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WO2019202679A1 - Film de revêtement, article, composition de revêtement et ventilateur centrifuge - Google Patents

Film de revêtement, article, composition de revêtement et ventilateur centrifuge Download PDF

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Publication number
WO2019202679A1
WO2019202679A1 PCT/JP2018/015971 JP2018015971W WO2019202679A1 WO 2019202679 A1 WO2019202679 A1 WO 2019202679A1 JP 2018015971 W JP2018015971 W JP 2018015971W WO 2019202679 A1 WO2019202679 A1 WO 2019202679A1
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WIPO (PCT)
Prior art keywords
vinyl ether
alternating copolymer
silica particles
mass
perfluoroalkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2018/015971
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English (en)
Japanese (ja)
Inventor
義則 山本
文彦 曽根
浩之 袴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Electric Corp
Original Assignee
Mitsubishi Electric Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Electric Corp filed Critical Mitsubishi Electric Corp
Priority to CN201880092276.3A priority Critical patent/CN112041400B/zh
Priority to JP2018546049A priority patent/JP6456569B1/ja
Priority to PCT/JP2018/015971 priority patent/WO2019202679A1/fr
Publication of WO2019202679A1 publication Critical patent/WO2019202679A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04D—NON-POSITIVE-DISPLACEMENT PUMPS
    • F04D29/00—Details, component parts, or accessories
    • F04D29/40—Casings; Connections of working fluid
    • F04D29/42—Casings; Connections of working fluid for radial or helico-centrifugal pumps
    • F04D29/44—Fluid-guiding means, e.g. diffusers

Definitions

  • the present invention relates to a coating film, an article, a coating composition, and a centrifugal blower.
  • Patent Document 1 includes (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and / or a partially hydrolyzed condensate thereof, and an average molecular weight equal to or less than the average molecular weight of component (A). And a fluorine-containing coating agent having a blending mass ratio of the component (A) to the component (B) of 40:60 to 95: 5.
  • the cured film formed from the fluorine-containing coating agent disclosed in Patent Document 1 has a problem of peeling due to physical impact such as cleaning because it has poor adhesion to the substrate.
  • an object of the present invention is to provide a coating film that can suppress the adhesion of oil and dust and has excellent adhesion to a substrate. .
  • the present invention relates to a fluoropolymer containing a perfluoroalkyl group, a fluoroethylene vinyl ether alternating copolymer having a hydroxyl value of 7 mgKOH / g to 110 mgKOH / g and hydrophilic silica particles having an average particle diameter of 10 nm to 300 nm.
  • a coating film dispersedly arranged wherein the fluoroethylene vinyl ether alternating copolymer is contained in an amount of 0.01% by mass to 20.0% by mass with respect to the perfluoroalkyl group-containing fluororesin,
  • the hydrophilic silica particles are contained in an amount of 0.001% by mass to 3.0% by mass with respect to the total of the fluoroalkyl group-containing fluororesin and the fluoroethylene vinyl ether alternating copolymer,
  • a portion is exposed on the surface of the coating film, and the hydrophilic Area of the exposed portion of the silica particles is a coating film, wherein the coating film is 50% or less than 1.5% of the total area of the surface of the.
  • the present invention it is possible to provide a coating film that can suppress the adhesion of oil and dust and has excellent adhesion to a substrate.
  • a coating film according to Embodiment 1 includes a perfluoroalkyl group-containing fluororesin, a fluoroethylene vinyl ether alternating copolymer having a hydroxyl value of 7 mgKOH / g to 110 mgKOH / g, and 10 nm to 300 nm. Hydrophilic silica particles having the following average particle diameter are dispersedly arranged, and the fluoroethylene vinyl ether alternating copolymer is 0.01% by mass or more and 20.0% by mass or less with respect to the perfluoroalkyl group-containing fluororesin.
  • the hydrophilic silica particles are contained in an amount of 0.001% by mass to 3.0% by mass with respect to the total of the perfluoroalkyl group-containing fluororesin and the fluoroethylene vinyl ether alternating copolymer. Part of the particles are exposed on the surface of the coating film, and hydrophilic silica Area of the exposed portion of the child, and wherein the 50% or less than 1.5% of the total area of the surface of the coating film.
  • FIG. 1 is a schematic cross-sectional view showing a state in which the coating film according to Embodiment 1 is formed on the surface of a substrate.
