composition according to any one of claims 1 to 6, wherein the dispersion containing the acrylic resin and the metal oxide particles further comprises hydrophilic silica particles having an average particle diameter of 5 nm to 500 nm. object. A first step of preparing a dispersion comprising an acrylic resin and one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide;
A second step of preparing a dispersion containing a fluorocarbon resin with a fluorocarbon solvent as a dispersion medium;
A method of producing a coating composition, comprising: a third step of mixing the dispersion of the first step and the dispersion of the second step to obtain a coating composition. Applying the coating composition according to any one of claims 1 to 7 to a substrate and drying it;
Curing the dried coating film. A coating film comprising an acrylic resin containing one or more metal oxide particles selected from the group consisting of tin oxide, antimony oxide and tungsten oxide and a fluorine resin, having a film thickness of 0.1 μm to 10 μm,
The coating film characterized in that the fluorine resin is scattered on the surface as particles and the average particle diameter is 10 nm or more and 1.0 μm or less. An inlet for taking in a gas, a heat exchanger for exchanging heat of the gas taken in from the inlet, a fan for circulating the gas heat-exchanged by the heat exchanger, and a gas carried by the fan An air conditioner comprising: an air passage forming member forming a passage; a vane and a flap for guiding gas introduced by the air passage forming member; and a cover containing the heat exchanger and the fan.
An air conditioner comprising the coating film according to claim 10 on any surface of the heat exchanger, the fan, the vane, the flap, the air path forming member, and the cover.

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