  • FIG. 2 is a schematic diagram showing a state of components in the coating film according to the first embodiment.
  • the fluoroethylene vinyl ether alternating copolymer 2 and the hydrophilic silica particles 3 are contained in the perfluoroalkyl group-containing fluororesin 1. Distributed.
  • the perfluoroalkyl group-containing fluororesin 1 is a resin composed of only a fluorine component having the smallest surface energy, it has an excellent effect of suppressing adhesion of oil droplets and oil smoke, but has poor adhesion to the base material 5. It is enough. Therefore, in the coating film 4, the adhesiveness with the base material 5 is improved by dispersing and arranging the fluoroethylene vinyl ether alternating copolymer 2 in the perfluoroalkyl group-containing fluororesin 1. Moreover, in the coating film 4, the effect which suppresses adhesion of dust is improved by disperse
  • the perfluoroalkyl group-containing fluororesin 1 is a fluororesin containing a perfluoro-substituted alkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • the perfluoroalkyl group-containing fluororesin 1 is not particularly limited, and those known in the technical field can be used. Specifically, as the fluororesin 1 containing a perfluoroalkyl group, “SFC Coat (registered trademark) -SFE-DP02”, “SFC Coat (registered trademark) -SFE-B002”, “SEF” manufactured by AGC Seimi Chemical Co., Ltd.
  • the fluoroethylene vinyl ether alternating copolymer 2 is obtained by alternately polymerizing a fluorine component that exhibits oil repellency and a vinyl ether component that improves adhesion to the substrate 5.
  • a fluoroethylene vinyl ether alternating copolymer 2 is represented by the following formula (I).
  • R represents a C1-C10 alkyl group
  • R 1 represents a C1-C16 alkyl group
  • R 2 represents a C1-C16 alkylene group
  • X represents fluorine
  • k, l, m and n in the following formula (I) are selected in the range where the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer 2 is 1,000 to 2,000,000.
  • the fluoroethylene vinyl ether alternating copolymer 2 is a solvent-soluble fluororesin (dissolvable in various solvents). Further, the fluoroethylene vinyl ether alternating copolymer 2 can be dried and cured at room temperature, unlike fluororesins for paints (for example, polyvinylidene fluoride PVDF, polychlorotrifluoroethylene PCTFE, polyvinyl fluoride PVF, etc.). .
  • the fluoroethylene vinyl ether alternating copolymer 2 is contained in an amount of 0.01% by mass or more and 20.0% by mass or less, preferably 0.5% by mass with respect to the perfluoroalkyl group-containing fluororesin 1. It is contained at 15.0 mass% or less.
  • the content of the fluoroethylene vinyl ether alternating copolymer 2 in the coating film 4 is less than 0.01% by mass, the effect of improving the adhesion with the substrate 5 cannot be obtained.
  • the content of the fluoroethylene vinyl ether alternating copolymer 2 in the coating film 4 exceeds 20.0 mass%, the oil adhesion suppressing performance cannot be sufficiently obtained.
  • the hydroxyl value (mgKOH / g) of the fluoroethylene vinyl ether alternating copolymer 2 is 7 mgKOH / g or more and 110 mgKOH / g or less.
  • the hydroxyl value is less than 7 mgKOH / g, sufficient adhesion with the substrate 5 cannot be obtained.
  • the hydroxyl value exceeds 110 mgKOH / g the oil adhesion suppression performance cannot be sufficiently obtained.
  • the hydroxyl value of the fluoroethylene vinyl ether alternating copolymer 2 is potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the fluoroethylene vinyl ether alternating copolymer 2 is acetylated according to JIS K0070. It means the number of mg of (KOH).
  • the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer 2 is not particularly limited, but is preferably 1,000 or more and 2,000,000 or less, more preferably 5,000 or more and 1,000,000. Hereinafter, it is most preferably from 10,000 to 500,000.
  • the weight average molecular weight of the fluoroethylene vinyl ether alternating copolymer 2 can be measured by a gel permeation chromatography (GPC) method. Specifically, after the fluoroethylene vinyl ether alternating copolymer 2 is adjusted to 2.0 g / L using a tetrahydrofuran (THF) solution, it is allowed to stand for 12 hours.
  • GPC gel permeation chromatography
  • the fluoroethylene vinyl ether alternating copolymer 2 is not particularly limited, and those known in the technical field can be used. Specifically, as the fluoroethylene vinyl ether alternating copolymer 2, “Lumiflon (registered trademark) -LF100”, “Lumiflon (registered trademark) -LF400”, “Lumiflon (registered trademark) -LF600” manufactured by Asahi Glass Co., Ltd., “Lumiflon (registered trademark) -LF200F”, “Lumiflon (registered trademark) -LF710F”, “Lumiflon (registered trademark) -LF916F”, “Lumiflon (registered trademark) -LF200”, “Lumiflon (registered trademark) -LF800”, etc. Is mentioned.
  • the hydrophilic silica particles 3 are not particularly limited as long as they have an average particle diameter of 10 nm or more and 300 nm or less.
  • the average particle diameter of the hydrophilic silica particles 3 means an average particle diameter measured by a laser light scattering method.
  • the average particle diameter of the hydrophilic silica particles 3 exceeds 300 nm, it becomes difficult to form fine irregularities on the surface of the coating film 4, and cracks are likely to occur on the surface of the coating film 4.
  • the average particle diameter of the hydrophilic silica particles 12 is less than 10 nm, the hydrophilic silica particles 3 easily aggregate.
  • the hydrophilic silica particles 3 are contained in an amount of 0.001% by mass to 3.0% by mass with respect to the total of the perfluoroalkyl group-containing fluororesin 1 and the fluoroethylene vinyl ether alternating copolymer 2. Preferably, it is contained in an amount of 0.1% by mass to 2.5% by mass.
  • the content of the hydrophilic silica particles 3 in the coating film 4 is less than 0.001% by mass, the dust adhesion suppressing effect cannot be sufficiently obtained.
  • the content of the hydrophilic silica particles 3 in the coating film 4 exceeds 3.0% by mass, the oil adhesion suppressing performance cannot be sufficiently obtained.
  • the hydrophilic silica particles 3 are not particularly limited, and those known in the technical field can be used. Specifically, as the hydrophilic silica particles 3, “organosilica sol (registered trademark) -MA-ST-M”, “organosilica sol (registered trademark) -MA-ST-L”, “manufactured by Nissan Chemical Industries, Ltd.” Organosilica sol (registered trademark) -IPA-ST, Organosilica sol (registered trademark) -ST-L, Organosilica sol (registered trademark) -IPA-ST-L, Organosilica sol (registered trademark) -IPA- ST-ZL ",” organosilica sol (registered trademark) -IPA-UP "," organosilica sol (registered trademark) -EG-ST “,” organosilica sol (registered trademark) -NPC-ST-30 “,” organosilica sol ( (Registered trademark) -PGM-ST “,” organosilica sol (registered trademark) -
  • a part of the hydrophilic silica particles 3 is exposed on the surface of the coating film 4.
  • the area of the exposed portion of the hydrophilic silica particles 3 is 1.5% or more and 50% or less, preferably 5% or more and 45% or less, of the total area of the surface of the coating film 4.
  • the area ratio of the exposed portion of the hydrophilic silica particles 3 is less than 1.5%, a fine uneven structure is not formed on the surface, and a dust adhesion suppressing effect cannot be sufficiently obtained.
  • the area ratio of the exposed portion of the hydrophilic silica particles 3 exceeds 50%, the oil adhesion suppressing performance cannot be sufficiently obtained.
  • the coating film 4 in the blade of the ventilation fan is suitable as the coating film 4 in the blade of the ventilation fan.
  • hydrophilic silica particles 3 are exposed on the surface of the coating film 4 is that, since the hydrophilic silica particles 3 have hydrophilicity, perfluoroalkyl group-containing fluororesin 1 and fluoroethylene vinyl ether alternating copolymer having oil repellency. This is because the compatibility with 2 is low.
  • the area ratio (%) of the exposed portion of the hydrophilic silica particles 3 was determined by photographing the surface of the coating film at 10,000 magnifications with a scanning electron microscope (SEM) manufactured by Hitachi High Technology Co., Ltd. The ratio of the area occupied by the hydrophilic silica particles to the total area is calculated, and the arithmetic average of them is calculated.
  • void portions having the same size as the dispersed hydrophilic silica particles 3.
  • Such a void portion is formed by repelling the hydrophilic group present on the surface of the hydrophilic silica particle 3 and the oil repellent group existing on the surface of the perfluoroalkyl group-containing fluororesin 1 in the vicinity of the hydrophilic silica particle 3. It is formed.
  • the coating composition used to form the coating film 4 described above includes perfluoroalkyl group-containing fluororesin 1, fluoroethylene vinyl ether alternating copolymer 2, and hydrophilic silica particles 3 having an average particle diameter of 10 nm to 300 nm. It is characterized by.
  • the fluoroethylene vinyl ether alternating copolymer 2 is contained in an amount of 0.01% by mass or more and 20.0% by mass or less, preferably with respect to the perfluoroalkyl group-containing fluororesin 1. Is contained in an amount of 0.5 mass% to 15.0 mass%. If the content of the fluoroethylene vinyl ether alternating copolymer 2 in the coating composition is less than 0.01% by mass, the effect of improving the adhesion with the substrate 5 cannot be obtained. On the other hand, when the content of the fluoroethylene vinyl ether alternating copolymer 2 in the coating composition exceeds 20.0% by mass, the oil adhesion suppressing performance cannot be sufficiently obtained.
  • the hydrophilic silica particles 3 are 0.001% by mass or more with respect to the total of the perfluoroalkyl group-containing fluororesin 1 and the fluoroethylene vinyl ether alternating copolymer 2. It is contained at 0% by mass or less, preferably 0.1% by mass or more and 2.5% by mass or less. If the content of the hydrophilic silica particles 3 in the coating composition is less than 0.001% by mass, the dust adhesion suppressing effect cannot be sufficiently obtained. On the other hand, when the content of the hydrophilic silica particles 3 in the coating composition exceeds 3.0% by mass, the oil adhesion suppressing performance cannot be sufficiently obtained.
  • a fluoroethylene vinyl ether alternating copolymer is dissolved in alcohol to obtain a first agent, and then hydrophilic silica particles, a perfluoroalkyl group-containing fluororesin, and fluorine are contained in the first agent. It can be produced by further adding a system solvent.
  • the coating composition produced in this way is excellent in stability without aggregation or the like.
  • the alcohol for dissolving the fluoroethylene vinyl ether alternating copolymer 2 is not particularly limited, and ethanol, n-propanol, 2-propanol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, n-amyl alcohol, hexyl alcohol, 2 -Ethylbutyl alcohol, methylamyl alcohol, cyclohexanol, 2-ethylhexyl alcohol, octyl alcohol, benzyl alcohol and the like. These alcohols may be used alone or in combination of two or more.
  • the fluorine-based solvent that dissolves the perfluoroalkyl group-containing fluororesin 1 is not particularly limited, and examples thereof include hydrofluoroether, hydrofluorocarbon, hydrochlorofluorocarbon, and the like. These fluorinated solvents may be used alone or in combination of two or more.
  • the solvent in which the hydrophilic silica particles 3 are dispersed is preferably a solvent that is compatible with water.
  • a solvent that is compatible with water preferably ethanol, n-propanol, 2-propanol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, n-amyl alcohol, hexyl alcohol, 2-ethylbutyl alcohol, methyl amyl alcohol, cyclohexanol, 2-ethylhexyl alcohol, octyl alcohol, benzyl alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl Methyle Ter, dipropylene glycol monomethyl
  • the coating composition described above may be applied to the substrate 5 and then dried.
  • the film thickness of the coating film 4 is preferably 0.02 ⁇ m or more and 1.0 ⁇ m or less. If the thickness of the coating film is less than 0.02 ⁇ m, sufficient adhesion with the substrate 5 may not be obtained. On the other hand, if the thickness of the coating film 4 exceeds 1.0 ⁇ m, defects such as cracks are likely to occur in the coating film 4 and the desired oil adhesion suppression performance may not be obtained. The film 4 may be peeled off.
  • the base material 5 on which the coating film 4 is formed is not particularly limited, and examples thereof include parts constituting various articles that require oil repellency. Examples of such components include a heat exchanger for an air conditioner, a ventilation fan blade, and the like. Examples of the material of the substrate 5 include plastics such as polypropylene, polystyrene, acrylonitrile / butadiene / styrene (ABS) and glass fiber reinforced styrene / acrylonitrile (ASG), metals such as stainless steel and aluminum, and glass. .
  • the method for applying the coating composition is not particularly limited, and methods known in the art can be used.
  • Specific examples of the application method include brush coating, spray coating, and immersion.
  • the drying method is not particularly limited, and it may be dried at room temperature or dried by heating.
  • drying time can be shortened by drying under airflow.
  • warm air may be blown or heated in a heating furnace.
  • FIG. 3 is a schematic cross-sectional view of a centrifugal blower according to Embodiment 2 of the present invention.
  • the centrifugal blower 16 includes a multi-blade impeller 13, an electric motor that rotationally drives the multi-blade impeller 13, and a fan casing 14.
  • the fan casing 14 has a suction port 21 into which an airflow is sucked by the rotation of the multiblade impeller 13 and a blowout port 22 from which the airflow is blown out.
  • the suction port 21 is a circular opening.
  • the opening center of the suction port 21 is located on the same axis as the rotation axis.
  • a space between the multiblade impeller 13 and the inner side surface 15 of the fan casing 14 is a spiral air passage through which an air flow blown from the multiblade impeller 13 flows.
  • the blower outlet 22 is an opening which becomes an outlet of a spiral air passage.
  • the multi-blade impeller 13 includes a plurality of wing parts 11 and a main plate 12 provided with a boss 10.
  • the plurality of wing parts 11 are arranged in a ring shape around the boss 10 on the main plate 12.
  • the main plate 12 is a circular plate material having the boss 10 as a center, and is formed so that the center portion is convex toward the suction port 21 side rather than the peripheral portion.
  • the boss 10 is connected to the shaft 20 of the electric motor.
  • the coating film 4 obtained by applying and drying the coating composition described in the first embodiment is provided on at least one surface of the multiblade impeller 13, the electric motor, the suction port 21, the air outlet 22, and the fan casing 14. Is.
  • the method for forming the coating film 4 is the same as that described in the first embodiment.
  • the coating film 4 described in the first embodiment can suppress the adhesion of oil and dust and has excellent adhesion to the base material, the electric motor, the suction port 21, the blower port 22, and the electric motor constituting the centrifugal blower 16.
  • Example 1 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SGC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SGC Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 2 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SF Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SF Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 19.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 0.0018 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 3 Fluoroethylene vinyl ether alternating copolymer (Lumiflon LF810 manufactured by Asahi Glass Co., Ltd., hydroxyl value 9 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (AGC Seimi Chemical Co., Ltd. SFC Coat SFE-DP02) ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • APC Seimi Chemical Co., Ltd. SFC Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • Hydrophilic silica particles organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 4 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF916N manufactured by Asahi Glass Co., Ltd., hydroxyl value 100 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SFC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • a fluoroethylene vinyl ether alternating copolymer Liiflon LF916N manufactured by Asahi Glass Co., Ltd., hydroxyl value 100 mgKOH / g
  • SFC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 5 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SGC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SGC Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 0.013% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 6 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SGC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SGC Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 19.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 7 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SF Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SF Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 0.0012 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 8> A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SGC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 2.9 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 9 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SF Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ST, manufactured by Nissan Chemical Industries, Ltd., average particle size 12 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SF Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 10 A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SGC Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.).
  • SGC Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • Hydrophilic silica particles particles combined with organosilica sol IPA-ST manufactured by Nissan Chemical Industries, Ltd., average particle size of 295 nm
  • a fluorinated solvent Alka Chemical Industries, Ltd.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin
  • the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 6.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 3.1 mass% with respect to the sum total of a fluororesin and a fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 0.009% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 20.3% by mass relative to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • ⁇ Comparative example 4> A fluoroethylene vinyl ether alternating copolymer (Lumiflon manufactured by Asahi Glass Co., Ltd., hydroxyl value 6 mgKOH / g) is dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SF Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.) Further, hydrophilic silica particles (organosilica sol IPA-ZL manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and a fluorine-based solvent (Asahiclin AC-6000 manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 0.0008 mass% with respect to the sum total of fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Hydrophilic silica particles particles combined with organosilica sol IPA-ZL manufactured by Nissan Chemical Industries, Ltd., average particle size 316 nm
  • a fluorinated solvent Alka Chemical Industries, Ltd.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin
  • the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 1.5 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • ⁇ Comparative Example 12> A fluoroethylene vinyl ether alternating copolymer (Lumiflon LF710F manufactured by Asahi Glass Co., Ltd., hydroxyl value 46 mgKOH / g) was dissolved in 1-propanol, and then a perfluoroalkyl group-containing fluororesin (SF Coat SFE-DP02 manufactured by AGC Seimi Chemical Co., Ltd.). ), Hydrophilic silica particles (organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm) and fluorine-based solvent (Asahiclin AC-6000, manufactured by Asahi Glass Co., Ltd.) were further added to obtain a coating composition.
  • SF Coat SFE-DP02 perfluoroalkyl group-containing fluororesin
  • Hydrophilic silica particles organosilica sol IPA-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size 80 nm
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin, and the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 4.9 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Hydrophilic silica particles particles combined with organosilica sol IPA-ZL manufactured by Nissan Chemical Industries, Ltd., average particle diameter of 80 nm
  • a fluorinated solvent Alka Chemical Industries, Ltd.
  • the content of the fluoroethylene vinyl ether alternating copolymer is 18.0% by mass with respect to the perfluoroalkyl group-containing fluororesin
  • the content of the hydrophilic silica particles is perfluoroalkyl group-containing. It was 0.0005 mass% with respect to the sum total of a fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • Example 1 to 10 and Comparative Examples 1 to 13 Details of the coating compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 13 are shown in Table 1. Each of the coating compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 13 was applied by immersing a 100 mm ⁇ 30 mm ⁇ 1 mm plastic substrate (ABS resin), and then an excess coating using an air stream. A coating film was formed by removing the composition.
  • the coating film was evaluated for the falling angle, dust adhesion suppression performance and adhesion according to the following methods.
  • ⁇ Tumble angle> The sliding angle is a PTFE (polytetrafluoroethylene) coating with an inner diameter of 0.1 mm using a contact angle meter (CX-150, manufactured by Kyowa Interface Science Co., Ltd.) for the coating film left for 1 hour at room temperature (25 ° C). 7 ⁇ L of oil droplets (Nisshin Oilio Co., Ltd. salad oil) were dripped onto the surface of the coating film from the tip of the needle. Thereafter, the tilt angle at the start of sliding was measured with a tilting device and evaluated according to the following criteria. It is judged that the smaller the falling angle, the higher the oil adhesion suppressing effect. The results are shown in Table 2.
  • the falling angle is less than 10 °. 2: A falling angle of 10 ° or more and less than 30 °. 3: A falling angle of 30 ° or more and less than 60 °. 4: The sliding angle is 60 ° or more and less than 90 °. 5: A falling angle of 90 ° or more.
  • Absorbance is less than 0.1.
  • 3 Absorbance of 0.2 or more and less than 0.3.
  • 4 Absorbance of 0.3 or more and less than 0.4.
  • 5 Absorbance of 0.4 or more.
  • ⁇ Adhesion> The adhesion was measured by reciprocating the surface of the coating film 20 times with a load of 90 gf / cm 2 using an abrasion tester clock meter (manufactured by Yasuda Kikai Co., Ltd.).
  • the peeled state of the coating film after the abrasion test was evaluated by image processing the residual state of the coating film using an electron microscope and calculating the residual area.
  • the peeled state after the wear test was evaluated according to the following criteria. The results are shown in Table 2.
  • the coating film was not peeled off.
  • the remaining area of the coating film is 1% or more and less than 20%.
  • the remaining area of the coating film is 20% or more and less than 60%.
  • the remaining area of the coating film is 60% or more and less than 90%.
  • the remaining area of the coating film is 90% or more.
  • the coating films formed from the coating compositions of Examples 1 to 10 have high oil adhesion suppression performance and dust adhesion suppression performance, and also have high adhesion to the substrate. I understand that.
  • the coating film formed from the coating composition of Example 1 had high oil adhesion suppression performance and dust adhesion suppression performance, and had the best adhesion to the substrate. This is presumably because fine irregularities were formed by the perfluoroalkyl group-containing fluororesin, the fluoroethylene vinyl ether alternating copolymer, and the hydrophilic silica particles.
  • FIG. 4 is a graph showing the critical significance of the hydroxyl value of the fluoroethylene vinyl ether alternating copolymer.
  • the hydroxyl value of the fluoroethylene vinyl ether alternating copolymer is less than 7 mg KOH / g, the adhesion of the coating film to the substrate deteriorates (Comparative Example 4).
  • the hydroxyl value of the fluoroethylene vinyl ether alternating copolymer exceeds 110 mgKOH / g, the falling angle increases and the oil adhesion suppression performance deteriorates (Comparative Example 5).
  • FIG. 5 is a graph showing the critical significance of the amount of the fluoroethylene vinyl ether alternating copolymer relative to the perfluoroalkyl group-containing fluororesin.
  • the amount of the fluoroethylene vinyl ether alternating copolymer is less than 0.01% by mass, sufficient adhesion of the coating film to the substrate cannot be obtained (Comparative Example 2).
  • the amount of the fluoroethylene vinyl ether alternating copolymer exceeds 20.0% by mass, the dust adhesion suppressing performance deteriorates (Comparative Example 3).
  • FIG. 6 is a graph showing the critical significance of the amount of hydrophilic silica particles relative to the total of perfluoroalkyl group-containing fluororesin and fluoroethylene vinyl ether alternating copolymer.
  • the amount of the hydrophilic silica particles is less than 0.001% by mass, sufficient adhesion of the coating film to the substrate cannot be obtained (Comparative Example 6).
  • the amount of the hydrophilic silica particles exceeds 3.0% by mass, the falling angle increases and the oil adhesion suppression performance deteriorates (Comparative Example 1).
  • FIG. 7 is a graph showing the critical significance of the average particle diameter of hydrophilic silica particles.
  • the average particle size of the hydrophilic silica particles is less than 10 nm, the dust adhesion suppressing performance deteriorates (Comparative Example 8).
  • the average particle diameter of the hydrophilic silica particles exceeds 300 nm, the falling angle increases, the oil adhesion suppression performance deteriorates and the dust adhesion suppression performance also deteriorates (Comparative Example 7).
  • FIG. 8 is a graph showing the critical significance of the area ratio of the exposed portion of the hydrophilic silica particles. If the area ratio of the exposed portion of the hydrophilic silica particles exceeds 50%, the falling angle increases and the oil adhesion suppression performance deteriorates (Comparative Example 12). On the other hand, when the area ratio of the exposed portion of the hydrophilic silica particles is less than 1.5%, the dust adhesion suppressing performance is deteriorated (Comparative Examples 6, 11 and 13).
  • the coating film of Comparative Example 9 that did not contain a perfluoroalkyl group-containing fluororesin resulted in a marked deterioration in oil adhesion suppression performance.
  • the coating film of Comparative Example 10 that did not contain the fluoroethylene vinyl ether alternating copolymer resulted in a deterioration in adhesion.
  • the coating film of Comparative Example 11 that did not contain hydrophilic silica particles resulted in deterioration in dust adhesion suppression performance.
  • the coating film according to the present invention can simultaneously realize excellent oil adhesion suppression performance, dust adhesion suppression performance and adhesion.
  • the coating film according to the present invention can maintain the suppression of the adhesion of oil smoke and oil droplets without oil or dust adhering or accumulating even when used repeatedly.

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Abstract

L'invention concerne un film de revêtement dans lequel un copolymère séquencé de fluoroéthylène/vinyléther possédant un indice d'hydroxyle de 7 à 110 mg de KOH/g, valeurs extrêmes incluses, et des particules de silice hydrophiles possédant un diamètre de particule moyen de 10 à 300 nm, valeurs extrêmes incluses, sont distribués et dispersés dans une résine fluorée possédant un groupe perfluoroalkyle, caractérisé en ce que : le copolymère séquencé de fluoroéthylène/vinyléther est contenu dans une quantité de 0,01-20,0 % en masse, valeurs extrêmes incluses, par rapport à la résine fluorée possédant un groupe perfluoroalkyle ; les particules de silice hydrophiles sont contenues dans une quantité de 0,001-3,0 % en masse, valeurs extrêmes incluses, par rapport à la quantité totale de la résine fluorée possédant un groupe perfluoroalkyle et du copolymère séquencé de fluoroéthylène/vinyléther ; une partie des particules de silice hydrophiles sont apparentes à la surface du film de revêtement ; et l'aire des parties apparentes des particules de silice hydrophiles est de 1,5 à 50 %, valeurs extrêmes incluses, de l'aire surfacique totale du film de revêtement.
PCT/JP2018/015971 2018-04-18 2018-04-18 Film de revêtement, article, composition de revêtement et ventilateur centrifuge Ceased WO2019202679A1 (fr)

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CN201880092276.3A CN112041400B (zh) 2018-04-18 2018-04-18 涂膜、物品、涂布组合物及离心送风机
JP2018546049A JP6456569B1 (ja) 2018-04-18 2018-04-18 コーティング膜、物品、コーティング組成物及び遠心送風機
PCT/JP2018/015971 WO2019202679A1 (fr) 2018-04-18 2018-04-18 Film de revêtement, article, composition de revêtement et ventilateur centrifuge

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